BR112019019618A2 - electrolysis electrode, laminated, and rolled body - Google Patents

Abstract

The present invention relates to an electrolysis electrode, a layered body, a coiled body, an electrolytic cell, a method to manufacture an electrolytic cell, a method to renew an electrode, a method to renew a layered body and a method for making a rolled body. The electrolysis electrode belonging to a modality of the present invention has a mass per unit area of 48 mg / cm2 or less and a force applied per unit mass / unit area of 0.08 N / mg · cm2 or greater.

Description

ELECTRODE FOR ELECTROLYSIS, LAMINATED, AND, WRAPPED BODY Technical Field

[001] The present invention relates to an electrolysis electrode, a laminate, a rolled body, an electrolyzer, a method to produce an electrolyzer, a method to renew an electrode, a method to renew a laminate and a method to produce a curled body. Fundamentals of Technique

[002] For the electrolysis of an aqueous alkali metal chloride solution, such as saline and water electrolysis, methods using an electrolyzer including a membrane, more specifically an ion exchange membrane or a microporous membrane, were used . This electrolyzer includes many electrolytic cells connected in series, in many cases. A membrane is interposed between each electrolytic cell to perform electrolysis. In an electrolytic cell, a cathodic chamber including a cathode and an anode chamber including an anode are disposed on the back with a dividing wall (back plate) interposed between them or through pressure by means of pressing, screw tightening, or the like.

[003] The anode and cathode for use in these electrolysers are now each attached to the anodic chamber or cathodic chamber of an electrolytic cell by a method such as welding and folding, and thereafter, stored or transported to customers. In the meantime, each membrane in a state of individual wrapping around a vinyl chloride (VC) tube is stored or transported to customers. Each customer fixes the electrolytic cell in the frame of an electrolyzer and interposes the membrane between the electrolytic cells to assemble the electrolyzer. In this way, electrolytic cells are produced and an electrolyzer is assembled by each customer. Each of the Patent Literature 1 and 2 describes a structure formed by the integration of a membrane and an electrode as a structure applicable to such an electrolyzer. Patent Literature Citation List Patent Literature 1

[004] Japanese patent open to public inspection No. 58-048686 Patent Literature 2

[005] Japanese patent open to public inspection No. 55-148775 Summary of the Invention Technical problem

[006] When the electrolysis operation is started and continued, each part deteriorates and the electrolytic performance is reduced due to several factors, and each part is replaced at a certain time. The membrane can be easily renewed by extracting it from an electrolytic cell and inserting a new membrane. In contrast, the anode and cathode are attached to the electrolytic cell and, thus, there is a problem with extremely complicated work on the electrode renovation, in which the electrolytic cell is removed from the electrolyzer and transported to a dedicated renovation plant, fixation as the welding is removed and the old electrode is separated, then a new electrode is placed and fixed by a method like welding, and the cell is transported to the electrolysis plant and placed back in the electrolyzer. Here, the structure formed by the integration of a membrane and an electrode by thermal compression is considered described in the Patent Literature | and 2 is used for the renovation described above, but the structure, which can be produced on a laboratory level with relative ease, is not easily produced in order to be adapted to an electrolytic cell in a commercially available actual size (e.g. 1.5 m long, 3 m wide). In addition, electrolytic performance (such as electrolysis voltage, current efficiency and common salt concentration in caustic soda) and durability are extremely poor, and chlorine gas and hydrogen gas are generated at the electrode that makes the interface with the membrane. Thus, when used in electrolysis for a long period, complete delamination occurs, and the structure cannot be used practically.

[007] The present invention was made in view of the problems above the conventional technique and aims to provide an electrolyte electrode, a laminate, a rolled body, an electrolyser, a method to produce an electrolyser, a method to renew an electrode, a method to renew a laminate and a method to produce a rolled-up body. (First objective)

[008] It is an objective of the present invention to provide an electrolysis electrode, a laminate and a rolled-up body that facilitate transport and handling, remarkably simplify work when a new electrolyzer is started or a degraded electrode is renewed and, in addition, can also maintain or improve electrolytic performance. (Second objective)

[009] It is an objective of the present invention to provide a laminate that can improve the work efficiency during the electrode renewal in an electrolyzer and can additionally present an excellent electrolytic performance also after the renovation. (Third objective)

[0010] It is an objective of the present invention to provide a laminate that can improve the work efficiency during the electrode renewal in an electrolyzer and can additionally present an excellent electrolytic performance also after the renovation, from a point of view different from the second objective described above. (Fourth objective)

[0011] It is a fourth objective of the present invention to provide an electrolyzer, a method for producing an electrolyzer and a method for renewing a laminate that has excellent electrolytic performance, as well

4/803 how it can prevent damage of a membrane. (Fifth objective)

[0012] It is an objective of the present invention to provide a method to produce an electrolyzer, a method to renew an electrode and a method to produce a rolled body that can improve the efficiency of the work during the electrode renewal in an electrolyzer. (Sixth objective)

[0013] It is an objective of the present invention to provide a method to produce an electrolyser that can improve the work efficiency during the electrode renewal in an electrolyser, from a point of view different from the fifth objective described above. (Seventh objective)

[0014] It is an objective of the present invention to provide a method to produce an electrolyser that can improve the work efficiency during the electrode renewal in an electrolyser, from a point of view different from the fifth and sixth objectives described above. Solution to the Problem

[0015] As a result of the intensive studies carried out by the present inventors to achieve the first objective, the production of an electrolysis electrode that has a small mass per unit area and can be connected to a membrane such as an ion exchange membrane and a membrane microporous or a degraded electrode with a weak force facilitates transport and handling can remarkably simplify work when a new electrolyzer is started or a degraded part is renewed and, in addition, can significantly improve characteristics compared to electrolytic performance in the art conventional. In addition, the present inventors have found that the characteristics can be equivalent or improved in relation to the electrolytic performance of a conventional electrolytic cell, for which the renovation work is complicated, thus having completed the present invention.

[0016] That is, the present invention includes the following.

[1] An electrolysis electrode with a mass per unit area of 48 mg / cm? or less and a force applied per unit mass-unit area of 0.08 N / mg: cm? or more.

P) The electrolysis electrode according to [1], in which the electrolysis electrode comprises an electrolyte electrode substrate and a catalytic layer, and the electrolysis electrode substrate has a thickness of 300 µm or less.

3) The electrolysis electrode according to [1] or [2], where a proportion measured by method (3) below is 75% or more: [Method (3)]

[0017] A membrane (170 mm square), which is obtained by applying particles of inorganic material and a binder on both surfaces of a perfluorocarbon polymer membrane into which an ion exchange group is introduced, and a sample of electrolysis electrode (130 mm square) are rolled in that order; and the laminate is placed on a curved surface of a polyethylene tube (external diameter: 145 mm) so that the electrode sample for electrolysis in that laminate is positioned outside under conditions of 23 + 2ºC and humidity relative to 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, a proportion (% ) of a portion area, in which the electrolyte electrode sample is in close contact with the membrane obtained by applying the particles of inorganic material and the binder on both surfaces of the perfluorocarbon polymer membrane in which the exchange group ionic is introduced.

[4] The electrolysis electrode according to any of [1] to

[3], in which the electrolysis electrode has a porous structure and has an opening ratio of 5 to 90%.

[5] The electrolysis electrode according to any of [1] to

[4], in which the electrode has a porous structure and has an opening ratio of 10 to 80%.

[6] The electrolysis electrode according to any of [1] to

[5], in which the electrolysis electrode has a thickness of 315 µm or less.

[7] The electrolysis electrode according to any of [1] to

[6], where a value obtained by measuring the electrode for electrolysis by method (A) below is 40 mm or less: [Method (A)]

[0018] Under temperature conditions of 23 + 2ºC and relative humidity of 30 + 5%, a sample obtained by laminating the ion exchange membrane and the electrolysis electrode is rolled up and fixed on a curved surface of a core material made of polyvinyl chloride with an external diameter of 32 mm and left to rest for 6 hours; thereafter, when the electrolysis electrode is separated from the sample and placed on a flat plate, heights in a vertical direction on both edges of the electrolysis electrode L, and L7 are measured, and an average value is used as a value of measurement.

[8] The electrolysis electrode according to any of [1] to

[7], where a ventilation resistance is 24 kPa-s / m or less when the electrolysis electrode is 50 mm x 50 mm in size, the ventilation resistance being measured under temperature conditions of 24ºC, humidity relative 32%, a piston speed of 0.2 cm / s and a ventilation volume of 0.4 cc / in? / s.

[9] The electrolysis electrode according to any of [1] to

[8], in which the electrode comprises at least one element selected from nickel (Ni) and titanium (Ti).

[10] A laminate comprising the electrolysis electrode as defined in any one of [1] to [9].

11) A coiled body comprising the electrolysis electrode as defined in any one of [1] to [9] or the laminate as defined in

[10].

[0019] As a result of intensive studies to achieve the second objective, the present inventors have found that a laminate that includes an electrode to be connected to a membrane such as an ion exchange membrane and a microporous membrane and to a supply conductor such as an existing degraded electrode with a weak force facilitates transport and handling, can significantly simplify work when a new electrolyzer is started or a degraded part is renewed and, in addition, it can also maintain or improve electrolytic performance, thus completing the present invention.

[0020] That is, the present invention includes the following aspects.

8/803 [2-1] A laminate comprising: an electrode for electrolysis, and a membrane or feed conductor in contact with the electrode for electrolysis, where a force applied per unit mass-unit area of the electrode for electrolysis in membrane or feed conductor is less than 1.5 N / mg: cm ?.

[2-2] The laminate according to [2-1], in which the force applied per unit mass-unit area of the electrode for electrolysis in the membrane or in the supply conductor is greater than 0.005 N / mg: -cm ?

[2-3] The laminate according to [2-1] or [2-2], where the feed conductor is a wire mesh, a non-woven metal fabric, a perforated metal, an expanded metal or a foamy metal.

[2-4] The laminate according to any one of [2-1] to [2-3], comprising, as at least one membrane surface layer, a layer comprising a mixture of hydrophilic oxide particles and a polymer in which ion exchange groups are introduced.

[2-5] The laminate according to any of [2-1] to [2-4], in which a liquid is interposed between the electrolysis electrode and the membrane or the supply conductor.

[0021] As a result of intensive studies to achieve the third objective, the present inventors have found that the problems described above can be solved by a laminate in which a membrane and an electrolysis electrode are partially fixed, thus completing the present invention.

[0022] That is, the present invention includes the following aspects.

B-1) A laminate comprising: a membrane, and an electrolysis electrode attached to at least one region of a membrane surface, where a proportion of the region on the membrane surface is greater than 0% and less than 93%.

[3-2] The laminate according to [3-1], in which the electrolysis electrode comprises at least one catalytic component selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy.

[3-3] The laminate according to [3-1] or [3-2], in which at least a portion of the electrolysis electrode penetrates the membrane and, therefore, is fixed in the region.

[3-4] The laminate according to any one of [3-1] to [3-3], in which at least a portion of the electrolyte electrode is located inside the membrane and, therefore, fixed in the region.

[3-5] The laminate according to any one of [3-1] to [3-4], additionally comprising a fixing member to fix the membrane and electrode for electrolysis.

[3-6] The laminate according to [3-5], in which at least a portion of the fixation member externally holds the membrane and electrode for electrolysis.

[3-7] The laminate according to [3-5] or [3-6], in which at least a portion of the fixing member fixes the membrane and the electrode for electrolysis by magnetic force.

[3-8] The laminate according to any one of [3-1] to [3-7], wherein the membrane comprises an ion exchange membrane comprising a surface layer comprising an organic resin, and the organic resin is present in the region.

[3-9] The laminate according to any of [3-1] to [3-8], wherein the membrane comprises a first layer of ion exchange resin and a second layer of ion exchange resin with an EW different from that of the first ion exchange resin layer.

[3-10] The laminate according to any one of [3-1] to [3-8], wherein the membrane comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a group different from that of the first ion exchange resin layer.

[0023] As a result of intensive studies to achieve the fourth objective, the present inventors have found that the problems described above can be solved by sandwiching at least a portion of a membrane laminate and an electrolyte electrode between a gasket on the side of the anode and a gasket on the cathode side, thus completing the present invention.

[0024] That is, the present invention includes the following aspects.

[4-1] An electrolyzer comprising: an anode, an anode frame that supports the anode, a gasket on the side of the anode that is arranged in the anode frame, a cathode that is opposite the anode, a cathode frame that supports the cathode, a cathode gasket that is arranged in the cathode frame and is opposite the anode gasket, and a membrane laminate and an electrolysis electrode, the laminate being arranged between the anode gasket and the cathode-side gasket, where at least a portion of the laminate is sandwiched between the anode-side gasket and the cathode-side gasket, and a ventilation resistance is 24 kPa-s / m or less when the electrode stops electrolysis has a size of 50 mm x 50 mm, the ventilation resistance being measured under temperature conditions of 24ºC, a relative humidity of 32%, a piston speed of 0.2 cm / s and a ventilation volume of 0.4 cc / in? / s.

[4-2] The electrolyser according to [4-1], where the electrolysis electrode has a thickness of 315 µm or less.

[4-3] The electrolyzer according to [4-1] or [4-2], in which a value obtained by measuring the electrode for electrolysis by method (A) below is 40 mm or less: [4-Method (THE)]

Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, a sample obtained by laminating the ion exchange membrane and the electrolysis electrode is rolled up and fixed on a curved surface of a core material made of polyvinyl chloride and with an external diameter of 32 mm and left to rest for 6 hours; thereafter, when the electrolysis electrode is separated from the sample and placed on a flat plate, heights in a vertical direction on both edges of the electrolysis electrode L1 and L2 are measured, and an average value is used as a measurement value .

[4-4] The electrolyzer according to any of [4-1] to [4-3], where a mass per unit area of the electrode for electrolysis is 48 mg / cm? or less.

[4-5] The electrolyzer according to any of [4-1] to [4-4], in which a force applied per unit of mass-unit area of the electrode for electrolysis is greater than 0.005 N / mg: cm.

[4-6] The electrolyzer according to any one of [4-1] to [4-5], in which an outer perimeter of the laminate is located farther outside than an outer perimeter of each one the anode-side gasket and the cathode-side gasket in the direction of a conductive surface.

[4-7] The electrolyzer according to any one of [4-1] to [4-6], where the electrolyte electrode comprises at least one catalytic component selected from the group consisting of Ru, Rh, Pd , Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, Tn, Sn, Sb , Ga, Ge, B, C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and

Dy.

[4-8] The electrolyzer according to any one of [4-1] to [4-7], in which at least a portion of the electrolysis electrode penetrates into the membrane and, therefore, is fixed in the laminate.

[4-9] The electrolyzer according to any one of [4-1] to [4-7], in which at least a portion of the electrolyte electrode is located inside the membrane and, therefore, fixed on the laminate.

[4-10] The electrolyzer according to any one of [4-1] to [4-9], in which the laminate additionally comprises a fixing member for fixing the membrane and electrode for electrolysis.

[4-11] The electrolyzer according to [4-10], in which, in the laminate, at least a portion of the fixing member penetrates and, therefore, fixes the membrane and electrode for electrolysis.

[4-12] The electrolyzer according to [4-10] or [4-11], in which, in the laminate, the fixing member comprises a soluble material that is soluble in an electrolyte solution.

[4-13] The electrolyzer according to any one of [4-10] to [4-12], in which, in the laminate, at least a portion of the fixing member externally holds the membrane and electrode for electrolysis.

[4-14] The electrolyzer according to any one of [4-10] to [4-13], in which, in the laminate, at least a portion of the fixing member fixes the membrane and the electrode for electrolysis by magnetic force .

14/803 [4-15] The electrolyzer according to any one of [4-1] to [4-14], wherein the membrane comprises an ion exchange membrane comprising a surface layer comprising an organic resin, and the electrolysis electrode is fixed by organic resin.

[4-16] The electrolyzer according to any of [4-1] to [4-15], wherein the membrane comprises a first layer of ion exchange resin and a second layer of ion exchange resin with an EW different from that of the first ion exchange resin layer.

[4-17] A method for producing the electrolyzer as defined in any one of [4-1] to [4-16], the method comprising: a laminating sandwich step between the anode-side gasket and the gasket on the side of the cathode.

[4-18] A method for renewing the laminate in the electrolyzer as defined in any one of [4-1] to [4-16], the method comprising: a step of separating the laminate from the anode and gasket side of the gasket. on the cathode side to remove the laminate from the electrolyzer, and a new laminating step between the anode-side gasket and the cathode-side gasket.

[0025] As a result of intensive studies to achieve the fifth objective, the present inventors have found that the problems described above can be solved by the use of an electrolysis electrode or an electrolysis electrode laminate and a new membrane, being in a form of rolled-up body, thus completing the present invention.

[0026] That is, the present invention includes the following aspects.

[5-1] A method for producing a new electrolyzer by arranging an electrolysis electrode or an electrolyte electrode laminate and a new membrane on an existing electrolyzer comprising an anode, a cathode that is opposite the anode, and a membrane that is arranged between the anode and the cathode, in which the electrolysis electrode or the laminate, being in a coiled body shape, is used.

[5-2] The method for producing the electrolyzer according to [5-1], comprising a step (A) of retaining the electrode for electrolysis or the laminate in a coiled state to obtain the coiled body.

[5-3] The method for producing the electrolyzer according to [5-1] or [5-2], comprising a step (B) of releasing the coiled state from the coiled body.

[5-4] The method for producing the electrolyzer according to [5-3], comprising a step (C) of arranging the electrode for electrolysis or the laminate on a surface of at least one of the anode and cathode after the step (B).

[5-5] A method for renewing an existing electrode using an electrolysis electrode, in which the electrolysis electrode, being in a coiled body shape, is used.

[5-6]

16/803 The method for renewing the electrode according to [5-5], comprising a step (A ') of electrode retention for electrolysis in a coiled state to obtain the coiled body.

[5-7] The method for renewing the electrode according to [5-5] or [5- 6], comprising a step (B ') of releasing the coiled state from the coiled body.

[5-8] The method for renewing the electrode according to [5-7], comprising a step (C *) of electrode arrangement for electrolysis on an existing electrode surface after step (B ”).

[5-9] A method for producing a coiled body to be used to renew an existing electrolyzer comprising an anode, a cathode that is opposite the anode, and a membrane that is arranged between the anode and the cathode, the method comprising: a winding step of an electrolysis electrode or a laminate of the electrolysis electrode and a new membrane to obtain the coiled body.

[0027] As a result of intensive studies to achieve the sixth objective, the present inventors found that the problems described above can be solved by integrating an electrolysis electrode with a new membrane at a temperature at which the membrane does not melt, thus completing the present invention.

[0028] That is, the present invention includes the following aspects.

[6-1] A method for producing a new electrolyzer by arranging a laminate on an existing electrolyzer comprising an anode, a cathode that is opposite the anode, and a membrane that is arranged between the anode

17/803 and the cathode, the method comprising: a step (A) of integration of an electrolysis electrode with a new membrane at a temperature where the membrane does not melt to obtain the laminate, and a step (B) of replacement of the membrane in the existing electrolyser by the laminate after step (A).

[6-2] The method for producing the electrolyzer according to [6-1], in which the integration is carried out under normal pressure.

[0029] As a result of intensive studies to achieve the seventh objective, the present inventors have found that the problems described above can be solved by an operation in an electrolyzer frame, thus completing the present invention.

[0030] That is, the present invention includes the following aspects.

[7-1] A method for producing a new electrolyzer by arranging a laminate comprising an electrolyte electrode and a new membrane on an existing electrolyzer comprising an anode, a cathode that is opposite the anode, a membrane that is fixed between the anode and the cathode, and an electrolyzer frame supporting the anode, cathode and membrane, the method comprising: a step (A) of releasing a membrane fixation on the electrolyzer frame, and a step (B) of replacing the membrane with laminated after step (A).

[7-2] The method for producing the electrolyzer according to [7-1], in which step (A) is carried out by sliding the anode and cathode in an arrangement direction, respectively.

18/803 [7-3] The method for producing the electrolyzer according to [7-1] or [7-2], in which the laminate is fixed to the electrolyzer frame by pressing the anode and cathode after step ( B).

[7-4] The method for producing the electrolyzer according to any one of [7-1] to [7-3], in which the laminate is fixed on a surface of at least one of the anode and cathode at a temperature wherein the laminate does not melt in step (B).

[7-5] A method for producing a new electrolyzer by arranging an electrolyte electrode on an existing electrolyzer comprising an anode, a cathode that is opposite the anode, a membrane that is attached between the anode and the cathode, and an electrolyzer frame that supports the anode, cathode and membrane, the method comprising: a step (A) of releasing a membrane fixation in the electrolyzer frame, and a step (B ') of electrode arrangement for electrolysis between the membrane and the anode or cathode after step (A).

Advantageous Effects of the Invention

[0031] (1) According to the electrolysis electrode of the present invention, it is possible to facilitate transport and handling, remarkably simplify work when a new electrolyzer is started or a degraded electrode is renewed and, in addition, also maintain or improve electrolytic performance.

[0032] (2) According to the laminate of the present invention, it is possible to improve the work efficiency during the electrode renewal in an electrolyzer and, in addition, to present an excellent electrolytic performance also after the renovation.

[0033] (3) According to the laminate of the present invention, it is possible to improve the work efficiency during the electrode renewal in an electrolyser and, in addition, to develop an excellent electrolytic performance also after the renovation, from a different point of view (2) described above.

[0034] (4) According to the electrolyser of the present invention, the electrolyser has excellent electrolytic performance, as well as can prevent damage to the membrane.

[0035] (5) According to the method for producing an electrolyzer of the present invention, it is possible to improve the work efficiency during the electrode renewal in an electrolyzer.

[0036] (6) According to the method for producing an electrolyzer of the present invention, it is possible to improve the work efficiency during the renewal of the electrode in an electrolyzer, from a different point of view than (5) described above.

[0037] (7) According to the method for producing an electrolyzer of the present invention, it is possible to improve the work efficiency during the electrode renewal in an electrolyzer, from a different point of view than (5) and (6) described above. Brief Description of Drawings

[0038] [Figure 1] The Figure | illustrates a schematic cross-sectional view of an electrolysis electrode according to an embodiment of the present invention.

[0039] [Figure 2] Figure 2 illustrates a schematic cross-sectional view showing an ion exchange membrane modality.

[0040] [Figure 3] Figure 3 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane.

[0041] [Figure 4] Figure 4 illustrates a schematic view for

/ 803 explain a method for forming the continuous holes in the ion exchange membrane.

[0042] [Figure 5] Figure 5 illustrates a schematic cross-sectional view of an electrolytic cell.

[0043] [Figure 6] Figure 6 illustrates a schematic cross-sectional view showing a state of two electrolytic cells connected in series.

[0044] [Figure 7] Figure 7 illustrates a schematic view of an electrolyzer.

[0045] [Figure 8] Figure 8 illustrates a schematic perspective view showing an electrolyzer assembly step.

[0046] [Figure 9] Figure 9 illustrates a schematic cross-sectional view of a reverse current absorber included in the electrolytic cell.

[0047] [Figure 10] Figure 10 illustrates a schematic view of a method for evaluating an applied force per unit mass-unit area (1) described in the Examples.

[0048] [Figure 11] Figure 11 illustrates a schematic view of a method for assessing winding around a 280 mm diameter column (1) described in the Examples.

[0049] [Figure 12] Figure 12 illustrates a schematic view of a method for evaluating winding around a 280 mm diameter column (2) described in the Examples.

[0050] [Figure 13] Figure 13 illustrates a schematic view of a method for assessing winding around a 145 mm diameter column (3) described in the Examples.

[0051] [Figure 14] Figure 14 illustrates a schematic view of the electrode strain test described in the Examples.

[0052] [Figure 15] Figure 15 illustrates a schematic view of a method for assessing smoothness after plastic deformation.

[0053] [Figure 16] Figure 16 illustrates a schematic view of an electrode produced in Comparative Example 13.

[0054] [Figure 17] Figure 17 illustrates a schematic view of a structure used to place the electrode produced in Comparative Example 13 in a nickel mesh feed conductor.

[0055] [Figure 18] Figure 18 illustrates a schematic view of an electrode produced in Comparative Example 14.

[0056] [Figure 19] Figure 19 illustrates a schematic view of a structure used to place the electrode produced in Comparative Example 14 in a nickel mesh feed conductor.

[0057] [Figure 20] Figure 20 illustrates a schematic view of an electrode produced in Comparative Example 15.

[0058] [Figure 21] Figure 21 illustrates a schematic view of a structure used to place the electrode produced in the Comparative Example in a nickel mesh feed conductor.

[0059] [Figure 22] Figure 22 illustrates a schematic cross-sectional view of an electrode for electrolysis in one embodiment of the present invention.

[0060] [Figure 23] Figure 23 illustrates a schematic cross-sectional view showing an ion exchange membrane modality.

[0061] [Figure 24] Figure 24 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane.

[0062] [Figure 25] Figure 25 illustrates a schematic view to explain a method for forming the continuous holes in the ion exchange membrane.

[0063] [Figure 26] Figure 26 illustrates a schematic cross-sectional view of an electrolytic cell.

[0064] [Figure 27] Figure 27 illustrates a schematic cross-sectional view showing a state of two electrolytic cells connected in series.

[0065] [Figure 28] Figure 28 illustrates a schematic view of an electrolyzer.

[0066] [Figure 29] Figure 29 illustrates a schematic perspective view showing an electrolyzer assembly step.

[0067] [Figure 30] Figure 30 illustrates a schematic cross-sectional view of a reverse current absorber included in the electrolytic cell.

[0068] [Figure 31] Figure 31 illustrates a schematic view of a method for evaluating an applied force per unit mass-unit area (1) described in the Examples.

[0069] [Figure 32] Figure 32 illustrates a schematic view of a method for evaluating winding around a 280 mm diameter column (1) described in the Examples.

[0070] [Figure 33] Figure 33 illustrates a schematic view of a method for evaluating winding around a 280 mm diameter column (2) described in the Examples.

[0071] [Figure 34] Figure 34 illustrates a schematic view of a method for assessing winding around a 145 mm diameter column (3) described in the Examples.

[0072] [Figure 35] Figure 35 illustrates a schematic view of the electrode strain test described in the Examples.

[0073] [Figure 36] Figure 36 illustrates a schematic view of a method for assessing smoothness after plastic deformation.

[0074] [Figure 37] Figure 37 illustrates a schematic view of an electrode produced in Example 34.

23/803

[0075] [Figure 38] Figure 38 illustrates a schematic view of a structure used to place the electrode produced in Example 34 in a nickel mesh feed conductor.

[0076] [Figure 39] Figure 39 illustrates a schematic view of an electrode produced in Example 35.

[0077] [Figure 40] Figure 40 illustrates a schematic view of a structure used to place the electrode produced in Example 35 in a nickel mesh feed conductor.

[0078] [Figure 41] Figure 41 illustrates a schematic view of an electrode produced in Example 36.

[0079] [Figure 42] Figure 42 illustrates a schematic view of a structure used to place the electrode produced in Example 36 in a nickel mesh feed conductor.

[0080] [Figure 43] Figure 43 illustrates a schematic cross-sectional view of an electrode for electrolysis in one embodiment of the present invention.

[0081] [Figure 44] Figure 44 illustrates a schematic cross-sectional view that illustrates an ion exchange membrane modality.

[0082] [Figure 45] Figure 45 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane.

[0083] [Figure 46] Figure 46 illustrates a schematic view to explain a method for forming the continuous holes in the ion exchange membrane.

[0084] [Figure 47] Figure 47A illustrates a schematic cross-sectional view of a laminate that illustrates an aspect in which at least a portion of an electrolysis electrode penetrates a membrane and is thus fixed. Figure 47B illustrates an explanatory view that illustrates a step

24/803 to obtain the structure of Figure 47A.

[0085] [Figure 48] Figure 48A illustrates a schematic cross-sectional view of a laminate that illustrates an aspect in which at least a portion of an electrolysis electrode is located within the membrane and is thus fixed. Figure 48B illustrates an explanatory view that illustrates a step of obtaining the structure of Figure 48A.

[0086] [Figure 49] Figures 49A to 49C illustrate schematic cross-sectional views of a laminate that illustrates an aspect where a wire-like fixation member is used for fixation as a fixation member to fix a membrane and an electrode for electrolysis.

[0087] [Figure 50] Figure 50 illustrates a schematic cross-sectional view of a laminate that illustrates an aspect in which an organic resin is used for fixation as a fixing member to fix a membrane and electrode for electrolysis.

[0088] [Figure 51] Figure SIA illustrates a schematic cross-sectional view of a laminate that illustrates an aspect in which at least a portion of a fixation member externally attaches a membrane and an electrolysis electrode to fix them. Figure SIB illustrates a schematic cross-sectional view of the laminate that illustrates an aspect in which at least a portion of a fixing member fixes the membrane and the electrode for magnetic force electrolysis.

[0089] [Figure 52] Figure 52 illustrates a schematic cross-sectional view of an electrolytic cell.

[0090] [Figure 53] Figure 53 illustrates a schematic cross-sectional view showing a state of two electrolytic cells connected in series.

[0091] [Figure 54] Figure 54 illustrates a schematic view of an electrolyzer.

[0092] [Figure 55] Figure 55 illustrates a perspective view

/ 803 schematic showing an electrolyzer assembly step.

[0093] [Figure 56] Figure 56 illustrates a schematic cross-sectional view of a reverse current absorber that can be included in an electrolytic cell.

[0094] [Figure 57] Figure 57 illustrates an explanatory view showing a laminate in Example 1.

[0095] [Figure 58] Figure 58 illustrates an explanatory view showing a laminate in Example 2.

[0096] [Figure 59] Figure 59 illustrates an explanatory view showing a laminate in Example 3.

[0097] [Figure 60] Figure 60 illustrates an explanatory view showing a laminate in Example 4.

[0098] [Figure 61] Figure 61 illustrates an explanatory view showing a laminate in Example 5.

[0099] [Figure 62] Figure 62 illustrates an explanatory view showing a laminate in Example 6.

[00100] [Figure 63] Figure 63 illustrates a schematic cross-sectional view of an electrolytic cell.

[00101] [Figure 64] Figure 64A illustrates a schematic cross-sectional view showing a state of two electrolytic cells connected in series in a conventional electrolyser. Figure 64B illustrates a schematic cross-sectional view showing a state of two electrolytic cells connected in series in the electrolyzer of the present embodiment.

[00102] [Figure 65] Figure 65 illustrates a schematic view of an electrolyzer.

[00103] [Figure 66] Figure 66 illustrates a schematic perspective view showing an electrolyzer assembly step.

[00104] [Figure 67] Figure 67 illustrates a schematic view in

26/803 cross section of a reverse current absorber that can be included in an electrolytic cell.

[00105] [Figure 68] Figure 68 illustrates a schematic cross-sectional view of an electrode for electrolysis in one embodiment of the present invention.

[00106] [Figure 69] Figure 69 illustrates a schematic cross-sectional view illustrating an ion exchange membrane modality.

[00107] [Figure 70] Figure 70 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane.

[00108] [Figure 71] Figure 71 illustrates a schematic view to explain a method for forming the continuous holes in the ion exchange membrane.

[00109] [Figure 72] Figure 72 illustrates an explanatory view to explain the positional relationship between the laminate and the gaskets.

[00110] [Figure 73] Figure 73 illustrates an explanatory view to explain the positional relationship between the laminate and the gaskets.

[00111] [Figure 74] Figure 74A illustrates a schematic cross-sectional view of a laminate that illustrates an aspect in which at least a portion of an electrolysis electrode penetrates a membrane and is thus fixed. Figure 74B illustrates an explanatory view that illustrates a step of obtaining the structure of Figure 12A.

[00112] [Figure 75] Figure 75A illustrates a schematic cross-sectional view of a laminate that illustrates an aspect in which at least a portion of an electrolysis electrode is located within the membrane and is thus fixed. Figure 13B illustrates an explanatory view that illustrates a step of obtaining the structure of Figure 75A.

[00113] [Figure 76] Figures 76A to C illustrate schematic views

27/803 in cross section of a laminate that illustrates an aspect in which a wire-like fixation member is used for fixation as a fixation member to fix a membrane and an electrolysis electrode.

[00114] [Figure 77] Figure 77 illustrates a schematic cross-sectional view of a laminate that illustrates an aspect in which an organic resin is used for fixation as a fixation member to fix a membrane and electrode for electrolysis.

[00115] [Figure 78] Figure 78A illustrates a schematic cross-sectional view of a laminate that illustrates an aspect in which at least a portion of a fixation member externally attaches a membrane and an electrolysis electrode to fix them. Figure 78B illustrates a schematic cross-sectional view of the laminate that illustrates an aspect in which at least a portion of a fixing member fixes the membrane and the electrode for magnetic force electrolysis.

[00116] [Figure 79] Figure 79 illustrates a schematic view of a method for evaluating an applied force per unit mass-unit area (1) described in the Examples.

[00117] [Figure 80] Figure 80 illustrates a schematic view of a method for evaluating winding around a 280 mm diameter column (1) described in the Examples.

[00118] [Figure 81] Figure 81 illustrates a schematic view of a method for assessing winding around a 280 mm diameter column (2) described in the Examples.

[00119] [Figure 82] Figure 82 illustrates a schematic view of a method for evaluating winding around a 145 mm diameter column (3) described in the Examples.

[00120] [Figure 83] Figure 83 illustrates a schematic view of the flexibility assessment of the electrode described in the Examples.

[00121] [Figure 84] Figure 84 illustrates a schematic view of a

28/803 method to assess smoothness after plastic deformation.

[00122] [Figure 85] Figure 85 illustrates a schematic view of an electrode produced in Example 35.

[00123] [Figure 86] Figure 86 illustrates a schematic view of a structure used to place the electrode produced in Example 35 in a nickel mesh feed conductor.

[00124] [Figure 87] Figure 87 illustrates a schematic view of an electrode produced in Example 36.

[00125] [Figure 88] Figure 88 illustrates a schematic view of a structure used to place the electrode produced in Example 36 in a nickel mesh feed conductor.

[00126] [Figure 89] Figure 89 illustrates a schematic view of an electrode produced in Example 37.

[00127] [Figure 90] Figure 90 illustrates a schematic view of a structure used to place the electrode produced in Example 37 in a nickel mesh feed conductor.

[00128] [Figure 91] Figure 91 illustrates a schematic cross-sectional view of an electrolytic cell.

[00129] [Figure 92] Figure 92 illustrates a schematic cross-sectional view showing a state of two electrolytic cells connected in series.

[00130] [Figure 93] Figure 93 illustrates a schematic view of an electrolyzer.

[00131] [Figure 94] Figure 94 illustrates a schematic perspective view showing an electrolyzer assembly step.

[00132] [Figure 95] Figure 95 illustrates a schematic cross-sectional view of a reverse current absorber that can be included in an electrolytic cell.

[00133] [Figure 96] Figure 96 illustrates a schematic view in

29/803 cross section of an electrolysis electrode in an embodiment of the present invention.

[00134] [Figure 97] Figure 97 illustrates a schematic cross-sectional view illustrating a modality of an ion exchange membrane.

[00135] [Figure 98] Figure 98 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane.

[00136] [Figure 99] Figure 99 illustrates a schematic view to explain a method for forming the continuous holes in the ion exchange membrane.

[00137] [Figure 100] Figure 100 illustrates a schematic view of a laminate produced in Example 1.

[00138] [Figure 101] Figure 101 illustrates a schematic view of the case where the laminate produced in Example 1 is rolled up to form a rolled-up body.

[00139] [Figure 102] Figure 102 illustrates a schematic view of a laminate produced in Example 4.

[00140] [Figure 103] Figure 103 illustrates a schematic cross-sectional view of an electrolytic cell.

[00141] [Figure 104] Figure 104 illustrates a schematic cross-sectional view showing a state of two electrolytic cells connected in series.

[00142] [Figure 105] Figure 105 illustrates a schematic view of an electrolyzer.

[00143] [Figure 106] Figure 106 illustrates a schematic perspective view showing an electrolyzer assembly step.

[00144] [Figure 107] Figure 107 illustrates a schematic cross-sectional view of a reverse current absorber that can be included

/ 803 in an electrolytic cell.

[00145] [Figure 108] Figure 108 illustrates a schematic cross-sectional view of an electrode for electrolysis in one embodiment of the present invention.

[00146] [Figure 109] Figure 109 illustrates a schematic cross-sectional view that illustrates an ion exchange membrane modality.

[00147] [Figure 110] Figure 110 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane.

[00148] [Figure 111] Figure 111 illustrates a schematic view to explain a method for forming the continuous holes in the ion exchange membrane.

[00149] [Figure 112] Figure 112 illustrates a schematic cross-sectional view of an electrolytic cell.

[00150] [Figure 113] Figure 113 illustrates a schematic cross-sectional view showing a state of two electrolytic cells connected in series.

[00151] [Figure 114] Figure 114 illustrates a schematic view of an electrolyzer.

[00152] [Figure 115] Figure 115 illustrates a schematic perspective view showing an electrolyzer assembly step.

[00153] [Figure 116] Figure 116 illustrates a schematic cross-sectional view of a reverse current absorber that can be included in an electrolytic cell.

[00154] [Figure 117] Figure 117 (A) illustrates a schematic view of an electrolyzer to explain an example of each step according to a first aspect of the present embodiment. Figure 117 (B) illustrates a schematic perspective view corresponding to Figure 117 (A).

[00155] [Figure 118] Figure 118 (A) illustrates a schematic view of an electrolyzer to explain an example of each step according to a second aspect of the present modality. Figure 118 (B) illustrates a schematic perspective view corresponding to Figure 118 (A).

[00156] [Figure 119] Figure 119 illustrates a schematic cross-sectional view of an electrode for electrolysis in one embodiment of the present invention.

[00157] [Figure 120] Figure 120 illustrates a schematic cross-sectional view that illustrates an ion exchange membrane modality.

[00158] [Figure 121] Figure 121 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane.

[00159] [Figure 122] Figure 122 illustrates a schematic view to explain a method for forming the continuous holes in the ion exchange membrane. Description of Modalities

[00160] Hereinafter, regarding the modalities of the present invention (hereinafter, they can be called present modalities), <First modality> to <Seventh modality> will be described, each, in detail, with reference to the drawings as required . The modalities below are illustrations to explain the present invention, and the present invention is not limited to the content below. The attached drawings illustrate an example of the modalities, and the modalities should not be considered limited to it. The present invention can be appropriately modified and carried out in the spirit thereof. In drawings, positional relationships, such as top, bottom, left and right, are based on the positional relationships shown in the drawing, unless otherwise noted. The dimensions and ratios in the drawings are not limited to those shown.

<First modality>

[00161] Here, a first embodiment of the present invention will be described in detail with reference to Figures 1 to 21. [Electrode for electrolysis]

[00162] An electrode for electrolysis of the first modality (hereinafter, in the section of <First modality>, simply called “the present modality”) can provide a good handling property, it has a good adhesive force to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a feed conductor without catalyst coating and the like, and additionally, has a mass per unit area of 48 mg / cm? or less from the point of view of economics. Is the mass per unit area preferably 30 mg / cm? or less, even more preferably 20 mg / cm? or less in relation to the above, and in addition it is preferably 15 mg / cm? or less from a comprehensive point of view including handling, adhesion and economy properties. The lower limit value is not particularly limited, but is in the order of 1 mg / cm?, For example.

[00163] The mass per unit area described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness and the like, for example. More specifically, for example, when the thickness is constant, a larger opening ratio tends to lead to a smaller mass per unit area, and a smaller opening ratio tends to lead to a mass per unit area greater.

[00164] The electrolysis electrode of the present modality has a force applied per unit mass-unit area of 0.08 N / (mg: cm?) Or more from the point of view of enabling a good handling property and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a feed conductor without catalyst coating and the like. The force applied by

33/803 unit of mass-unit area is preferably 0.1 N / (mg: cm?) Or more, more preferably 0.14 N / (mg: cm?) Or more with respect to the above, and more preferably 0 , 2 N / (mg: cm?) Or more from the point of view of facilitating handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is not particularly limited, but is preferably 1.6 N / (mg: cm?) Or less, more preferably less than 1.6 N / (mg: cm?), Even more preferably 1.5 N / (mg-in?), even more preferably 1.2 N / mg-cm? or less, even more preferably 1.20 N / mg: cm? or less. Is the upper limit value even more preferably 1.1 N / m? or less, even more preferably 1.10 N / mg-cm? or less, particularly preferably 1.0 N / m? or less, especially preferably 1.00 N / mg: cm? or less.

[00165] From the point of view that the electrolyte electrode of the present modality, if it is an electrode with a wide region of elastic deformation, can provide a better handling property and has a better adhesive force to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a feed conductor with no catalyst coating, and the like, the electrode thickness for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, still more preferably 150 µm or less, particularly preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 um or more, more

34/803 preferably 5 µm or more for practical reasons, more preferably 20 µm or more. In the present modality, “having a wide region of elastic deformation” means that when an electrolysis electrode is wound to form a wound body, it is unlikely that distortion derived from the winding will occur after the wound state is released. The thickness of the electrolysis electrode refers, when a catalyst layer mentioned below is included, to the total thickness of both the electrolysis electrode substrate and the catalyst layer.

[00166] The electrolyte electrode of the present modality, which has a good adhesive strength to a membrane, such as an ion exchange membrane and a microporous membrane, a degraded electrode, a feed conductor without catalyst coating, and the like, as described above, it can be integrated with a membrane, such as an ion exchange membrane and a microporous membrane and used. For this reason, by renewing the electrode, the electrode can be renewed by a job as simple as renewing the membrane, without a complicated replacement job like removing the electrode attached to the electrolytic cell, and thus, the work efficiency is noticeably improved. Even in the case where only one supply conductor is placed in a new electrolytic cell (that is, an electrode including no layer of catalyst placed), only affixing the electrode for the electrolysis of this modality to the supply conductor allows the electrode to function. Thus, it may also be possible to significantly reduce or eliminate the catalyst coating.

[00167] In addition, according to the electrode for electrolysis of the present modality, it is possible to make the electrolytic performance comparable or superior to that of a new electrode.

[00168] The electrolyte electrode of the present modality can be stored or transported to customers in a state where the electrode is wrapped around a vinyl chloride tube or similar (in a state

/ 803 laminate or similar), making handling noticeably easier.

[00169] The applied force can be measured by the methods (1) or (ii) described below, which are as described in the Examples in detail. As for the applied force, the value obtained by measuring the method (1) (also called “the applied force (1)”) and the value obtained by measuring the method (ii) (also called “the applied force (2) ”) Can be the same or different, and any of the values is 0.08 N / (mg: cm?) Or more.

[00170] The applied force described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness, arithmetic mean surface roughness and the like, for example. More specifically, for example, a higher opening ratio tends to lead to a lower applied force, and a lower opening ratio tends to lead to a higher applied force. [Method (i)]

[00171] A nickel plate obtained by stripping processing with grain size 320 alumina (1.2 mm thick, 200 square mm), an ion exchange membrane that is obtained by applying particles of inorganic material and a binder on both surfaces of a perfluorocarbon polymer membrane where an ion exchange group (170 mm square, the detail of the ion exchange membrane referred to here is as described in the Examples) and an electrode sample for electrolysis (130 square mm) are rolled in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. The arithmetic mean roughness of the surface (Ra) of the nickel plate after the pickling treatment was 0.7 µm. The specific method for calculating the arithmetic mean surface roughness (Ra) is as described in the Examples.

[00172] Under conditions of temperature of 23 + 2ºC and relative humidity

36/803 of 30 + 5%, only the electrolyte sample for electrolysis in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the load when the electrode sample stops electrolysis is elevated by 10 mm in a vertical direction is measured. This measurement is repeated three times and the average value is calculated.

[00173] This average value is divided by the area of the overlapping portion of the electrode sample and the ion exchange membrane and the mass of the portion that overlaps the ion exchange membrane in the electrode sample for electrolysis to calculate the force applied by unit of mass-unit of area (1) (N / mg-ecm?).

[00174] The force applied per unit mass-unit area (1) obtained by method (i) is 0.08 N / (mg-in?) Or more, preferably 0.1 N / (mg: cm?) or more from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating, and more preferably 0.2 N / (mg: cm?) or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is not particularly limited, but is preferably 1.6 N / (magnet?) Or less, more preferably less than 1.6 N / (mg: ecm?), Even more preferably 1.5 N / ( mg: cm?), even more preferably 1.2 N / mg: -cm? or less, even more preferably 1.20 N / mg: cm? or less. The upper limit value is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg-cm? or less.

[00175] When the electrolyte electrode of the present modality satisfies the applied force (1), the electrode can be integrated with a membrane such as an ion exchange membrane and a membrane

37/803 microporous, for example, is used. Thus, when renewing the electrode, the work of replacing the cathode and anode fixed to the electrolytic cell by a method such as welding is eliminated, and the work efficiency is noticeably improved. Additionally, by using the electrode for the electrolysis of the present modality as an electrode integrated with the ion exchange membrane, it is possible to make the electrolytic performance comparable or superior to that of a new electrode.

[00176] When sending a new electrolytic cell, an electrode fixed on an electrolytic cell was conventionally subjected to the catalyst coating. Since only the combination of an electrode without a catalyst coating with the electrolyte electrode of the present modality can allow the electrode to function as an electrode, it is possible to remarkably reduce or eliminate the production step and the quantity of the catalyst for the coating of catalyst. A conventional electrode whose catalyst coating is noticeably reduced or eliminated can be electrically connected to the electrolyte electrode of the present modality and allowed to serve as a supply conductor for the passage of an electric current. [Method (ii)]

[00177] A nickel plate obtained by stripping processing with alumina of grain size 320 (1.2 mm thickness, 200 square mm, a nickel plate similar to the method (1) above) and an electrode sample for electrolysis (130 mm square) is laminated in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, only the electrolyte sample for electrolysis in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the load when the sample of

38/803 electrode for electrolysis is raised by 10 mm in a vertical direction is measured. This measurement is repeated three times and the average value is calculated.

[00178] This average value is divided by the area of the overlapping portion of the electrolysis electrode sample and the nickel plate and the mass of the electrode sample for electrolysis in the portion that overlaps the nickel plate to calculate the adhesive force per unit of mass unit of area (2) (N / mg: cm?).

[00179] The force applied per unit mass-unit area (2) obtained by method (ii) is 0.08 N / (mg-cm?) Or more, preferably 0.1 N / (mg: cm?) or more from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating, and more preferably 0.14 N / (mg: in?) or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is not particularly limited, but is preferably 1.6 N / (mg: cm?) Or less, more preferably less than 1.6 N / (mg: ecm?), Even more preferably 1.5 N / (mg: in?), even more preferably 1.2 N / mg: cm? or less, even more preferably 1.20 N / mg: cm? or less. The upper limit value is even more preferably 1.1 N / mg: in? or less, even more preferably 1.10 N / mg-cm? or less, particularly preferably 1.0 N / mg: cm? or less, especially preferably 1.00 N / mg: ecm? or less.

[00180] The electrolysis electrode of the present modality, if it satisfies the applied force (2), can be stored or transported to customers in a state where the electrode is wrapped around a vinyl chloride tube or similar (in a laminated or similar state), making handling remarkably easier. When attaching the electrolysis electrode of this

39/803 modality to a degraded electrode, it is possible to make the electrolytic performance comparable or superior to that of a new electrode.

[00181] In the present modality, as the liquid included between the membrane, such as an ion exchange membrane and a microporous membrane, the electrode for electrolysis or the feed conductor (electrode or degraded electrode without catalyst coating) and the electrode for Electrolysis, any liquid such as water and organic solvents, can be used as long as the liquid generates a surface tension. The greater the surface tension of the liquid, the greater the force applied between the membrane and the electrolysis electrode or the metal plate and electrode for electrolysis. Thus, a liquid with a higher surface tension is preferred. Examples of the liquid include the following (the numerical value in parentheses is the surface tension of the liquid): hexane (20.44 mN / m), acetone (23.30 mN / m), methanol (24.00 mN / m), ethanol (24.05 mN / m), ethylene glycol (50.21 mN / m) and water (72.76 mN / m).

[00182] A liquid with a high surface tension allows the membrane and electrode for electrolysis or the porous metal plate or metal plate (feed conductor) and the electrode for electrolysis to be integrated (to be a laminate) to facilitate renovation the electrode. The liquid between the membrane and the electrolysis electrode or the porous metal plate or metal plate (feed conductor) and the electrolysis electrode can be present in an amount such that both adhere to each other by surface tension. As a result, after the laminate is placed in an electrolytic cell, the liquid, if mixed in the electrolytic solution, does not affect the electrolysis itself due to the small amount of the liquid.

[00183] From a practical point of view, a liquid with a surface tension of 20 mN / m to 80 mN / m, such as ethanol, ethylene glycol and water, is

40/803 preferably used as the liquid. Particularly preferred is water or an aqueous alkaline solution prepared by dissolving caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate or the like in water. Alternatively, the surface tension can be adjusted by allowing these liquids to contain a surfactant. When a surfactant is contained, the adhesion between the membrane and the electrolysis electrode or the metal plate and the electrolysis electrode varies to allow the handling property to be adjusted. The surfactant is not particularly limited and ionic and non-ionic surfactants can be used.

[00184] The electrolysis electrode of the present embodiment preferably includes a substrate for electrolysis electrode and a layer of catalyst. The substrate thickness for the electrolysis electrode (gauge thickness) is not particularly limited, but is preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, more preferably 135 µm or less, even more preferably 125 µm or less, even more preferably 120 µm or less, even more preferably 100 µm or less from the point of view of enabling a good handling property to be provided, having a good adhesive strength to a membrane, such as an exchange membrane ion and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating, be able to be properly laminated on a roll and folded satisfactorily, facilitating handling in a large size (for example, a size of 1.5 mx 2.5 m), and even more preferably 50 µm or less from the point of view of a handling and economical property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

41/803

[00185] The proportion measured by the following method (2) of the electrode for electrolysis of the present embodiment is not particularly limited, but is preferably 90% or more, more preferably 92% or more from the point of view of allowing a good handling property is provided and has a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating, and more preferably 95% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (2)]

[00186] An ion exchange membrane (170 mm square) and an electrode sample for electrolysis (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 280 mm) so that the electrolyte sample for electrolysis in that laminate is positioned outside under conditions of 23 + 2ºC and relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) is then measured of an area of a portion where the ion exchange membrane (170 square mm) is in close contact with the electrode sample for electrolysis.

[00187] The proportion measured by the following method (3) of the electrode for electrolysis of the present embodiment is not particularly limited, but is preferably 75% or more, more preferably 80% or more from the point of view of allowing a good handling property provided, have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating and can be suitably

42/803 laminated on a roll and satisfactorily folded, and is more preferably 90% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 m x 2.5 m). The upper limit value is 100%. [Method (3)]

[00188] An ion exchange membrane (170 mm square) and an electrode sample for electrolysis (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 145 mm) so that the electrode sample for electrolysis in that laminate is positioned outside under conditions of 23 + 2ºC and relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) is then measured of an area of a portion where the ion exchange membrane (170 square mm) is in close contact with the electrode sample for electrolysis.

[00189] The electrolyte electrode of the present embodiment preferably has, but is not particularly limited to, a porous structure and an opening ratio or void ratio of 5 to 90% or less from the point of view of enabling a good handling property, have good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, and a feed conductor without catalyst coating, and to prevent the accumulation of gas from being generated during electrolysis. The opening ratio is more preferably at 80% or less, more preferably at 20 to 75%.

[00190] The opening ratio is a proportion of the opening portions per unit volume. The calculation method may differ depending on whether the opening portions in submicron size are considered or that only visible openings are considered. In the present modality,

43/803 a volume V was calculated from the values of the thickness of the gauge, width and length of the electrode and, in addition, a weight W was measured to thereby calculate an aperture ratio A using the following formula.

A = (1- (W / (YV xp)) x 100

[00191] p is the density of the electrode material (g / cm?). For example, p nickel is 8.908 g / cm ”, and p titanium is 4.506 g / cm ?. The opening ratio is appropriately adjusted by changing the area of metal to be drilled per unit area in the case of perforated metal, changing the SW (short diameter), LW (long diameter) and feed values in the case of expanded metal, changing the metal fiber line diameter and mesh number in the case of mesh, changing the pattern of a photoresist to be used in the case of electroforming, changing the diameter of the metal fiber and fiber density in the case of non-woven fabric, changing the mold to form voids in the case of foamed metal or similar.

[00192] The value obtained by measuring by the following method (A) of the electrolyte for electrolysis in the present embodiment is preferably 40 mm or less, more preferably 29 mm or less, even more preferably 10 mm or less, even more preferably 6.5 mm or less from the point of view of manipulation property. The specific measurement method is as described in the Examples. [Method (A)]

[00193] Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, a sample obtained by laminating the ion exchange membrane and the electrolysis electrode is rolled up and fixed on a curved surface of a core material made of polyvinyl chloride with an external diameter of 32 mm and left to rest for 6 hours; thereafter, when the electrolysis electrode is separated from the sample and placed on a flat plate, heights in a vertical direction on both edges of the electrolysis electrode L, and L7 are measured, and an average value is used as a value of

44/803 measurement.

[00194] In the electrode for electrolysis in the present mode, the ventilation resistance is preferably 24 kPa-s / m or less when the electrolysis electrode is 50 mm x 50 mm in size, the ventilation resistance being measured under the conditions the temperature of 24ºC, the relative humidity of 32%, a piston speed of 0.2 cm / s and a ventilation volume of 0.4 cc / in? / s (hereinafter, also called “measurement condition 1 ”) (Hereinafter, also called“ ventilation resistance 1 ”). Higher ventilation resistance means that air is unlikely to flow and refers to a state of high density. In this state, the electrolysis product remains on the electrode and it is more unlikely that the reaction substrate will diffuse inside the electrode, and thus the electrolytic performance (like the voltage) tends to deteriorate. The concentration on the membrane surface tends to increase. Specifically, the caustic concentration increases at the cathode surface, and the supply of brine tends to decrease at the anode surface. As a result, the product accumulates in high concentration at the interface at which the membrane is in contact with the electrode. This build-up causes damage to the membrane and also tends to increase the tension and damage to the membrane on the cathode surface and damage to the membrane on the anode surface. In the present embodiment, in order to avoid these defects, the ventilation resistance is preferably set at 24kPa-s / m or less. From a point of view similar to the above, the ventilation resistance is more preferably less than 0.19 kPa-s / m, more preferably 0.15 kPa-s / m or less, even more preferably 0.07 kPa-s / m or less.

[00195] In the present mode, when the ventilation resistance is greater than a certain value, the NaOH generated in the electrode tends to accumulate at the interface between the electrode and the membrane to result in a high concentration in the case of the cathode, and the supply brine tends to

45/803 decrease to make the brine concentration lower in the case of the anode. In order to avoid damage to the membrane that could be caused by such an accumulation, the ventilation resistance is preferably less than 0.19 kPa-s / m, more preferably 0.15 kPas / m or less, even more preferably 0.07 kPa -s / m or less.

[00196] In contrast, when the ventilation resistance is low, the electrode area is reduced and the electrolysis area is reduced. Thus, electrolytic performance (like voltage) tends to deteriorate. When the ventilation resistance is zero, the supply conductor functions as the electrode, as no electrolysis electrode is provided and the electrolytic performance (like the voltage) tends to deteriorate noticeably. From that point of view, a preferable lower limit value identified as the ventilation resistance | it is not particularly limited, but is preferably greater than 0 kPa-s / m, more preferably 0.0001 kPa-s / m or more, even more preferably 0.001 kPa-s / m or more.

[00197] When the ventilation resistance 1 is 0.07 kKPa-s / m or less, sufficient measurement accuracy may not be achieved because of the measurement method for it. From this point of view, it is also possible to evaluate an electrolysis electrode with ventilation resistance 1 of 0.07 kPa-s / m or less by means of a ventilation resistance (hereinafter, also called “ventilation resistance 2 ”) obtained by the following measurement method (hereinafter, also called“ measurement condition 2 ”). That is, ventilation resistance 2 is a measured ventilation resistance, when the electrolysis electrode has a size of 50 mm x 50 mm, under conditions of temperature of 24ºC, the relative humidity of 32%, a piston speed of 2 cm / s and a ventilation volume of 4 cc / in? / s.

[00198] Specific methods for measuring ventilation resistances | and 2 are described in the Examples.

46/803

[00199] Ventilation resistors 1 and 2 can be within the range described above, appropriately adjusting an opening ratio, electrode thickness and the like, for example. More specifically, for example, when the thickness is constant, a higher opening ratio tends to lead to ventilation resistances | and 2 smaller, and a smaller opening ratio tends to lead to greater ventilation resistances 1 and 2.

[00200] From now on, an aspect of the electrode for the electrolysis of the present modality will be described.

[00201] The electrolysis electrode according to the present embodiment preferably includes a substrate for electrolysis electrode and a layer of catalyst. The catalyst layer can be composed of a plurality of layers, as shown below, or it can be a single layer configuration.

[00202] As shown in Figure 1, an electrolysis electrode 100 according to the present embodiment includes an electrolyte electrode substrate 10 and a pair of first layers 20 with which both surfaces of the electrolysis electrode substrate 10 are covered. . The entire electrode substrate for electrolysis 10 is preferably covered with the first layers 20. This coating is likely to improve catalyst activity and electrode durability. A first layer 20 can be laminated only on one surface of the electrode substrate for electrolysis

10.

[00203] Also shown in Figure 1, the surfaces of the first layers 20 can be covered with the second layers 30. The first entire layers 20 are preferably covered by the second layers 30. Alternatively, a second layer 30 can be laminated only one surface of the first layer 20. (Electrode substrate for electrolysis)

[00204] As substrate for electrode for electrolysis 10, for example,

47/803 nickel, nickel alloys, stainless steel, and even valve metals including titanium can be used, although not limited to them. At least one element selected from nickel (Ni) and titanium (Ti) is preferably included. That is, the electrode substrate for electrolysis preferably includes at least one element selected from nickel (Ni) and titanium (Ti).

[00205] When stainless steel is used in a high-concentration aqueous alkaline solution, iron and chromium are eluted and the electrical conductivity of stainless steel is about one tenth that of nickel. In view of the above, a substrate containing nickel (Ni) is preferable as a substrate for the electrolysis electrode.

[00206] Alternatively, when the electrode substrate for electrolysis 10 is used in a high concentration saline solution close to saturation under an atmosphere in which chlorine gas is generated, the substrate material for electrode 10 is also preferably titanium with high corrosion resistance.

[00207] The shape of the electrode substrate for electrolysis 10 is not particularly limited, and a shape suitable for the purpose can be selected. As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. Among these, a perforated metal or expanded metal is preferable. Electroforming is a technique for producing a thin metal film with a precise pattern using photolithography and electroplating in combination. It is a method that includes the formation of a pattern on a substrate with a photoresist and electroplating of the portion not protected by the resistance to provide a thin metal film.

[00208] As for the shape of the substrate for the electrolysis electrode, an appropriate specification depends on the distance between the anode and the cathode in the electrolyzer. In the event that the distance between the anode and the cathode is finite,

48/803 a form of expanded metal or perforated metal can be used, and in the case of a so-called zero interstitial electrolyzer, in which the ion exchange membrane is in contact with the electrode, a woven mesh produced by fine knitted threads, foamy metal, non-woven metallic fabric, expanded metal, perforated metal, porous metal foil and the like, although not limited to it.

[00209] Examples of the electrode substrate for electrolysis 10 include a metal foil, wire mesh, metal nonwoven fabric, perforated metal, expanded metal or foamy metal.

[00210] As plate material before being processed into a perforated metal or expanded metal, laminated plate materials and electrolytic sheets are preferred. An electrolytic sheet is preferably still subjected to a galvanizing treatment using the same element as its base material, such as after-treatment, to thereby form roughness on the surface thereof.

[00211] The thickness of the electrode substrate for electrolysis 10 is, as mentioned above, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less, even more preferably 125 one or less, even more preferably 120 µm or less, even more preferably 100 µm or less, and even more preferably 50 µm or less from the point of view of a handling and economical property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[00212] On the electrode substrate for electrolysis, the residual stress during processing is preferably relaxed by annealing the electrode substrate for electrolysis in an oxidizing atmosphere. It is preferable to form roughness using a steel grid, alumina grid or similar on the surface of the electrode substrate for electrolysis followed by a

49/803 acid treatment to increase its surface area, in order to improve adhesion to a catalyst layer with which the surface is covered. It is preferable to give a galvanizing treatment using the same element as the substrate to increase the surface area.

[00213] In order to place the first layer 20 in close contact with the surface of the electrolyte electrode substrate 10, the electrode electrode substrate 10 is preferably subjected to a treatment to increase the surface area. Examples of the treatment of increasing the surface area include a pickling treatment using a cut wire, steel grid, alumina grid or similar, an acid treatment using sulfuric acid or hydrochloric acid, and a galvanizing treatment using the same element as the of the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 µm to 50 µm, more preferably 0.1 to 10 µm, even more preferably 0.1 to 5 µm.

[00214] Next, a case will be described in which the electrode for electrolysis of the present modality is used as an anode for electrolysis of common salt. (First layer)

[00215] In Figure 1, a first layer 20 as a catalyst layer contains at least one of the ruthenium oxides, iridium oxides and titanium oxides. Examples of ruthenium oxide include RuO; Examples of iridium oxide include IrO ,. Examples of titanium oxide include TiO,; The first layer 20 preferably contains two oxides: a ruthenium oxide and a titanium oxide or three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide. This makes the first layer 20 more stable and further improves adhesion with the second layer 30.

[00216] When the first layer 20 contains two oxides: a ruthenium oxide and a titanium oxide, the first layer 20 contains

50/803 preferably 1 to 9 mol, more preferably 1 to 4 mol of titanium oxide based on 1 mol of the ruthenium oxide contained in the first layer 20. With the composition ratio of the two oxides in this range, the electrolyte for electrolysis 100 excellent durability.

[00217] When the first layer 20 contains three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide, the first layer 20 preferably contains 0.2 to 3 mol, more preferably 0.3 to 2.5 mol of iridium oxide based on 1 mol of ruthenium oxide contained in the first layer 20. The first layer 20 preferably contains 0.3 to 8 mol, more preferably 1 to 7 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition of the three oxides in this range, the electrode for electrolysis 100 has excellent durability.

[00218] When the first layer 20 contains at least two of a ruthenium oxide, an iridium oxide and a titanium oxide, these oxides preferably form a solid solution. The formation of the solid oxide solution allows the electrolysis electrode 100 to have excellent durability.

[00219] In addition to the compositions described above, oxides of various compositions may be used provided that at least one oxide of a ruthenium oxide, an iridium oxide and titanium oxide is contained. For example, an oxide coating called DSA (R), which contains ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum and the like, can be used as a first layer 20.

[00220] The first layer 20 need not be a single layer and can include a plurality of layers. For example, the first layer 20 can include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 µm, more preferably 0.1 to 8 µm.

(Second layer)

[00221] The second layer 30 preferably contains ruthenium and titanium. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[00222] The second layer 30 preferably contains a palladium oxide, a solid solution of a palladium and platinum oxide, or an alloy of palladium and platinum. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[00223] A second thicker layer 30 can maintain electrolytic performance for a longer period, but from an economic point of view, the thickness is preferably 0.05 to 3 µm.

[00224] Next, a case will be described in which the electrolyte electrode of the present modality is used as a cathode for electrolysis of common salt. (First layer)

[00225] Examples of components of the first layer 20 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[00226] When the first layer 20 contains at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides, and alloys containing a platinum group metal, the metals of the platinum group platinum, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal preferably contain at least one platinum group metal of platinum, palladium, rhodium, ruthenium and iridium.

[00227] Like the platinum group metal, platinum is preferably contained.

[00228] Like the metal oxide of the platinum group, a ruthenium oxide is preferably contained.

[00229] Like the metal hydroxide of the platinum group, a ruthenium hydroxide is preferably contained.

[00230] Like the platinum group metal alloy, a platinum alloy with nickel, iron and cobalt is preferably contained.

[00231] In addition, as needed, an oxide or hydroxide of a lanthanide element is preferably contained as a second component. This allows the electrolysis electrode 100 to have excellent durability.

[00232] As the oxide or hydroxide of a lanthanide element, at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium and dysprosium is preferably contained.

[00233] Furthermore, as needed, an oxide or hydroxide of a transition metal is preferably contained as a third component.

[00234] The addition of the third component allows the electrolysis electrode 100 to have greater durability and the electrolysis voltage to be reduced.

[00235] Examples of a preferable combination include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + Platinum + Palladium, Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + cobalt, ruthenium + samarium + zinc, ruthenium + samarium + gallium, ruthenium + samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + nickel el + palladium, platinum + nickel + ruthenium, platinum and nickel alloys, platinum and cobalt alloys, and platinum and iron alloys.

[00236] When platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal are not contained, the main component of the catalyst is preferably the nickel element.

[00237] At least one of the nickel metals, oxides and hydroxides is preferably contained.

[00238] As the second component, a transition metal can be added. As the second component to be added, at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper and carbon is preferably contained.

[00239] Examples of a preferable combination include nickel + tin, nickel + titanium, nickel + molybdenum and nickel + cobalt.

[00240] As required, an intermediate layer can be placed between the first layer 20 and the electrode substrate for electrolysis

10. The durability of the electrolysis electrode 100 can be improved by placing the intermediate layer.

[00241] As the intermediate layer, those having affinity for both the first layer 20 and the electrode substrate for electrolysis 10 are preferred. As the intermediate layer, nickel oxides, platinum group metals, metal oxides are preferable of the platinum group and metal hydroxides of the platinum group. The intermediate layer can be formed by applying and cooking a solution containing a component that forms the intermediate layer. Alternatively, a

54/803 surface oxide layer can also be formed by subjecting a substrate to a heat treatment at a temperature of 300 to 600ºC in an air atmosphere. In addition, the layer can be formed by a known method, such as a thermal spray method and an ion galvanizing method. (Second layer)

[00242] Examples of components of the first layer 30 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. The first layer 30 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal. Examples of a preferable combination of elements contained in the second layer include the combinations listed for the first layer. The combination of the first layer and the second layer can be a combination in which the compositions are the same and the composition ratios are different or they can be a combination of different compositions.

[00243] As the thickness of the catalyst layer, the total thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 µm to 20 µm. With a thickness of 0.01 µm or more, the catalyst layer can sufficiently serve as the catalyst. With a thickness of 20 µm or less, it is possible to form a robust catalyst layer that is unlikely to fall off the substrate. The thickness is more preferably 0.05 µm to 15 µm. The thickness is more preferably 0.1 µm to 10 µm. The thickness is even more preferably 0.2 µm to 8 µm.

[00244] The thickness of the electrode, that is, the total thickness of the electrode substrate for electrolysis and the catalyst layer is preferably 315

One or less, more preferably 220 one or less, more preferably 170 One or less, even more preferably 150 one or less, particularly - preferably 145 one or less, even more preferably 140 one or less, even more preferably 138 one or less, even more preferably 135 µm or less with respect to the handling property of the electrode. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably one or more. The thickness of the electrode can be determined by measurement with a digital thickness gauge (Mitutoyo Corporation, minimum scale 0.001 mm). The thickness of the electrode substrate for electrolysis was measured in the same way as the thickness of the electrode. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode. (Method to produce electrode for electrolysis)

[00245] Next, an embodiment of the method for producing the electrolysis electrode 100 will be described in detail.

[00246] In the present embodiment, the electrolysis electrode 100 can be produced by forming the first layer 20, preferably the second layer 30, on the electrode electrode substrate by a method such as cooking a coating film under an oxygen atmosphere ( pyrolysis) or ion galvanizing, galvanizing or thermal spraying. Among these, the pyrolysis method, the galvanizing method, and the ion galvanizing method are preferable because the catalyst layer can be formed while avoiding deformation of the electrode substrate to

56/803 electrolysis. When the productivity point of view is added, the galvanizing method and the pyrolysis method are still preferable. The production method of the present modality as mentioned can achieve high productivity of the electrode for electrolysis 100. Specifically, in the pyrolysis method, a layer of catalyst is formed on the electrode substrate for electrolysis by an application step to apply a coating liquid containing a catalyst, a drying step to dry the coating liquid and a pyrolysis step to perform pyrolysis. Pyrolysis here means that a metal salt that is to be a precursor is decomposed by heating into a metal or metal oxide and a gaseous substance. The decomposition product depends on the metal species to be used, the type of salt and the atmosphere under which pyrolysis is carried out, and many metals tend to form oxides in an oxidizing atmosphere. In an industrial process for producing an electrolysis electrode, pyrolysis is generally performed in air, and a metal oxide or metal hydroxide is formed in many cases. (Formation of the first anode layer) (Application stage)

[00247] The first layer 20 is obtained by applying a solution in which at least one metallic salt of ruthenium, iridium and titanium is dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the liquid coating in the presence of oxygen. The ruthenium, iridium and titanium content in the first coating liquid is substantially equivalent to that of the first layer 20.

[00248] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The concentration

57/803 total metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating.

[00249] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[00250] After being applied to the electrode substrate for electrolysis 100, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[00251] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then

58/803 additionally post-cooked for a long period, as needed, can further improve the stability of the first layer 20. (Formation of the second anode layer)

[00252] The second layer 30, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second liquid of first layer 20 and then pyrolyzing the coating liquid in the presence of oxygen. (Formation of the first cathode layer by the pyrolysis method) (Application stage)

[00253] The first layer 20 is obtained by applying a solution in which metal salts of various combinations are dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the coating liquid in the presence of oxygen. The metal content in the first coating liquid is substantially equivalent to that of the first layer 20.

[00254] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as ethanol and butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is, but is not particularly limited to, preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating.

[00255] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersing the substrate to electrode for

59/803 electrolysis 10 in the first coating liquid, a brushing method of the first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in the opposite way and spraying is carried out. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[00256] After being applied to the electrode substrate for electrolysis 10, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[00257] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally baked for a long period, as needed, heating in the range of 350ºC to 650ºC can further improve the stability of the first layer 20. (Formation of the intermediate layer)

[00258] The intermediate layer, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound or a platinum compound (second coating liquid) in the

60/803 substrate and then pyrolyzing the coating liquid in the presence of oxygen. Alternatively, an intermediate layer of nickel oxide can be formed on the surface of the substrate just by heating the substrate, with no solution applied to it, in the range of 300ºC to 580ºC for one minute to 60 minutes. (Formation of the first cathode layer by ion galvanizing)

[00259] The first layer 20 can also be formed by ion plating.

[00260] An example includes a method in which the substrate is fixed in a chamber and the metal ruthenium target is irradiated with an electron beam. Evaporated metallic ruthenium particles are positively charged to the plasma in the chamber to deposit on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and deposits of ruthenium as ruthenium oxide in the substrate. (Formation of the first cathode layer by galvanizing)

[00261] The first layer 20 can also be formed by a method of galvanizing.

[00262] For example, when the substrate is used as a cathode and subjected to electrolytic galvanization in an electrolytic solution containing nickel and tin, nickel and tin alloy galvanizing can be formed. (Formation of the first cathode layer by thermal spray)

[00263] The first layer 20 can also be formed by thermal spraying.

[00264] As an example, the nickel oxide particles sprayed by plasma on the substrate can form a catalyst layer in which the metal nickel and nickel oxide are mixed.

[00265] The electrolyte electrode of the present modality can be integrated with a membrane, such as an ion exchange membrane and a microporous membrane, and used. Thus, the electrode can be used as an electrode integrated into the membrane. Then, the work of replacing the cathode and anode in electrode renewal is eliminated, and the work efficiency is noticeably improved.

[00266] The electrolyte electrode of the present modality forms a laminate with a membrane such as an ion exchange membrane and a microporous membrane to be an integrated part of the membrane and the electrode, and then can make the electrolytic performance comparable or higher than that of a new electrode. The membrane is not particularly limited as long as the membrane can be laminated with the electrode and will be described in detail below. [Ion exchange membrane]

[00267] The ion exchange membrane has a membrane body containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and a coating layer provided on at least one surface of the membrane body. The coating layer contains particles of inorganic material and a binder, and the specific surface area of the coating layer is 0.1 to 10 m / g. In the ion exchange membrane that has such a structure, the influence of the gas generated during electrolysis on the electrolytic performance is small, and the stable electrolytic performance can be presented.

[00268] The ion exchange membrane described above includes a layer of sulfonic acid with an ion exchange group derived from a sulfo group (a group represented by -SO3 ', here also called a "sulfonic acid group") or a layer of carboxylic acid with an ion exchange group derived from a carboxyl group (a group represented by -CO ;, here also called a "carboxylic acid group"). From the point of view of strength and dimensional stability, reinforcement core materials are preferably included.

[00269] The particles of inorganic material and binder will be

62/803 described in detail in the coating layer description section below.

[00270] Figure 2 illustrates a schematic cross-sectional view showing an ion exchange membrane modality. An ion exchange membrane | it has a membrane body 10 containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and coating layers 11a and 11b formed on both surfaces of the membrane body 10.

[00271] In the ion exchange membrane 1, the membrane body 10 includes a layer of sulfonic acid 3 and a layer of carboxylic acid 2, and the reinforcement core materials 4 increase strength and dimensional stability. The ion exchange membrane 1, including the sulfonic acid layer 3 and the carboxylic acid layer 2, is suitably used as an ion exchange membrane.

[00272] The ion exchange membrane can include the sulfonic acid layer or the carboxylic acid layer. The ion exchange membrane may not necessarily be reinforced by reinforcement core materials, and the arrangement of the reinforcement core materials is not limited to the example in Figure 2. (Membrane body)

[00273] First, the membrane body 10 which constitutes the ion exchange membrane 1 will be described.

[00274] The membrane body 10 must be one that has the function of selectively allowing cations to permeate and comprises a hydrocarbon polymer or a fluorine-containing polymer with an ion exchange group. Its configuration and material are not particularly limited, and the preferred ones can be selected appropriately.

[00275] The hydrocarbon polymer or fluorine-containing polymer with an ion exchange group on the membrane body 10 can be obtained from a hydrocarbon polymer or fluorine-containing polymer with a

63/803 ion exchange group precursor capable of forming an ion exchange group by hydrolysis or similar. Specifically, for example, after a polymer comprising a fluorinated hydrocarbon backbone that has, as a pendant side chain, a group convertible into an ion exchange group by hydrolysis or similar (precursor to the ion exchange group), and is processable by melting (hereinafter called "fluorine-containing polymer (a)" in some cases), be used to prepare a precursor to the membrane body 10, the membrane body 10 can be obtained by converting the precursor to the ion exchange group in an ion exchange group.

[00276] The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. The fluorine-containing polymer (a) can also be produced by homopolymerizing a monomer selected from any of the following first group, the following second group and the following third group.

[00277] Examples of the monomers of the first group include vinyl fluoride compounds. Examples of the vinyl fluoride compounds include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and perfluoralkyl vinyl ethers. Particularly when the ion exchange membrane is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoro monomer, and a perfluoro monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and perfluoralkylvinyl ethers is preferable.

[00278] Examples of the monomers of the second group include vinyl compounds with a functional group convertible into an ion exchange group of the carboxylic acid type (carboxylic acid group). Examples of vinyl compounds with a functional group convertible to an acid group

64/803 carboxylic include monomers represented by CF = CF (OCF; CYF); - O (CZF) .- COOR, where s represents an integer from O to 2, t represents an integer from 1 to 12, Y and Z each independently represents F or CF; 3, and R represents a lower alkyl group (a lower alkyl group is an alkyl group with 1 to 3 carbon atoms, for example).

[00279] Among them, compounds represented by CF; = CF (OCF; CYF), - O (CF2) n-COOR are preferable. Where n represents an integer from 0 to 2, m represents an integer from 1 to 4, Y represents F or CF; 3, and R represents CH3, CoHs, or C3H ;.

[00280] When the ion exchange membrane is used as a cation exchange membrane for alkaline electrolysis, a perfluoro compound is preferably at least used as the monomer, but the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis and, therefore, the alkyl group (R) need not be a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[00281] Of the monomers above, the monomers shown below are more preferable than the monomers of the second group: CF; = CFOCF; -CF (CF;) OCF; COOCH ;, CF; = CFOCF; CF (CF3) O (CF3) -COOCH ;, CF; = CF [OCF3-CF (CF3) 12O (CF>) - COOCH ;, CF; = CFOCF; CF (CF3) O (CF3); 5COOCH ;, CF3 = CFO (CF3); COOCH; , and CF; = CFO (CF;); COOCH ;.

[00282] Examples of the monomers of the third group include vinyl compounds with a functional group convertible into an ion exchange group of the sulfone type (sulfonic acid group). As vinyl compounds with a functional group convertible to a sulfonic acid group, for example, monomers represented by CF; = CFO-X-CF; -SO, F are preferred, where X represents a perfluoroalkylene group. Examples

Specific 65/803 of these include the monomers represented below: CF; = CFOCFCFSOF, CF3 = CFOCF; CF (CF3) OCF; CF3SO, F, CF; = CFOCF: CF (CF3) OCF; CFCF3SO) F, CF3 = CF (CF3 ); SOF, CF3 = CFO [CF; CF (CF3) O] 1CF.CFE3SOF, and CF. = CFOCF; CF (CF; OCF3) OCF; CFSO »xF.

[00283] Among them, CF = CFOCF; CF (CF3) OCF; CF; CFSO0.F = and CF; = CFOCF; CF (CF3) OCF; CF3SO, F are more preferable.

[00284] The copolymer obtained from these monomers can be produced by a polymerization method developed for homopolymerization and copolymerization of ethylene fluoride, particularly a general polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, a polymerization reaction can be carried out in the presence of a radical polymerization initiator such as a perfluorocarbon peroxide or an azo compound under the conditions of a temperature of 0 to 200ºC and a pressure of 0, 1 to 20 MPa using an inert solvent such as a perfluorohydrocarbon or a chlorofluorocarbon.

[00285] In the above copolymerization, the type of combination of the above monomers and their proportion are not particularly limited and are selected and determined depending on the type and quantity of the desired functional group to be imparted to the fluorine-containing polymer to be obtained. For example, when a fluorine-containing polymer containing only one carboxylic acid group is formed, at least one monomer must be selected from each of the first group and the second group described above and copolymerized. In addition, when a fluorine-containing polymer containing only one sulfonic acid group is formed, at least one monomer must be selected from each of the first group and the third group and copolymerized. In addition, when a fluorine-containing polymer with a

66/803 carboxylic acid group and a sulfonic acid group is formed, at least one monomer must be selected from each of the first group, the second group and the third group described above and copolymerized. In that case, the target fluorine-containing polymer can also be obtained by separately preparing a copolymer comprising the monomers of the first group and the second group described above and a copolymer comprising the monomers of the first group and the third group described above, and then mixing the copolymers. The mixing ratio of the monomers is not particularly limited, and when the number of functional groups per unit of polymer is increased, the proportion of the selected monomers from the second and third groups described above should be increased.

[00286] The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, more preferably 0.6 to 1.5 mg equivalent / g. The total ion exchange capacity here refers to the exchange group equivalent per unit weight of the dry resin and can be measured by neutralization titration or the like.

[00287] In the membrane body 10 of the ion exchange membrane 1, a layer of sulfonic acid 3 containing a polymer containing fluorine with a group of sulfonic acid and a layer of carboxylic acid 2 containing a polymer containing fluorine with a group of carboxylic acid are laminated. By providing the membrane body 10 with this layer configuration, the selective permeability for cations, such as sodium fons, can be further improved.

[00288] The ion exchange membrane | it is arranged in an electrolyzer in such a way that, generally, the sulfonic acid layer 3 is located on the anode side of the electrolyzer and the carboxylic acid layer 2 is located on the cathode side of the electrolyzer.

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[00289] The sulfonic acid layer 3 is preferably made of a material with low electrical resistance and has a membrane thickness greater than that of the carboxylic acid layer 2 from the point of view of the membrane resistance. The membrane thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, more preferably 3 to 15 times that of the carboxylic acid layer 2.

[00290] The carboxylic acid layer 2 preferably has high anion exclusion properties, even if it has a small membrane thickness. The anion exclusion properties here refer to the property of trying to prevent anion intrusion and permeation into and through the ion exchange membrane 1. In order to increase the anion exclusion properties, it is effective to lay out a layer of carboxylic acid with a small ion exchange capacity to the sulfonic acid layer.

[00291] As the fluorine-containing polymer for use in the sulfonic acid layer 3, a polymer obtained using CF; = CFOCF; CF (CF3) OCF; CF3SO, 3F as the monomer of the third group is preferred.

[00292] As the fluorine-containing polymer for use in the carboxylic acid-2 layer, a polymer obtained using CF; = CFOCF; CF (CF3) O (CF;); COOCH; as the monomer of the second group. (Coating layer)

[00293] The ion exchange membrane has a coating layer on at least one surface of the membrane body. As shown in Figure 2, on the ion exchange membrane 1, coating layers 11a and 11b are formed on both surfaces of the membrane body 10.

[00294] The coating layers contain particles of inorganic material and a binder.

[00295] The average particle size of the particles of inorganic material is preferably 0.90 µm or more. When the average size of

68/803 particle of particles of inorganic material is 0.90 µm or more, the durability to impurities is greatly improved, in addition to gas display. That is, increasing the average particle size of the particles of inorganic material, as well as satisfying the value of the specific surface area mentioned above, can achieve a particularly remarkable effect. Irregular inorganic material particles are preferable because the average particle size and specific surface area, as above, are satisfied. Particles of inorganic material obtained by melting and particles of inorganic material obtained by grinding ore can be used. Particles of inorganic material obtained by grinding raw ore can preferably be used.

[00296] The average particle size of inorganic material particles can be 2 µm or less. When the average particle size of the particles of inorganic material is 2 µm or less, it is possible to avoid damage to the membrane due to the particles of inorganic material. The average particle size of the inorganic material particle is more preferably 0.90 to 1.2 µm.

[00297] Here, the average particle size can be measured by a particle size analyzer (“SALD2200”, SHIMADZU CORPORATION).

[00298] Particles of inorganic material are preferably irregularly shaped. Such shapes further improve resistance to impurities. Particles of inorganic material preferably have a wide particle size distribution.

[00299] Particles of inorganic material preferably contain at least one inorganic material selected from the group consisting of oxides of Group IV elements in the Periodic Table, nitrides of Group IV elements in the Periodic Table and carbides of Group IV elements in Periodic table. From the point of view of durability, the particle

69/803 zirconium oxide is more preferable.

[00300] The particles of inorganic material are preferably particles of inorganic material produced by grinding the raw ore of the particles of inorganic material or particles of inorganic material, such as spherical particles with a uniform diameter, obtained by purification by melting the raw ore of the particles of inorganic material.

[00301] Examples of means for grinding raw ore include, but are not particularly limited to, ball mills, ball mills, colloid mills, taper mills, disc mills, roller mills, grain mills, hammer mills, granules, VSI mills, Wiley mills, laminators and jet mills. After grinding, the particles are preferably washed. As a washing method, the particles are preferably treated with acid. This treatment can reduce impurities, such as iron affixed to the surface of particles of inorganic material.

[00302] The coating layer preferably contains a binder. The binder is a component that forms the coating layers retaining particles of inorganic material on the surface of the ion exchange membrane. The binder preferably contains a polymer containing fluorine from the point of view of durability to the electrolytic solution and electrolysis products.

[00303] As the binder, it is preferable a polymer containing fluorine with a carboxylic acid group or a sulfonic acid group, from the point of view of durability to the electrolytic solution and products of electrolysis and adhesion to the surface of the ion exchange membrane. When a coating layer is provided on a layer containing a fluorine-containing polymer with a sulfonic acid group (sulfonic acid layer), a fluorine-containing polymer with a sulfonic acid group is still preferably used as the binder of the coating layer. Alternatively, when

70/803 a coating layer is provided in a layer containing a fluorine-containing polymer with a carboxylic acid group (carboxylic acid layer), a fluorine-containing polymer with a carboxylic acid group is still preferably used as the binder of the coating layer.

[00304] In the coating layer, the content of the particles of inorganic material is preferably 40 to 90% by weight, more preferably 50 to 90% by weight. The content of the binder is preferably 10 to 60% by weight, more preferably 10 to 50% by weight.

[00305] The distribution density of the coating layer on the ion exchange membrane is preferably 0.05 to 2 mg per 1 µm. When the ion exchange membrane has roughness on its surface, the distribution density of the coating layer is preferably 0.5 to 2 mg per 1 in °.

[00306] As the method for forming the coating layer, which is not particularly limited, a known method can be used. An example is a method that includes spraying or the like of a coating liquid obtained by dispersing particles of inorganic material in a solution containing a binder. (Reinforcement core materials)

[00307] The ion exchange membrane preferably has reinforcement core materials arranged within the membrane body.

[00308] The reinforcement core materials are members that enhance the resistance and dimensional stability of the ion exchange membrane. By arranging the reinforcement core materials within the membrane body, particularly the expansion and contraction of the ion exchange membrane can be controlled in the desired range. Such an ion exchange membrane does not expand or contract more than necessary during electrolysis and the like and can maintain excellent dimensional stability in the long run.

[00309] The configuration of the reinforcement core materials is not particularly limited and, for example, the reinforcement core materials can be formed by spinning threads called reinforcement threads. The reinforcement threads here refer to threads that are members that make up the reinforcement core materials, can provide the desired dimensional stability and mechanical resistance to the ion exchange membrane and can be stably present in the ion exchange membrane. By using the reinforcement core materials obtained by spinning such reinforcement threads, better dimensional stability and mechanical resistance to the ion exchange membrane can be provided.

[00310] The material of the reinforcement core materials and the reinforcement yarns used for them is not particularly limited, but is preferably a material resistant to acids, alkalis, etc., and a fiber comprising a fluorine-containing polymer is preferable because the long-term thermal resistance and chemical resistance are required.

[00311] Examples of the fluorine-containing polymer to be used in the reinforcement core materials include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroethyl vinyl ether (PFA) copolymers, tetrafluoroethylene-ethylene (ETFE) copolymers, tetrafluoroethylene-copolymers, hexetrafluoroethylene-copolymers, tetrafluoroethylene-copolymers. trifluorochlorethylene-ethylene and polymers of vinylidene fluoride (PVDF). Among these, fibers comprising polytetrafluoroethylene are preferably used from the point of view of heat resistance and chemical resistance.

[00312] The wire diameter of the reinforcement threads used for the reinforcement core materials is not particularly limited, but is preferably 20 to 300 deniers, more preferably 50 to 250 deniers. The weave density (fabric count per unit length) is preferably 5 to 50 / inch (1 inch = 2.54 cm). The shape of the reinforcement core materials is not particularly limited, for example,

a woven fabric, a nonwoven fabric and a knitted fabric are used, but it is preferably in the form of a woven fabric. The thickness of the woven fabric to be used is preferably 30 to 250 µm, more preferably 30 to 150 µm.

[00313] As woven fabric or knitted fabric, monofilaments, multifilaments, or yarns thereof, a slit yarn, or the like, and various types of weaving methods, such as single weft, leno weft, knitted weft, weft, can be used cord and sirsaca, can be used.

[00314] The weft and arrangement of the reinforcement core materials in the membrane body are not particularly limited, and the preferred arrangement can be adequately provided considering the size and shape of the ion exchange membrane, desired physical properties for the membrane of ion exchange, the environment of use and the like.

[00315] For example, the reinforcement core materials can be arranged along a predetermined direction of the membrane body, but from the point of view of dimensional stability, it is preferable that the reinforcement core materials are arranged over a predetermined first direction, and other reinforcement core materials along a second direction substantially perpendicular to the first direction. By arranging the plurality of reinforcement core materials substantially orthogonally within the membrane body, it is possible to provide better dimensional stability and mechanical strength in several directions. For example, the arrangement in which reinforcement core materials arranged along the longitudinal direction (warp yarns) and reinforcement core materials arranged along the transverse direction (weft threads) are woven on the surface side of the body membrane is preferred. The arrangement is most preferably in the form of driven flat weft and woven fabric allowing the warps and wefts to alternately move between themselves and underneath each other, smooth weft in which two warps are woven into wefts while twisted, weft in a driven and woven basket by insertion in two or more warps arranged in parallel, wefts of the same or similar number, from the point of view of dimensional stability, mechanical resistance and ease of production.

[00316] It is preferred that, in particular, the reinforcement core materials are arranged along both directions, the MD (Machine Direction) and TD (Transversal Direction) of the ion exchange membrane. In other words, the reinforcement core materials are preferably single woven in MD and TD. Here, MD refers to the direction in which the membrane body and various core materials (for example, the reinforcement core materials, reinforcement wires and sacrificial wires described below) are transported in a production step of ion exchange membrane described later (flow direction) and TD refers to the direction substantially perpendicular to the MD. The threads woven along the MD are called MD threads, and the threads woven along the TD are called TD threads. Typically, the ion exchange membrane used for electrolysis is rectangular, and in many cases, the longitudinal direction is the MD, and the width direction is the TD. By weaving the reinforcement core materials that are MD yarns and the reinforcement core materials that are TD yarns, it is possible to provide better dimensional stability and mechanical strength in many directions.

[00317] The range of arrangement of the reinforcement core materials is not particularly limited, and the preferred arrangement can be adequately provided considering the desired physical properties for the ion exchange membrane, the environment of use and the like.

[00318] The orifice ratio for the reinforcement core materials is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The orifice ratio is preferably 30% or more from the point of view of the electrochemical properties of the ion exchange membrane, and preferably 90% or

74/803 less from the point of view of the mechanical resistance of the ion exchange membrane.

[00319] The orifice ratio for reinforcement core materials refers to a ratio of a total area of a surface through which substances such as fons (an electrolyte solution and cations contained therein (for example, sodium fons)) they can pass (B) to the area of one of the surfaces of the membrane body (A) (B / A). The total surface area through which substances such as fons can pass (B) can refer to the total areas of regions in which the ion exchange membrane, cations, an electrolyte solution and the like are not blocked by the reinforcement core materials and similar substances contained in the ion exchange membrane.

[00320] Figure 3 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane. Figure 3, in which a portion of the ion exchange membrane is enlarged, shows only the arrangement of the reinforcement core materials 21 and 22 in the regions, omitting the illustration of the other members.

[00321] By subtracting the total area of the reinforcement core materials (C) from the area of the region surrounded by the reinforcement core materials 21 arranged along the longitudinal direction and the reinforcement core materials 22 arranged along the transverse direction, the region including the area of the reinforcement core materials (A), the total area of regions through which substances such as phons can pass (B) in the area of the region described above (A) can be obtained. That is, the orifice ratio can be determined by the following formula (1): Orifice ratio = (B) / (A) = ((A) - (O0)) / (A) ... (D

[00322] Among the materials of the reinforcement core, a particularly preferred form are highly oriented tape yarns or monofilaments comprising PTFE from the point of view of chemical resistance and heat resistance. Specifically, reinforcement core materials forming a single web in which 50 to 300 denier ribbon yarns obtained by cutting a high strength porous sheet comprising PTFE into a ribbon form, or highly oriented 50 to 300 denier monofilaments are used comprising PTFE and having a weave density of 10 to 50 threads or monofilaments / inch and having a thickness in the range of 50 to 100 µm are more preferred. The orifice ratio of an ion exchange membrane comprising such reinforcement core materials is still preferably 60% or more.

[00323] Examples of the shape of the reinforcement threads include round threads and ribbon threads. (Continuous holes)

[00324] The ion exchange membrane preferably has continuous holes inside the membrane body.

[00325] Continuous holes refer to holes that can be flow paths for fons generated in electrolysis and an electrolyte solution. The continuous holes, which are tubular holes formed inside the membrane body, are formed by dissolving the sacrificial core materials (or sacrificial threads) described below. The shape, diameter or the like of the continuous holes can be controlled by selecting the shape or diameter of the sacrificial core materials (sacrificial threads).

[00326] Forming the continuous holes inside the ion exchange membrane can guarantee the mobility of an electrolyte solution in electrolysis. The shape of the continuous holes is not particularly limited, but it may be the shape of the sacrificial core materials to be used for forming the continuous holes according to the production method described below.

[00327] The continuous holes are preferably formed in order to pass alternately on the anode side (sulfonic acid layer side) and on the cathode side (carboxylic acid layer side) of the reinforcement core materials. With this structure, in a portion in which are formed

76/803 continuous holes on the cathode side of the reinforcement core materials, fons (for example, sodium fons) carried by the electrolyte solution with which the continuous holes are filled can also flow on the cathode side of the reinforcement core materials . As a result, the flow of cations is not interrupted and, therefore, it is possible to further reduce the electrical resistance of the ion exchange membrane.

[00328] Continuous holes can be formed along only a predetermined direction of the membrane body that constitutes the ion exchange membrane, but are preferably formed both in the longitudinal and transverse direction of the membrane body from the point of view of presenting a more stable electrolytic performance. [Production method]

[00329] A suitable example of a method for producing an ion exchange membrane includes a method including the following steps (1) to (6): step (1): the step of producing a fluorine-containing polymer with an exchange group ionic or an ion exchange group precursor capable of forming an ion exchange group by hydrolysis, step (2): the weaving step of at least a plurality of reinforcement core materials, as required, and sacrificial yarns with a proprietary dissolving in an acid or an alkali, and forming continuous holes to obtain a reinforcement material in which the sacrifice wires are arranged between the reinforcement core materials adjacent to each other, step (3): the formation step in a fluorine-containing polymer film above with an ion exchange group or a precursor to the ion exchange group capable of forming an ion exchange group by hydrolysis, step (4): the step of embedding the reinforcement materials above, as required, in the film above to obtain a membrane body within which the reinforcement materials are arranged,

step (5): the hydrolysis step of the membrane body obtained in step (4) (hydrolysis step), and step (6): the step of providing a coating layer on the membrane body obtained in step (5) (application stage).

[00330] Next, each of the steps will be described in detail. Step (1): Fluorine-containing polymer production step

[00331] In step (1), the raw material monomers described in the first group for the third group above are used to produce a fluorine-containing polymer. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the raw material monomers must be adjusted in the production of the fluorine-containing polymer that forms the layers. Step (2): Reinforcement materials production step

[00332] The reinforcement material is a woven fabric obtained by weaving reinforcement threads or the like. The reinforcement material is embedded in the membrane to form reinforcement core materials. When an ion exchange membrane with continuous holes is formed, the sacrificial threads are additionally woven into the reinforcement material. The amount of the sacrificial yarns contained in that case is preferably 10 to 80% by weight, more preferably 30 to 70% by weight based on the entire reinforcement material. Weaving the sacrificial yarns can also prevent the yarn from slipping the reinforcement core materials.

[00333] As sacrificial threads, which have solubility in the membrane production stage or under an electrolysis environment, rayon, polyethylene terephthalate (PET), cellulose, polyamide and the like are used. Also preferred are monofilaments or multifilaments having a thickness of 20 to 50 deniers and comprising polyvinyl alcohol and the like.

[00334] In step (2), the orifice ratio, the arrangement of continuous and similar holes can be controlled by adjusting the arrangement of the reinforcement core materials and the sacrifice wires. Step (3): Film forming step

[00335] In step (3), the fluorine-containing polymer obtained in step (1) is formed into a film using an extruder. The film can be a single layer configuration, a two layer configuration of a sulfonic acid layer and a layer of carboxylic acid, as mentioned above, or a multilayer configuration of three layers or more.

[00336] Examples of the film-forming method include the following: a method in which a fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are formed separately in films; and a method in which the fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are coextruded into a composite film.

[00337] The number of each film can be more than one. Coextrusion of different films is preferred because of their contribution to an increase in adhesive strength at the interface. Stage (4): Stage of obtaining the membrane body

[00338] In step (4), the reinforcement material obtained in step (2) is embedded in the film obtained in step (3) to provide a membrane body including the reinforcement material therein.

[00339] Preferred examples of the method for forming a membrane body include (1) a method in which a fluorine-containing polymer with a precursor to the carboxylic acid group (e.g., carboxylate functional group) (hereinafter, a layer comprising the same called the first layer) located on the cathode side and a fluorine-containing polymer with a precursor to the sulfonic acid group (for example,

functional group of sulfonyl fluoride) (hereinafter, a layer comprising the same is called the second layer) are formed in a film by a coextrusion method and, using a heat source and a vacuum source as necessary, a material reinforcement and the second layer / first layer composite film are laminated in that order on heat-resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while air between each layer it is evacuated under reduced pressure; and (11) a method in which, in addition to the composite film of the second layer / first layer, a fluorine-containing polymer with a precursor to the sulfonic acid group is formed separately in a film (the third layer) in advance and, using a heat source and a vacuum source as needed, the third layer film, the reinforcement core materials and the composite film comprising the second layer / first layer are laminated in that order on heat resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated under reduced pressure.

[00340] The coextrusion of the first layer and the second layer contributes to an increase in the adhesive strength at the interface.

[00341] The method including integration under reduced pressure is characterized by making the third layer in the reinforcement material thicker than that of the pressure method of applying pressure. In addition, since the reinforcement material is fixed on the inner surface of the membrane body, the method has a property of sufficiently retaining the mechanical resistance of the ion exchange membrane.

[00342] The lamination variations described here are exemplary, and coextrusion can be performed after a preferred lamination pattern (for example

80/803 example, the layer combination) be appropriately selected considering the desired layer configuration of the membrane body and physical properties, and the like.

[00343] In order to further improve the electrical properties of the ion exchange membrane, it is also possible to additionally interpose a fourth layer comprising a fluorine-containing polymer with a precursor of the carboxylic acid group and a precursor of the sulfonic acid group between the first layer and the second layer or using a fourth layer comprising a fluorine-containing polymer with a carboxylic acid group precursor and a sulfonic acid group precursor instead of the second layer.

[00344] The method for forming the fourth layer can be a method in which a fluorine-containing polymer with a carboxylic acid group precursor and a fluorine-containing polymer with a sulfonic acid group precursor are separately produced and then mixed or can be a method wherein a monomer with a precursor to the carboxylic acid group and a monomer with a precursor to the sulfonic acid group are copolymerized.

[00345] When the fourth layer is used as a component of the ion exchange membrane, a coextruded film of the first layer and the fourth layer is formed, in addition, the third layer and the second layer are formed separately in films, and the lamination can be performed by the method mentioned above. Alternatively, the three layers of the first layer / fourth layer / second layer can be simultaneously formed into a film by coextrusion.

[00346] In this case, the direction in which the extruded film flows is the MD. As mentioned above, it is possible to form a membrane body containing a fluorine-containing polymer with an ion exchange group in a reinforcement material.

[00347] Additionally, the ion exchange membrane preferably has protruding portions composed of the fluorine-containing polymer with a sulfonic acid group, that is, projections, on the surface side composed of the sulfonic acid layer. As a method for forming such projections, which is not particularly limited, one can also use a known method including forming projections on a resin surface. A specific example of the method is a method of embossing the surface of the membrane body. For example, the above projections can be formed using release paper embossed in advance when the composite film mentioned above, reinforcement material and the like are integrated. In the case where the projections are formed by embossing, the height and density of arrangement of the projections can be controlled by controlling the form of embossing to be transferred (shape of the release paper). (5) Hydrolysis step

[00348] In step (5), a hydrolysis step of the membrane body obtained in step (4) is carried out to convert the precursor of the ion exchange group into an ion exchange group (hydrolysis step).

[00349] In step (5), it is also possible to form dissolution holes in the membrane body by dissolving and removing the sacrifice wires included in the membrane body with acid or alkali. The sacrifice wires can remain in the continuous holes without being completely dissolved and removed. The sacrifice wires that remain in the continuous holes can be dissolved and removed by the electrolyte solution when the ion exchange membrane is subjected to electrolysis.

[00350] The sacrifice wire has solubility in acid or alkali in the production stage of an ion exchange membrane or under an electrolysis environment. The sacrifice wires are eluted to form continuous holes at the corresponding locations.

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[00351] Step (5) can be carried out by immersing the membrane body obtained in step (4) in a hydrolysis solution containing acid or alkali. An example of the hydrolysis solution that can be used is a mixed solution containing KOH and dimethyl sulfoxide (DMSO).

[00352] The mixed solution preferably contains KOH of 2.5 to 4.0 Ne and DMSO of 25 to 35% by weight.

[00353] The temperature for hydrolysis is preferably 70 to 100 ° C. The higher the temperature, the greater the apparent thickness. The temperature is more preferably 75 to 100 ° C.

[00354] The time for hydrolysis is preferably 10 to 120 minutes. The longer the time, the greater the apparent thickness. The time is most preferably 20 to 120 minutes.

[00355] The step of forming continuous holes eluting the sacrificial wire will now be described in more detail. Figures 4 (a) and (b) are schematic views to explain a method for forming the continuous holes in the ion exchange membrane.

[00356] Figures 4 (a) and (b) show the reinforcement wires 52, the sacrifice wires 504a and the continuous holes 504 formed only by the sacrifice wires 504a, omitting the illustration of the other members, such as a body of membrane.

[00357] Firstly, the reinforcement wires 52 constituting reinforcement core materials in the ion exchange membrane and the sacrifice wires 504a to form the continuous holes 504 in the ion exchange membrane are used as interlaced reinforcement materials. Then, in step (5), the sacrifice threads 504a are eluted to form continuous holes 504.

[00358] The above method is simple because the method for interlacing reinforcement wires 52 and sacrifice wires 504a can be adjusted depending on the arrangement of the reinforcement core materials and the continuous holes in the membrane body of the ion exchange membrane.

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[00359] Figure 4 (a) exemplifies the single fabric reinforcement material in which reinforcement threads 52 and sacrifice threads 504a are interwoven along the longitudinal and lateral direction on the paper, and the arrangement of the reinforcement 52 and the sacrifice wires 504a in the reinforcement material may vary as required. (6) Application stage

[00360] In step (6), a coating layer can be formed by preparing a coating liquid containing particles of inorganic material obtained by grinding raw ore or melting raw ore and a binder, applying the coating liquid on the surface of the ion exchange membrane obtained in step (5), and drying of the coating liquid.

[00361] A preferred binder is a binder obtained by hydrolysis of a fluorine-containing polymer with an ion exchange group precursor with an aqueous solution containing dimethylsulfoxide (DMSO) and potassium hydroxide (KOH) and then immersion of the polymer in hydrochloric acid to replace the counter-ion of the ion exchange group with H + (for example, a fluorine-containing polymer with a carboxyl group or a sulfo group). Thus, the polymer is more likely to dissolve in water or ethanol mentioned below, which is preferable.

[00362] This binder is dissolved in a mixed solution of water and ethanol. The volume ratio between water and ethanol is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 2: 1 to 1: 2. The particles of inorganic material are dispersed with a ball mill in the dissolution liquid thus obtained to provide a coating liquid. In this case, it is also possible to adjust the average particle size and the like of the particles by adjusting the time and speed of rotation during dispersion. The preferable amount of the particles of inorganic material and the binder to be mixed is as mentioned above.

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[00363] The concentration of the particles of inorganic material and the binder in the coating liquid is not particularly limited, but a thin-coated liquid is preferable. This allows uniform application to the surface of the ion exchange membrane.

[00364] Additionally, a surfactant can be added to the dispersion when the particles of inorganic material are dispersed. Like the surfactant, nonionic surfactants are preferable and examples of them include HS-210, NS-210, P-210 and E-212 manufactured by NOF CORPORATION.

[00365] The coating liquid obtained is applied to the surface of the ion exchange membrane by spray application or roller coating, thus providing an ion exchange membrane. [Microporous membrane]

[00366] The microporous membrane of the present modality is not particularly limited as long as the membrane can be formed in a laminate with the electrolysis electrode, as mentioned above. Several microporous membranes can be used.

[00367] The porosity of the microporous membrane of the present embodiment is not particularly limited, but it can be from 20 to 90, for example, and is preferably from 30 to 85. The porosity above can be calculated by the following formula: Porosity = (1 - (the weight of the membrane in a dry state) / (the weight calculated from the volume calculated from the thickness, width and length of the membrane and the density of the membrane material)) x 100

[00368] The average pore size of the microporous membrane of the present embodiment is not particularly limited, and can be 0.01 µm to 1 µm, for example, preferably 0.05 µm to 5 µm. Regarding the average pore size, for example, the membrane is cut vertically in the direction of thickness, and the section is observed with an FE-SEM. The size

85/803 pore average can be obtained by measuring the diameter of about 100 pores observed and averaging the measurements.

[00369] The thickness of the microporous membrane of the present embodiment is not particularly limited, and can be from 10 µm to 1000 µm, for example, preferably 50 µm to 600 µm. The above thickness can be measured using a micrometer (manufactured by Mitutoyo Corporation) or similar, for example.

[00370] Specific examples of the microporous membrane as mentioned above include Zirfon Perl UTP 500 manufactured by Agfa (also called Zirfon membrane in the present embodiment) and those described in International Publication No. WO 2013-183584 and International Publication No. WO 2016-203701. [Laminate]

[00371] The laminate of this modality comprises the electrode for electrolysis of the present modality and a membrane or supply conductor in contact with the electrode for electrolysis. The laminate of the present modality, as configured as described above, can improve the work efficiency during the electrode renewal in an electrolyzer and, in addition, it can present an excellent electrolytic performance also after the renovation.

[00372] That is, according to the laminate of this modality, when renewing the electrode, the electrode can be renewed by a job as simple as renewing the membrane, without a complicated job like removing the electrode fixed in the electrolytic cell, and so , work efficiency is noticeably improved.

[00373] In addition, according to the laminate of the present invention, it is possible to maintain the electrolytic performance comparable to that of a new electrode or to improve the electrolytic performance. Even in the case where only one supply conductor is placed in a new cell

86/803 electrolytic (that is, an electrode including no layer of catalyst placed), just attaching the electrode for the electrolysis of this modality to the supply conductor allows the electrode to function. Thus, it may also be possible to significantly reduce or eliminate the catalyst coating.

[00374] The laminate of the present modality can be stored or transported to customers in a state where the laminate is wrapped around a vinyl chloride or similar tube (in a laminated or similar state), making handling notably easier .

[00375] As the supply conductor of the present modality, several substrates mentioned below can be used, such as a degraded electrode (ie, the existing electrode) and an electrode without catalyst coating.

[00376] In the laminate of the present embodiment, the force applied per unit mass-unit area of the electrode for electrolysis in the membrane or feed conductor is preferably 0.08 N / (mg: cm?) Or more, more preferably 0, 1 N / (mg: cm?) Or more, even more preferably 0.14 N / (mg: -em?) Or more, and even more preferably, from the point of view of further facilitating handling in a large size ( for example, a size of 1.5 mx 2.5 m), is 0.2 N / (mg: cm?) or more. The upper limit value is not particularly limited, but is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mg: in?), Even more preferably 1.5 N / (mg: -ecm?), even more preferably 1.2 N / mg: cm? or less, even more preferably 1.20 N / mg: cm? or less. The upper limit value is even more preferably 1.1 N / mg: cm? or less, even more preferably 1.10 N / mgcm? or less, particularly preferably 1.0 N / mg: cm? or less, especially preferably 1.00 N / mg: -cm? or less. [Wrapped body]

87/803

[00377] The rolled body of the present modality includes the electrode for electrolysis of the present modality or the laminate of the present modality. That is, the rolled body of the present modality is obtained by winding the electrode for electrolysis of the present modality or the laminate of the present modality. Reducing the size of the electrode for electrolysis of the present modality or the laminate of the present modality by winding, such as the rolled body of the present modality, can further improve the handling property. [Electrolyser]

[00378] The electrolyzer of the present modality includes the electrode for electrolysis of the present modality. Hereinafter, the case of conducting common salt electrolysis using an ion exchange membrane as the membrane is taken as an example, and an embodiment of the electrolyzer will be described in detail. [Electrolytic cell]

[00379] Figure 5 illustrates a cross-sectional view of an electrolytic cell 1.

[00380] The electrolytic cell 1 comprises an anodic chamber 10, a cathodic chamber 20, a partition wall 30 placed between the anodic chamber 10 and the cathodic chamber 20, an anode 11 placed in the anodic chamber and a cathode 21 placed in the cathodic chamber 20 As required, the electrolytic cell 1 has a substrate 18a and a reverse current absorbent layer 18b formed on the substrate 18a and can comprise a reverse current absorber 18 placed in the cathode chamber. Anode 11 and cathode 21 belonging to electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 comprises the following cathode structure. Cathode structure 40 comprises cathode chamber 20, cathode 21 placed in cathode chamber 20 and reverse current absorber 18 placed in cathode chamber 20, current absorber

Reverse 88/803 18 has substrate 18a and reverse current absorbing layer 18b on substrate 18a, as shown in Figure 9, and cathode 21 and reverse current absorbing layer 18b are electrically connected. The cathodic chamber 20 also has a collector 23, a support 24 supporting the collector and an elastic metal body 22. The elastic metal body 22 is placed between the collector 23 and the cathode 21. The support 24 is placed between the collector 23 and the partition wall 30. The collector 23 is electrically connected to the cathode 21 through the elastic metal body 22. The partition wall 30 is electrically connected to the collector 23 through the support 24. Therefore, the partition wall 30, the support 24, the collector 23, the elastic metal body 22 and the cathode 21 are electrically connected. Cathode 21 and reverse current absorbing layer 18b are electrically connected. Cathode 21 and the reverse current absorbing layer can be directly connected or they can be indirectly connected through the collector, the support, the elastic metal body, the partition wall or the like. The entire surface of cathode 21 is preferably covered with a layer of catalyst for the reduction reaction. The electrical connection form can be a form in which the partition wall 30 and the support 24, the support 24 and the collector 23, and the collector 23 and the elastic metal body 22 are each directly attached and the cathode 21 it is laminated to the elastic metal body 22. Examples of a method for directly affixing these constituent components to each other include welding and the like. Alternatively, the reverse current absorber 18, cathode 21 and collector 23 can be collectively called a cathode structure 40.

[00381] Figure 6 illustrates a cross-sectional view of two electrolytic cells 1 that are adjacent to the electrolyzer 4. Figure 7 shows an electrolyzer 4. Figure 8 shows an assembly step of the electrolyzer 4. As shown in Figure 6, an electrolytic cell 1, a cation exchange membrane 2 and an electrolytic cell 1 are arranged in

89/803 series in the order mentioned. An ion exchange membrane 2 is arranged between the anode chamber of an electrolytic cell 1 between the two adjacent electrolytic cells in the electrolyzer and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent to it are separated by the cation exchange membrane 2. As shown in Figure 7, the electrolyzer 4 is composed of a plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer comprising the plurality of electrolytic cells 1 arranged in series and ion exchange membranes 2, each arranged between adjacent electrolytic cells 1. As shown in Figure 8, electrolyzer 4 is assembled arranging the plurality of cells electrolytics 1 in series through the ion exchange membrane 2 and coupling the cells by means of a pressure device 5.

[00382] Electrolyser 4 has an anodic terminal 7 and a cathodic terminal 6 to be connected to a power supply. Anode 11 of electrolytic cell 1 located at the far end between the plurality of electrolytic cells 1 coupled in series in electrolyzer 4 is electrically connected to anode terminal 7. Cathode 21 of the electrolytic cell located at the opposite end to anode terminal 7 between the plurality of electrolytic cells 1 coupled in series in the electrolyzer 4 is electrically connected to the cathodic terminal 6. The electrical current during electrolysis flows from the side of the anodic terminal 7, through the anode and cathode of each electrolytic cell 1, towards the cathodic terminal 6. At the two ends of the coupled electrolytic cells 1, an electrolytic cell with only one anodic chamber (anode terminal cell) and an electrolytic cell with only one cathodic chamber (cathode terminal cell) can be arranged. In this case, anode terminal 7 is connected to the anode terminal cell, arranged at one end, and cathode terminal 6 is

90/803 connected to the cathode terminal cell, arranged at the other end.

[00383] In the case of electrolytic brine, brine is provided for each anodic chamber 10 and pure water or an aqueous solution of low concentration sodium hydroxide is provided for each cathodic chamber 20. Each liquid is supplied from a supply tube of electrolytic solution (not shown in the Figure), through an electrolytic solution supply hose (not shown in the Figure), for each electrolytic cell 1. The electrolyte solution and electrolysis products are recovered from an electrolyte recovery tube (not shown in the figure). During electrolysis, the sodium ions in the brine migrate from the anode chamber 10 of the electrolytic cell 1, through the ion exchange membrane 2, to the cathode chamber 20 of the adjacent electrolytic cell 1. Thus, the electric current during electrolysis flows in the direction wherein electrolytic cells 1 are coupled in series. That is, the electric current flows, through the cation exchange membrane 2, from the anodic chamber 10 towards the cathodic chamber 20. As the brine is electrolyzed, chlorine gas is generated on the anode side 11, and sodium hydroxide (solute ) and hydrogen gas are generated on the cathode side

21. (Anodic chamber)

[00384] Anodic chamber 10 has anode 11 or the anode supply conductor 11. When the electrode for the electrolysis of the present mode is inserted on the anode side, 11 serves as the anode supply conductor. When the electrode for electrolysis of the present modality is not inserted on the anode side, 11 serves as an anode. The anodic chamber 10 has an electrolytic solution supply unit on the anode side that provides an electrolytic solution to the anodic chamber 10, a baffle plate that is arranged above the anode side electrolytic solution supply unit to be substantially parallel or oblique to the partition wall 30, and a liquid and gas separation unit on the anode side arranged above the baffle to separate the gas from the electrolytic solution including the mixed gas. (Anode)

[00385] When the electrode for electrolysis of the present modality is not inserted on the side of the anode, anode 11 is provided in the frame of anodic chamber 10. As anode 11, a metal electrode such as the so-called DSA (R) can be used . DSA is an electrode that includes a titanium substrate whose surface is covered with an oxide that contains ruthenium, iridium and titanium as components.

[00386] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Anode feed conductor)

[00387] When the electrode for electrolysis of the present modality is inserted on the anode side, the anode 11 feeder conductor is provided in the anode chamber 10 frame. As the anode 11 feeder conductor, a metal electrode can be used , such as the so-called DSA (R), and titanium without catalyst coating can also be used. Alternatively, DSA with a thinner catalyst coating can also be used. In addition, a used anode can also be used.

[00388] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Anode side electrolyte solution supply unit)

[00389] The electrode solution supply unit on the anode side, which supplies the electrolyte solution to the anode chamber 10, is connected to the electrolyte solution supply tube. The unit of

92/803 supply of electrolytic solution on the anode side is preferably arranged below the anode chamber 10. As the supply unit of electrolytic solution on the anode side, for example, a tube can be used on the surface from which orifice portions are formed. (dispersion tube) and the like. Such a tube is most preferably arranged along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell. This tube is connected to an electrolytic solution supply tube (liquid supply nozzle) that supplies the electrolytic solution to the electrolytic cell 1. The electrolyte solution supplied from the liquid supply nozzle is transported with a tube into the electrolytic cell 1 and supplied from the orifice portions provided on the surface of the tube into the anodic chamber 10. The arrangement of the tube along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell is preferable because the electrolyte solution can be uniformly supplied into the anodic chamber

10. (Liquid and gas separation unit on the anode side)

[00390] The liquid and gas separation unit on the anode side is preferably arranged above the baffle plate. The liquid and gas separation unit on the anode side has the function of separating the produced gas such as chlorine gas from the electrolytic solution during electrolysis. Unless otherwise specified, above means the upper direction in electrolytic cell 1 in Figure 5, and below means the lower direction in electrolytic cell 1 in Figure 5.

[00391] During electrolysis, the produced gas generated in electrolytic cell 1 and the electrolytic solution form a mixed phase (mixed gas-liquid phase), which is then emitted out of the system. Subsequently, pressure fluctuations within the electrolytic cell 1 cause vibration, which can result in physical damage to the ion exchange membrane. In order to avoid this event, the electrolytic cell 1 of the present modality is preferably

93/803 provided with a liquid and gas separation unit on the anode side to separate the gas from the liquid. The liquid and gas separation unit on the anode side is preferably provided with an anti-foam plate to eliminate bubbles. When the flow of the mixed gas-liquid phase passes through the antifoam plate, the bubbles burst, thus allowing the electrolyte solution and the gas to be separated. As a result, vibration during electrolysis can be avoided. (Baffle plate)

[00392] The baffle plate is preferably arranged above the electrolyte solution supply unit on the anode side and arranged substantially in parallel or obliquely to the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. When the deflector plate is provided, it is possible to make the electrolyte solution (brine or similar) circulate internally in the anodic chamber 10 to thus make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged in such a way as to separate the space in the vicinity of anode 11 from the space near the partition wall 30. From such a point of view, the baffle plate is preferably placed so as to be opposite the surface of anode 11 and the surface of the dividing wall 30. In the space next to the anode divided by the deflector plate, as the electrolysis progresses, the concentration of the electrolytic solution (brine concentration) is reduced and the gas produced, such as chlorine gas is generated. This results in a difference in specific gas-liquid gravity between the space near anode 11 and the space near the dividing wall 30 divided by the deflector plate. By using the difference, it is possible to promote the internal circulation of the electrolytic solution in the anodic chamber 10 to thus make the distribution of concentration of the electrolytic solution in the anodic chamber 10 more uniform.

[00393] Although not shown in Figure 5, a collector can be

94/803 additionally provided inside the anodic chamber 10. The material and configuration of such a collector can be the same as the collector of the cathodic chamber mentioned below. In anode chamber 10, anode 11 per se can also serve as a collector. (Partition wall)

[00394] The partition wall 30 is arranged between the anode chamber 10 and the cathode chamber 20. The partition wall 30 can be called a separator, and the anode chamber 10 and the cathode chamber 20 are divided by the partition wall 30. As the wall partition 30, one known as electrolysis separator can be used, and an example of this includes a partition wall formed by welding a plate comprising nickel next to the cathode and a plate comprising titanium beside the anode. (Cathodic chamber)

[00395] In the cathodic chamber 20, when the electrode for electrolysis of the present modality is inserted on the side of the cathode, 21 serves as a supply conductor for the cathode. When the electrode for electrolysis of the present modality is not inserted on the cathode side, 21 serves as a cathode. When a reverse current absorber is included, the cathode or cathode supply conductor 21 is electrically connected to the reverse current absorber. The cathode chamber 20, similarly to the anode chamber 10, preferably has an electrolytic solution supply unit on the cathode side and a liquid and gas separation unit on the cathode side. Among the components that make up the cathodic chamber 20, components similar to those that make up the anode chamber 10 will not be described. (Cathode)

[00396] When the electrode for electrolysis of the present modality is not inserted on the side of the cathode, a cathode 21 is provided in the frame of the cathodic chamber 20. The cathode 21 preferably has a nickel substrate and a

95/803 layer of catalyst covering the nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include metals such as Ru, C, Si, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, alloy galvanizing, composite dispersion / galvanizing, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Cathode 21 can be subjected to a reduction treatment as needed. As the cathode 21 substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[00397] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Cathode supply conductor)

[00398] When the electrode for electrolysis of the present modality is inserted in the cathode side, a cathode 21 conductor is provided in the cathode chamber 20 frame. The cathode 21 catheter can be covered with a catalytic component. The catalytic component can be a component that is originally used as the cathode and remains. Examples of the catalyst layer components include metals such as Ru, C, S1, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh , Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, I, Gd, Tb, Dy , Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / plating

96/803 composite, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. As the cathode 21 feed conductor substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[00399] As the feeder conductor 21, nickel, nickel alloys and nickel or galvanized iron with no catalyst coating can be used.

[00400] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Reverse current absorbing layer)

[00401] A material with a less noble redox potential than the element's redox potential for the catalyst layer mentioned above can be selected as a material for the reverse current absorbing layer. Examples of it include nickel and iron. (Collector)

[00402] The cathodic chamber 20 preferably comprises the collector

23. Collector 23 improves the efficiency of the current collection. In the present embodiment, the collector 23 is a porous plate and is preferably arranged substantially parallel to the surface of the cathode 21.

[00403] The collector 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. Collector 23 can be a mixture, alloy or composite oxide of these metals. The collector 23 can have any shape, as long as the shape allows the function of the collector and can have a plate or network shape. (Elastic metal body)

[00404] Place the elastic metal body 22 between the collector 23 and the

97/803 cathode 21 presses each cathode 21 of the plurality of electrolytic cells 1 connected in series to the ion exchange membrane 2 to reduce the distance between each anode 11 and each cathode 21. Then, it is possible to reduce the voltage to be applied entirely through the plurality of electrolytic cells 1 connected in series. Reducing the voltage reduces energy consumption. With the elastic metal body 22 in place, the pressure caused by the elastic metal body 22 allows the electrolysis electrode to be held steadily in place when the laminate including the electrolysis electrode according to the present invention is placed in the electrolytic cell.

[00405] As the elastic metal body 22, spring members such as spiral springs and coils and damping mats can be used. As the elastic metal body 22, a suitable one can be used appropriately, taking into account a tension to pressure the ion exchange membrane and the like. The elastic metal body 22 can be provided on the surface of the collector 23 on the side of the cathode chamber 20 or it can be provided on the surface of the partition wall on the side of the anode chamber 10. Both chambers are normally divided in such a way that the cathode chamber 20 it becomes smaller than the anodic chamber 10. Thus, from the point of view of the strength of the frame and the like, the elastic metal body 22 is preferably provided between the collector 23 and the cathode 21 in the anodic chamber

20. The elastic metal body 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. (Support)

[00406] The cathodic chamber 20 preferably comprises the support 24 that electrically connects the collector 23 to the partition wall 30. This can achieve an efficient current flow.

[00407] The support 24 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. The support 24 can take any form as long as the support can support the

98/803 collector 23 and can have a rod, plate or network shape. The support 24 has a plate shape, for example. A plurality of supports 24 is arranged between the partition wall 30 and the collector 23. The plurality of supports 24 are aligned in such a way that their surfaces are in parallel with each other. The supports 24 are arranged substantially perpendicular to the partition wall 30 and the collector 23. (Gasket on the anode side and gasket on the cathode side)

[00408] The anode-side gasket is preferably arranged on the surface of the structure that constitutes the anode chamber 10. The cathode-side gasket is preferably arranged on the surface of the structure that constitutes the cathodic chamber 20. The electrolytic cells are connected to each other others such that the anode-side gasket included in an electrolytic cell and the cathode-side gasket of an electrolytic cell adjacent to the cell sandwich the ion exchange membrane 2 (see Figures 5 and 6). These gaskets can make the connection points airtight when the plurality of electrolytic cells 1 is connected in series through the ion exchange membrane 2.

[00409] The gaskets form a seal between the ion exchange membrane and the electrolytic cells. Specific examples of gaskets include picture frame rubber sheets, in the center of which a hole portion is formed. Gaskets are required to be resistant to corrosive electrolyte solutions or gas produced and to be usable for a long period. Thus, with regard to chemical resistance and hardness, vulcanized products and products cross-linked with ethylene-propylene-diene rubber peroxide (EPDM rubber) and ethylene-propylene rubber (EPM rubber) are normally used as gaskets. Alternatively, gaskets of which the region to be in contact with liquid (liquid contact portion) with a fluorine-containing resin such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers

99/803 can be used as needed. Such gaskets may have an orifice portion so as not to inhibit the flow of the electrolyte solution, and the shape of the orifice portion is not particularly limited. For example, a picture frame gasket is affixed with an adhesive or similar along the peripheral edge of each hole portion of the anodic chamber frame that constitutes the anodic chamber 10 or the cathodic chamber frame that constitutes the cathodic chamber 20. So, for example, in the case where the two electrolytic cells 1 are connected via the ion exchange membrane 2 (see Figure 6), each electrolytic cell 1 to which the gasket is attached must be tightened via the ion exchange membrane 2. This Tightening can prevent the electrolyte solution, alkali metal hydroxide, chlorine gas, hydrogen gas and the like, generated from electrolysis, from escaping from electrolytic cells 1. (Ion exchange membrane 2)

[00410] The ion exchange membrane 2 is as described in the section of the ion exchange membrane described above. (Water electrolysis)

[00411] The electrolyser of the present modality, like an electrolyser in the case of water electrolysis, has a configuration in which the ion exchange membrane in an electrolyser for use in the case of common salt electrolysis mentioned above is replaced by a microporous membrane. The raw material to be supplied, which is water, is different from that for the electrolyser in the case of electrolysis of the common salt mentioned above. As for the other components, components similar to those of the electrolyser in the case of electrolysis of common salt can also be used in the electrolyser in the case of water electrolysis. Since chlorine gas is generated in the anodic chamber in the case of common salt electrolysis, titanium is used as the material in the anodic chamber, but in the case of water electrolysis, only oxygen gas is generated in the anodic chamber. Thus, a material identical to that of the cathode chamber can be

100/803 used. An example of this is nickel. For the anode coating, the catalyst coating for oxygen generation is suitable. Examples of the catalyst coating include metals, oxides and hydroxides of the metals of the platinum group and metals of the transition metal group. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used. <Second modality>

[00412] Here, a second embodiment of the present invention will be described in detail with reference to Figures 22 to 42. [Laminate]

[00413] A laminate of the second modality (hereinafter, in the section of <Second modality>, simply called “the present modality”) comprises an electrolyte electrode and a membrane or feed conductor in contact with the electrolyte electrode, where a force applied per unit mass-unit area of the electrode for electrolysis in the membrane or in the supply conductor is less than 1.5 N / mg: cm ?. The laminate of the present modality, as configured as described above, can improve the work efficiency during the electrode renewal in an electrolyzer and, in addition, it can present an excellent electrolytic performance also after the renovation.

[00414] That is, according to the laminate of the present modality, when renewing the electrode, the electrode can be renewed by a job as simple as renewing the membrane, without a complicated job like removing the existing electrode fixed in the electrolytic cell, and thus, work efficiency is noticeably improved.

[00415] Furthermore, according to the laminate of the present invention, it is possible to maintain or improve the electrolytic performance of a new electrode. Thus, the electrode attached to a new conventional electrolytic cell and serving as an anode and / or cathode is only needed to serve

101/803 as a supply conductor. Thus, it may also be possible to significantly reduce or eliminate the catalyst coating.

[00416] The laminate of the present modality can be stored or transported to customers in a state where the laminate is wrapped around a vinyl chloride or similar tube (in a laminated or similar state), making handling notably easier .

[00417] As the supply conductor of the present modality, several substrates mentioned below can be used, such as a degraded electrode (ie, the existing electrode) and an electrode without catalyst coating.

[00418] The laminate of the present embodiment can partially have a fixed portion as long as the laminate has the configuration described above. That is, in the case where the laminate of the present modality has a fixed portion, a portion that does not have fixation is subjected to measurement, and the resulting force applied per unit mass of electrode area for electrolysis must be less than 1.5 N / mg: cm ?. [Electrode for electrolysis]

[00419] The electrolyte electrode of the present modality has a force applied per unit mass-unit area of less than 1.5 N / mg: one hundred, preferably 1.2 N / mg: cm? or less, more preferably 1.20 N / mg-cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a supply conductor (a degraded electrode and an uncoated electrode) catalyst) and the like. The strength is more preferably 1.1 N / mg: ecm? or less, more preferably 1.10 N / mg: cm? or less, even more preferably 1.0 N / mg: cm? or less, even more preferably 1.00 N / mg: cm? or less.

[00420] From the point of view of further improving performance

102/803 electrolytic, the strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: in?) Or more, even more preferably 0.1 N / mg: cm? or more, even more preferably 0.14 N / (mg: cm?) or more. By force it is even more preferably 0.2 N / (mg: cm?) Or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 m x 2.5 m).

[00421] The applied force described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness, arithmetic mean surface roughness and the like, for example. More specifically, for example, a higher opening ratio tends to lead to a lower applied force, and a lower opening ratio tends to lead to a higher applied force.

[00422] Is the mass per unit area preferably 48 mg / cm? or less, more preferably 30 mg / cm? or less, even more preferably 20 mg / cm? or less from the point of view of allowing a good handling property, having a good adhesive strength for a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a conductive conductor without catalyst coating and economy, and in addition it is preferably 15 mg / cm? or less from a comprehensive point of view including handling, grip and economy properties. The lower limit value is not particularly limited, but is in the order of 1 mg / cm?, For example.

[00423] The mass per unit area described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness and the like, for example. More specifically, for example, when the thickness is constant, a larger opening ratio tends to lead to a smaller mass per unit area, and a smaller opening ratio tends to lead to a mass per unit area greater.

[00424] The applied force can be measured by methods (1) or (ii)

103/803 described below, which are as described in the Examples, specifically. As for the applied force, the value obtained by measuring the method (1) (also called “the applied force (1)”) and the value obtained by measuring the method (11) (also called “the applied force (2) ”) Can be the same or different, and any of the values is less than 1.5 N / (mg: in?). [Method (i)]

[00425] A nickel plate obtained by stripping processing with grain size alumina 320 (thickness 1.2 mm, 200 mm square), an ion exchange membrane that is obtained by the application of particles of inorganic material and a binder on both surfaces of a perfluorocarbon polymer membrane into which an ion exchange group (170 square mm, the detail of the ion exchange membrane referred to here is as described in the Examples) and an electrode sample (130 mm square) ) are rolled in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. The arithmetic mean roughness of the surface (Ra) of the nickel plate after blasting treatment is 0.5 to 0.8 µm. The specific method for calculating the arithmetic mean surface roughness (Ra) is as described in the Examples.

[00426] Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the charge when the electrode sample is raised by 10 mm in a vertical direction is measured. This measurement is repeated three times and the average value is calculated.

[00427] This average value is divided by the area of the overlapping portion of the electrode sample and the ion exchange membrane and the mass of the portion that overlaps the ion exchange membrane in the electrode sample to calculate the

104/803 force applied per unit mass-unit area (1) (N / mg-ecm?).

[00428] The force applied per unit mass-unit area (1) obtained by method (1) is less than 1.5 N / mg: -cn ?, preferably 1.2 N / mg: cm? or less, more preferably 1.20 N / mg: cm? or less, even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg-ecm? or less, even more preferably 1.0 N / mg-cm? or less, even more preferably 1.00 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The strength is preferably greater than 0.005 N / (mg: cm?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg: cm?) Or more of the point view of further improving electrolytic performance, and furthermore, it is even more preferably 0.14 N / (mg: cm?), even more preferably 0.2 N / (mg: cm?) or more from the point of view to further facilitate handling in a large size (for example, a size of 1.5 mx 2.5 m).

[00429] When the electrode for electrolysis of the present modality satisfies the applied force (1), the electrode can be integrated with a membrane such as an ion exchange membrane and a microporous membrane or a supply conductor, for example, and used ( that is, as a laminate). Thus, when renewing the electrode, the work of replacing the cathode and anode fixed to the electrolytic cell by a method such as welding is eliminated, and the work efficiency is noticeably improved. Additionally, by using the electrode for the electrolysis of the present modality as a laminate integrated with the ion exchange membrane, microporous membrane, or feed conductor, it is possible to make the electrolytic performance comparable or superior to that of a new electrode.

[00430] When sending a new electrolytic cell, an electrode fixed in

105/803 an electrolytic cell has been subjected to the catalyst coating conventionally. Since only the combination of an electrode without a catalyst coating with the electrolyte electrode of the present modality can allow the electrode to function as an electrode, it is possible to remarkably reduce or eliminate the production step and the quantity of the catalyst for the coating of catalyst. A conventional electrode whose catalyst coating is noticeably reduced or eliminated can be electrically connected to the electrolyte electrode of the present modality and allowed to serve as a supply conductor for the passage of an electric current. [Method (ii)]

[00431] A nickel plate obtained by stripping processing with alumina of grain size 320 (thickness 1.2 mm, 200 mm square, a nickel plate similar to that of method (1) above) and an electrode sample ( 130 mm square) is laminated in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the load when the electrode sample is raised by 10 mm in a vertical direction it is measured. This measurement is repeated three times and the average value is calculated.

[00432] This average value is divided by the area of the overlapping portion of the electrode sample and the nickel plate and the mass of the electrode sample in the portion that overlaps the nickel plate to calculate the adhesive force per unit mass-unit of area (2) (N / mg: -cm?).

[00433] The force applied per unit mass-unit area (2) obtained by method (ii) is less than 1.5 N / mg-em ?, preferably 1.2

106/803 N / mg: cm? or less, more preferably 1.20 N / mg: cm? or less, even more preferably 1.1 N / mg-cm? or less, even more preferably 1.10 N / mg-em? or less, even more preferably 1.0 N / mg-cm? or less, even more preferably 1.00 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The strength is preferably greater than 0.005 N / (mg: cm?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg: cm?) Or more of the point to further improve electrolytic performance, and it is even more preferably 0.14 N / (mg: cm?) or more from the point of view of further facilitating handling at a large size (for example, a size of 1 , 5 mx2.5 Mm).

[00434] The electrolyte electrode of the present modality, if it satisfies the applied force (2), can be stored or transported to customers in a state where the electrode is wrapped around a vinyl chloride tube or similar (in a laminated or similar state), making handling remarkably easier. By attaching the electrolyte electrode of the present modality to an existing electrode degraded to provide a laminate, it is possible to make the electrolytic performance comparable or superior to that of a new electrode.

[00435] From the point of view that the electrolyte electrode of the present modality, if it is an electrode with a wide region of elastic deformation, can provide a better handling property and has a better adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a feed conductor with no catalyst coating, and the like, the electrode thickness for electrolysis is preferably 315 µm or less, more

107/803 preferably 220 µm or less, more preferably 170 µm or less, even more preferably 150 µm or less, particularly preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 one or less. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 um or more, more preferably 5 um or more for practical reasons, more preferably 20 um or more. In the present modality, “having a wide region of elastic deformation” means that when an electrolysis electrode is wound to form a wound body, it is unlikely that distortion derived from the winding will occur after the wound state is released. The thickness of the electrolysis electrode refers, when a catalyst layer mentioned below is included, to the total thickness of both the electrolysis electrode substrate and the catalyst layer.

[00436] The electrolyte electrode of the present embodiment preferably includes an electrode electrode substrate and a catalyst layer. The substrate thickness for the electrolysis electrode (gauge thickness) is, but is not particularly limited to, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less , even more preferably 125 µm or less, even more preferably 120 µm or less, even more preferably 100 µm or less from the point of view of enabling a good handling property to be provided, having a good adhesive strength to a membrane, such as a ion exchange membrane and a microporous membrane, an electrode

108/803 degraded (feeder conductor), and an electrode (feeder conductor) without catalyst coating, be able to be properly laminated on a roll and folded satisfactorily, facilitating handling in a large size (for example, a size of 1.5 mx 2.5 Mm), and it is even more preferably 50 µm or less from the point of view of a handling and economy property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[00437] In the present embodiment, a liquid is preferably interposed between the membrane such as an ion exchange membrane and a microporous membrane and the electrode, or the metallic porous plate or metallic plate (i.e., feed conductor) such as an electrode existing degraded electrode without catalyst coating and electrode for electrolysis. Like the liquid, any liquid, such as water and organic solvents, can be used as long as the liquid generates a surface tension. The greater the surface tension of the liquid, the greater the force applied between the membrane and the electrolysis electrode or the porous metal plate or the metal plate and electrode for electrolysis. Thus, a liquid with a higher surface tension is preferred. Examples of the liquid include the following (the numerical value in parentheses is the surface tension of the liquid at 20ºC): hexane (20.44 mN / m), acetone (23.30 mN / m), methanol (24.00 mN / m ), ethanol (24.05 mN / m), ethylene glycol (50.21 mN / m) and water (72.76 mN / m).

[00438] A liquid with a high surface tension allows the membrane and electrode for electrolysis or the porous metal plate or metal plate (feed conductor) and the electrode for electrolysis to be integrated (to be a laminate) to facilitate renovation the electrode. The liquid between the membrane and the electrolysis electrode or the porous metal plate or metal plate (supply conductor) and the electrode for

109/803 electrolysis can be present in an amount such that both adhere to each other by surface tension. As a result, after the laminate is placed in an electrolytic cell, the liquid, if mixed in the electrolytic solution, does not affect the electrolysis itself due to the small amount of the liquid.

[00439] From a practical point of view, a liquid with a surface tension of 24 mN / m to 80 mN / m, such as ethanol, ethylene glycol and water, is preferably used as the liquid. Particularly preferred is water or an aqueous alkaline solution prepared by dissolving caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate or the like in water. Alternatively, the surface tension can be adjusted by allowing these liquids to contain a surfactant. When a surfactant is contained, the adhesion between the membrane and the electrolysis electrode or the metallic porous plate or the metallic plate (feed conductor) and the electrolysis electrode varies to allow the handling property to be adjusted. The surfactant is not particularly limited and ionic and non-ionic surfactants can be used.

[00440] The proportion measured by the following method (2) of the electrode for electrolysis of the present embodiment is not particularly limited, but it is preferably 90% or more, more preferably 92% or more from the point of view of allowing a good handling property is provided and has a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and more preferably 95% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (2)]

110/803

[00441] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 280 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[00442] The proportion measured by the following method (3) of the electrode for electrolysis of the present embodiment is not particularly limited, but is preferably 75% or more, more preferably 80% or more from the point of view of allowing a good handling property be provided, have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating and can be properly laminated in a roll is satisfactorily folded, and is more preferably 90% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (3)]

[00443] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 145 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are

111/803 sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of an area of a portion in which the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[00444] The electrode for electrolysis of the present modality has a porous structure and an opening ratio or void ratio of 5 to 90% or less from the point of view of enabling a good handling property, having a good adhesive force to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and to prevent gas buildup from being generated during electrolysis, although not particularly limited . The opening ratio is more preferably 10 to 80% or less, more preferably 20 to 75%.

[00445] The opening ratio is a proportion of the opening portions per unit volume. The calculation method may differ depending on whether the opening portions in submicron size are considered or that only visible openings are considered. In the present embodiment, a volume V was calculated from the values of the thickness of the gauge, width and length of the electrode and, in addition, a weight W was measured to thereby calculate an aperture ratio A using the following formula.

A = (1- (W / (YV xp)) x 100

[00446] p is the density of the electrode material (g / cm?). For example, p nickel is 8.908 g / cm ”, and p titanium is 4.506 g / cm ?. The opening ratio is appropriately adjusted by changing the area of metal to be drilled per unit area in the case of perforated metal, changing the SW (short diameter), LW (long diameter) and feed values in the case of expanded metal, changing the metal fiber line diameter and mesh number in the case of mesh, changing the pattern of a photoresist to be used in the case of electroforming, changing the diameter of the metal fiber and fiber density in the case of non-woven fabric, changing the mold to form voids in the case of foamed metal or similar.

[00447] The value obtained by measuring by the following method (A) of the electrode for electrolysis in the present embodiment is preferably 40 mm or less, more preferably 29 mm or less, even more preferably 10 mm or less, even more preferably 6.5 mm or less from the point of view of manipulation property. The specific measurement method is as described in the Examples. [Method (A)]

[00448] Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, a sample obtained by laminating the ion exchange membrane and the electrolysis electrode is rolled up and fixed on a curved surface of a core material made of polyvinyl chloride with an external diameter of 32 mm and left to rest for 6 hours; thereafter, when the electrolysis electrode is separated from the sample and placed on a flat plate, heights in a vertical direction on both edges of the electrolysis electrode L, and L7 are measured, and an average value is used as a value of measurement.

[00449] In the electrolysis electrode in the present embodiment, the ventilation resistance is preferably 24 kPa-s / m or less when the electrolysis electrode has a size of 50 mm x 50 mm, the ventilation resistance being measured under conditions of temperature of 24ºC, the relative humidity of 32%, a piston speed of 0.2 cm / s and a ventilation volume of 0.4 cc / in? / s (hereinafter, also called “measurement condition 1” ) (hereinafter, also called “ventilation resistance 1”). Higher ventilation resistance means that air is unlikely to flow and refers to a state of high density. In this state, the electrolysis product remains on the electrode and is more unlikely

113/803 that the reaction substrate diffuses inside the electrode, and thus the electrolytic performance (like the voltage) tends to deteriorate. The concentration on the membrane surface tends to increase. Specifically, the caustic concentration increases at the cathode surface, and the supply of brine tends to decrease at the anode surface. As a result, the product accumulates in high concentration at the interface at which the membrane is in contact with the electrode. This build-up causes damage to the membrane and also tends to increase the tension and damage to the membrane on the cathode surface and damage to the membrane on the anode surface. In the present embodiment, in order to avoid these defects, the ventilation resistance is preferably set at 24kPa-s / m or less. From a point of view similar to the above, the ventilation resistance is more preferably less than 0.19 kPa-s / m, more preferably 0.15 kPa-s / m or less, even more preferably 0.07 kPa-s / m or less.

[00450] In the present mode, when the ventilation resistance is greater than a certain value, the NaOH generated in the electrode tends to accumulate at the interface between the electrode and the membrane to result in a high concentration in the case of the cathode, and the supply brine tends to decrease to make the brine concentration lower in the case of the anode. In order to avoid damage to the membrane that could be caused by such an accumulation, the ventilation resistance is preferably less than 0.19 kPa-s / m, more preferably 0.15 kPas / m or less, even more preferably 0.07 kPa -s / m or less.

[00451] In contrast, when the ventilation resistance is low, the electrode area is reduced and the electrolysis area is reduced. Thus, electrolytic performance (like voltage) tends to deteriorate. When the ventilation resistance is zero, the supply conductor functions as the electrode, as no electrolysis electrode is provided and the electrolytic performance (like the voltage) tends to deteriorate noticeably. From that

114/803 point of view, a preferable lower limit value identified as the ventilation resistance | it is not particularly limited, but is preferably greater than 0 kPa-s / m, more preferably 0.0001 kPa-s / m or more, even more preferably 0.001 kPa-s / m or more.

[00452] When the ventilation resistance 1 is 0.07 kKPa-s / m or less, sufficient measurement accuracy may not be achieved because of the measurement method for it. From this point of view, it is also possible to evaluate an electrolysis electrode with ventilation resistance 1 of 0.07 kPa-s / m or less by means of a ventilation resistance (hereinafter, also called “ventilation resistance 2 ”) obtained by the following measurement method (hereinafter, also called“ measurement condition 2 ”). That is, ventilation resistance 2 is a measured ventilation resistance, when the electrolysis electrode has a size of 50 mm x 50 mm, under conditions of temperature of 24ºC, the relative humidity of 32%, a piston speed of 2 cm / s and a ventilation volume of 4 cc / in? / s.

[00453] Specific methods for measuring ventilation resistances 1 and 2 are described in the Examples.

[00454] Ventilation resistors | and 2 may be within the range described above, appropriately adjusting an aperture ratio, electrode thickness and the like, for example. More specifically, for example, when the thickness is constant, a higher opening ratio tends to lead to ventilation resistances | and 2 smaller, and a smaller opening ratio tends to lead to greater ventilation resistances 1 and 2.

[00455] In the electrode for electrolysis of the present modality, as mentioned above, the force applied per unit of mass-unit area of the electrode for electrolysis in the membrane or in the supply conductor is less than 1.5 N / mg-ecm ?. In this way, the electrode for electrolysis of the present modality touches with a moderate adhesive force on the membrane or

115/803 supply conductor (for example, the anode or cathode in the electrolyzer) to allow a laminate to be formed with the membrane or supply conductor. That is, it is not necessary to make the membrane or the supply conductor adhere firmly to the electrode for electrolysis by a complicated method, such as thermal compression. The laminate is formed only by a relatively weak force, for example, a surface tension derived from the moisture contained in the membrane, such as an ion exchange membrane and a microporous membrane, and thus a laminate of any scale can be easily formed. In addition, such a laminate has excellent electrolytic performance. Thus, the laminate of the present embodiment is suitable for electrolysis applications, and can be particularly preferably used for applications related to members of electrolysers and renewal of members.

[00456] Hereinafter, an aspect of the electrode for electrolysis of the present modality will be described.

[00457] The electrolysis electrode according to the present embodiment preferably includes a substrate for electrolysis electrode and a layer of catalyst. The catalyst layer can be composed of a plurality of layers, as shown below, or it can be a single layer configuration.

[00458] As shown in Figure 22, an electrolysis electrode 100 according to the present embodiment includes an electrode substrate for electrolysis 10 and a pair of first layers 20 with which both surfaces of the electrode substrate for electrolysis 10 are covered. . The entire electrolyte electrode substrate 10 is preferably covered with the first 20 layers. This coating is likely to improve the activity of the catalyst and the durability of the electrolysis electrode. A first layer 20 can be laminated only on one surface of the electrode substrate for electrolysis 10.

116/803

[00459] Also shown in Figure 22, the surfaces of the first layers 20 can be covered with the second layers 30. The first entire layers 20 are preferably covered by the second layers 30. Alternatively, a second layer 30 can be laminated only one surface of the first layer 20. (Electrode substrate for electrolysis)

[00460] As an electrode substrate for electrolysis 10, for example, nickel, nickel alloys, stainless steel or valve metals including titanium can be used, although not limited to them. The substrate 10 preferably contains at least one element selected from nickel (Ni) and titanium (Ti).

[00461] When stainless steel is used in an aqueous alkaline solution of high concentration, iron and chromium are eluted and the electrical conductivity of stainless steel is about one tenth that of nickel. In view of the above, a substrate containing nickel (Ni) is preferable as a substrate for the electrolysis electrode.

[00462] Alternatively, when the electrode substrate for electrolysis 10 is used in a high concentration saline solution close to saturation under an atmosphere in which chlorine gas is generated, the substrate material for electrode 10 is also preferably titanium with high corrosion resistance.

[00463] The shape of the electrode substrate for electrolysis 10 is not particularly limited, and a shape suitable for the purpose can be selected. As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. Among these, a perforated metal or expanded metal is preferable. Electroforming is a technique for producing a thin metal film with a precise pattern using photolithography and

117/803 electroplating in combination. It is a method that includes the formation of a pattern on a substrate with a photoresist and electroplating of the portion not protected by the resistance to provide a thin metal film.

[00464] As for the shape of the substrate for the electrolysis electrode, an appropriate specification depends on the distance between the anode and the cathode in the electrolyzer. In the case where the distance between the anode and the cathode is finite, a form of expanded metal or perforated metal can be used, and in the case of a so-called zero-interstitial electrolyzer, in which the ion exchange membrane is in contact with the electrode, a woven mesh produced by fine knitted threads, wire mesh, foamy metal, non-woven metallic fabric, expanded metal, perforated metal, porous metal foil and the like can be used, although not limited to it.

[00465] Examples of the electrode substrate for electrolysis 10 include a porous metallic foil, a wire mesh, a nonwoven metal fabric, a perforated metal, an expanded metal and a foamy metal.

[00466] As plate material before being processed into a perforated metal or expanded metal, laminated plate materials and electrolytic sheets are preferred. An electrolytic sheet is preferably still subjected to a galvanizing treatment using the same element as its base material, such as after-treatment, to thereby form roughness and one or both surfaces.

[00467] The thickness of the electrode substrate for electrolysis 10 is, as mentioned above, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less, even more preferably 125 one or less, even more preferably 120 µm or less, even more preferably 100 µm or less, and even more preferably 50 µm or less from the point of view of a handling and economical property. The lower limit value is not particularly limited, but it is 1 um, for

118/803 example, preferably 5 µm, more preferably 15 µm.

[00468] In the electrode substrate for electrolysis, the residual stress during processing is preferably relaxed by annealing the electrode substrate for electrolysis in an oxidizing atmosphere. It is preferable to form roughness using a steel grid, alumina powder or similar on the surface of the electrode substrate for electrolysis followed by an acid treatment to increase the surface area of the electrode, in order to improve the adhesion to a catalyst layer with which the surface is covered. Alternatively, it is preferable to give a galvanizing treatment using the same element as the substrate to increase the surface area.

[00469] In order to place the first layer 20 in close contact with the surface of the electrolyte electrode substrate 10, the electrode electrode substrate 10 is preferably subjected to a treatment to increase the surface area. Examples of the treatment of increasing the surface area include a pickling treatment using a cut wire, steel grid, alumina grid or similar, an acid treatment using sulfuric acid or hydrochloric acid, and a galvanizing treatment using the same element as the of the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 µm to 50 µm, more preferably 0.1 to 10 µm, even more preferably 0.1 to 8 µm.

[00470] Next, a case will be described in which the electrode for electrolysis of the present modality is used as an anode for electrolysis of common salt. (First layer)

[00471] In Figure 22, a first layer 20 as a catalyst layer contains at least one of the ruthenium oxides, iridium oxides and titanium oxides. Examples of ruthenium oxide include RuO; Examples of iridium oxide include IrO ,. Examples of titanium oxide include TiO ,. THE

119/803 first layer 20 preferably contains two oxides: a ruthenium oxide and a titanium oxide or three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide. This makes the first layer 20 more stable and further improves adhesion with the second layer 30.

[00472] When the first layer 20 contains two oxides: a ruthenium oxide and a titanium oxide, the first layer 20 preferably contains 1 to 9 mol, more preferably 1 to 4 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition ratio of the two oxides in this range, the electrode for electrolysis 100 has excellent durability.

[00473] When the first layer 20 contains three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide, the first layer 20 preferably contains 0.2 to 3 mol, more preferably 0.3 to 2.5 mol of iridium oxide based on 1 mol of ruthenium oxide contained in the first layer 20. The first layer 20 preferably contains 0.3 to 8 mol, more preferably 1 to 7 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition of the three oxides in this range, the electrode for electrolysis 100 has excellent durability.

[00474] When the first layer 20 contains at least two of a ruthenium oxide, an iridium oxide and a titanium oxide, these oxides preferably form a solid solution. The formation of the solid oxide solution allows the electrolysis electrode 100 to have excellent durability.

[00475] In addition to the compositions described above, oxides of various compositions can be used provided that at least one oxide of a ruthenium oxide, an iridium oxide and titanium oxide is contained. For example, an oxide coating called DSA (R), which contains ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum and the like, can

120/803 be used as the first layer 20.

[00476] The first layer 20 need not be a single layer and can include a plurality of layers. For example, the first layer 20 can include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 µm, more preferably 0.1 to 8 µm. (Second layer)

[00477] The second layer 30 preferably contains ruthenium and titanium. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[00478] The second layer 30 preferably contains a palladium oxide, a solid solution of a palladium and platinum oxide, or an alloy of palladium and platinum. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[00479] A second thicker layer 30 can maintain the electrolytic performance for a longer period, but from an economic point of view, the thickness is preferably 0.05 to 3 µm.

[00480] Next, a case will be described in which the electrode for electrolysis of the present modality is used as a cathode for electrolysis of common salt. (First layer)

[00481] Examples of components of the first layer 20 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[00482] The first layer 20 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal.

121/803

[00483] When the first layer 20 contains at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides, and alloys containing a platinum group metal, the metals of the platinum group platinum, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal preferably contain at least one platinum group metal of platinum, palladium, rhodium, ruthenium and iridium.

[00484] Like the platinum group metal, platinum is preferably contained.

[00485] Like the metal oxide of the platinum group, a ruthenium oxide is preferably contained.

[00486] Like the metal hydroxide of the platinum group, a ruthenium hydroxide is preferably contained.

[00487] Like the platinum group metal alloy, a platinum alloy with nickel, iron and cobalt is preferably contained.

[00488] Furthermore, as needed, an oxide or hydroxide of a lanthanide element is preferably contained as a second component. This allows the electrolysis electrode 100 to have excellent durability.

[00489] As the oxide or hydroxide of a lanthanide element, at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium and dysprosium is preferably contained.

[00490] Furthermore, as needed, an oxide or hydroxide of a transition metal is preferably contained as a third component.

[00491] The addition of the third component allows the electrolysis electrode 100 to have greater durability and the electrolysis voltage to be reduced.

122/803

[00492] Examples of a preferable combination include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + Platinum + Palladium, Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + cobalt, ruthenium + samarium + zinc, ruthenium + samarium + gallium, ruthenium + samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + nickel el + palladium, platinum + nickel + ruthenium, platinum and nickel alloys, platinum and cobalt alloys, and platinum and iron alloys.

[00493] When platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal are not contained, the main component of the catalyst is preferably the nickel element.

[00494] At least one of the nickel metals, oxides and hydroxides is preferably contained.

[00495] As the second component, a transition metal can be added. As the second component to be added, at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper and carbon is preferably contained.

[00496] Examples of a preferable combination include nickel + tin, nickel + titanium, nickel + molybdenum and nickel + cobalt.

[00497] As required, an intermediate layer can be placed between the first layer 20 and the electrode substrate for electrolysis

123/803

10. The durability of the electrolysis electrode 100 can be improved by placing the intermediate layer.

[00498] As the intermediate layer, those having affinity for both the first layer 20 and the electrode substrate for electrolysis 10 are preferred. As the intermediate layer, nickel oxides, platinum group metals, metal oxides are preferable of the platinum group and metal hydroxides of the platinum group. The intermediate layer can be formed by applying and cooking a solution containing a component that forms the intermediate layer. Alternatively, a surface oxide layer can also be formed by subjecting a substrate to a heat treatment at a temperature of 300 to 600ºC in an air atmosphere. In addition, the layer can be formed by a known method, such as a thermal spray method and an ion galvanizing method. (Second layer)

[00499] Examples of components of the first layer 30 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[00500] The first layer 30 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal. Examples of a preferable combination of elements contained in the second layer include the combinations listed for the first layer. The combination of the first layer and the second layer can be a combination in which the compositions are the same and the composition reasons are different or can be a combination of different compositions.

124/803

[00501] As the thickness of the catalyst layer, the total thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 µm to 20 µm. With a thickness of 0.01 µm or more, the catalyst layer can sufficiently serve as the catalyst. With a thickness of 20 µm or less, it is possible to form a robust catalyst layer that is unlikely to fall off the substrate. The thickness is more preferably 0.05 µm to 15 µm. The thickness is more preferably 0.1 µm to 10 µm. The thickness is even more preferably 0.2 µm to 8 µm.

[00502] The electrode electrode thickness, that is, the total thickness of the electrolysis electrode substrate and the catalyst layer is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, even more preferably 150 µm or less, particularly preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less with respect to the electrode manipulation property for electrolysis. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably 20 µm or more. The thickness of the electrode can be determined by measurement with a digital thickness gauge (Mitutoyo Corporation, minimum scale 0.001 mm). The thickness of the electrolysis electrode substrate can be measured in the same way as in the case of the electrolysis electrode. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode for electrolysis.

125/803 (Method to produce electrode for electrolysis)

[00503] Next, an embodiment of the method for producing the electrolysis electrode 100 will be described in detail.

[00504] In the present embodiment, the electrolysis electrode 100 can be produced by forming the first layer 20, preferably the second layer 30, on the electrode electrode substrate by a method such as cooking a coating film under an oxygen atmosphere ( pyrolysis) or ion galvanizing, galvanizing or thermal spraying. The production method of the present embodiment as mentioned can achieve a high productivity of the electrode for electrolysis 100. Specifically, a catalyst layer is formed on the electrode substrate for electrolysis by an application step to apply a coating liquid containing a catalyst, a drying step to dry the coating liquid and a pyrolysis step to perform pyrolysis. Pyrolysis here means that a metal salt that is to be a precursor is decomposed by heating into a metal or metal oxide and a gaseous substance. The decomposition product depends on the metal species to be used, the type of salt and the atmosphere under which pyrolysis is carried out, and many metals tend to form oxides in an oxidizing atmosphere. In an industrial electrode production process, pyrolysis is usually carried out in air, and a metal oxide or metal hydroxide is formed in many cases. (Formation of the first anode layer) (Application stage)

[00505] The first layer 20 is obtained by applying a solution in which at least one metallic salt of ruthenium, iridium and titanium is dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the liquid coating in the presence of oxygen. The ruthenium, iridium and titanium content in the first coating liquid is substantially equivalent to that of the first layer 20.

126/803

[00506] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[00507] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[00508] After being applied to the electrode substrate for electrolysis 100, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the point

127/803 view of the electrode productivity, 3 to 60 minutes is preferable, 5 to 20 minutes is more preferable.

[00509] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the second layer)

[00510] The second layer 30, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second liquid of first layer 20 and then pyrolyzing the coating liquid in the presence of oxygen. (Formation of the first cathode layer by the pyrolysis method) (Application stage)

[00511] The first layer 20 is obtained by applying a solution in which metal salts of various combinations are dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the coating liquid in the presence of oxygen. The metal content in the first coating liquid is substantially equivalent to that of the first layer 20.

[00512] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably at

128/803 range from 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating.

[00513] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[00514] After being applied to the electrode substrate for electrolysis 10, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[00515] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20.

129/803 (Formation of the intermediate layer)

[00516] The intermediate layer, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound or a platinum compound (second coating liquid) to the substrate and then pyrolyzing the coating liquid in the presence of oxygen. Alternatively, an intermediate layer of nickel oxide can be formed on the surface of the substrate just by heating the substrate, without applying a solution on it. (Formation of the first cathode layer by ion galvanizing)

[00517] The first layer 20 can also be formed by ion plating.

[00518] An example includes a method in which the substrate is fixed in a chamber and the metal ruthenium target is irradiated with an electron beam. Evaporated metallic ruthenium particles are positively charged to the plasma in the chamber to deposit on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and deposits of ruthenium as ruthenium oxide in the substrate. (Formation of the first cathode layer by galvanizing)

[00519] The first layer 20 can also be formed by a method of galvanization.

[00520] For example, when the substrate is used as a cathode and subjected to electrolytic galvanization in an electrolytic solution containing nickel and tin, nickel and tin alloy galvanization can be formed. (Formation of the first cathode layer by thermal spray)

[00521] The first layer 20 can also be formed by thermal spraying.

[00522] As an example, the nickel oxide particles sprayed by plasma on the substrate can form a catalyst layer in which the metallic nickel and nickel oxide are mixed.

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[00523] The electrolyte electrode of the present modality can be integrated with a membrane, such as an ion exchange membrane and a microporous membrane, and used. Thus, the electrode can be used as an electrode integrated into the membrane. Then, the work of replacing the cathode and anode in electrode renewal is eliminated, and the work efficiency is noticeably improved.

[00524] The electrode integrated into the membrane, such as an ion exchange membrane and a microporous membrane, can make the electrolytic performance comparable or superior to that of a new electrode.

[00525] In the following, the ion exchange membrane will be described in detail. [Ion exchange membrane]

[00526] The ion exchange membrane has a membrane body containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and a coating layer provided on at least one surface of the membrane body. The coating layer contains particles of inorganic material and a binder, and the specific surface area of the coating layer is 0.1 to 10 m / g. In the ion exchange membrane that has such a structure, the influence of the gas generated during electrolysis on the electrolytic performance is small, and the stable electrolytic performance can be presented.

[00527] The membrane of a perfluorocarbon polymer into which an ion exchange group is introduced described above includes a layer of sulfonic acid with an ion exchange group derived from a sulfo group (a group represented by -SO3 ', here also called a "sulfonic acid group") or a layer of carboxylic acid with an ion exchange group derived from a carboxyl group (a group represented by -CO ;, here also called a "carboxylic acid group"). From the point of view of strength and dimensional stability, reinforcement core materials are preferably included.

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[00528] The particles of inorganic material and binder will be described in detail in the coating layer description section below.

[00529] Figure 23 illustrates a schematic cross-sectional view showing an ion exchange membrane modality. An ion exchange membrane | it has a membrane body 10 containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and coating layers 11a and 11b formed on both surfaces of the membrane body 10.

[00530] In the ion exchange membrane 1, the membrane body 10 comprises a layer of sulfonic acid 3 with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called an “acid group sulfonic ”) and a layer of carboxylic acid 2 with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a“ carboxylic acid group ”), and the core materials of reinforcement 4 intensifies strength and dimensional stability. The ion exchange membrane 1, comprising the sulfonic acid layer 3 and the carboxylic acid layer 2, is suitably used as an anion exchange membrane.

[00531] The ion exchange membrane can include the sulfonic acid layer or the carboxylic acid layer. The ion exchange membrane may not necessarily be reinforced by reinforcement core materials, and the arrangement of the reinforcement core materials is not limited to the example in Figure 23. (Membrane body)

[00532] First, the membrane body 10 which constitutes the ion exchange membrane 1 will be described.

[00533] The membrane body 10 must be one that has the function of selectively allowing cations to permeate and comprises a hydrocarbon polymer or a fluorine-containing polymer with a group of

132/803 ion exchange. Its configuration and material are not particularly limited, and the preferred ones can be selected appropriately.

[00534] The hydrocarbon polymer or fluorine-containing polymer with an ion exchange group in the membrane body 10 can be obtained from a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group precursor capable of forming a group of ion exchange by hydrolysis or similar. Specifically, for example, after a polymer comprising a fluorinated hydrocarbon backbone that has, as a pendant side chain, a group convertible into an ion exchange group by hydrolysis or similar (precursor to the ion exchange group), and is processable by melting (hereinafter called "fluorine-containing polymer (a)" in some cases), be used to prepare a precursor to the membrane body 10, the membrane body 10 can be obtained by converting the precursor to the ion exchange group in an ion exchange group.

[00535] The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. The fluorine-containing polymer (a) can also be produced by homopolymerizing a monomer selected from any of the following first group, the following second group and the following third group.

[00536] Examples of the monomers of the first group include vinyl fluoride compounds. Examples of the vinyl fluoride compounds include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and perfluoralkyl vinyl ethers. Particularly when the ion exchange membrane is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoro monomer, and a perfluoro monomer selected from the group consisting of

133/803 tetrafluoroethylene, hexafluoropropylene and perfluoralkyl vinyl ethers.

[00537] Examples of the monomers of the second group include vinyl compounds with a functional group convertible into an ion exchange group of the carboxylic acid type (carboxylic acid group). Examples of vinyl compounds with a functional group convertible to a carboxylic acid group include monomers represented by CF = CF (OCF; CYF); - O (CZF) .- COOR, where s represents an integer from 0 to 2, t represents an integer from 1 to 12, Y and Z each independently represent F or CF; 3, and R represents a lower alkyl group (a lower alkyl group is an alkyl group with 1 to 3 carbon atoms, for example).

[00538] Among them, compounds represented by CF; = CF (OCF; CYF), - O (CF2) n-COOR are preferable. Where n represents an integer from 0 to 2, m represents an integer from 1 to 4, Y represents F or CF; 3, and R represents CH3, CoHs, or C3H ;.

[00539] When the ion exchange membrane is used as a cation exchange membrane for alkaline electrolysis, a perfluoro compound is preferably at least used as the monomer, but the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis and, therefore, the alkyl group (R) need not be a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[00540] Of the monomers above, the monomers shown below are more preferable than the monomers of the second group: CF; = CFOCF; -CF (CF;) OCF; COOCH ;, CF; = CFOCF; CF (CF3) O (CF3) -COOCH ;, CF; = CF [OCF3-CF (CF3) 12O (CF>) - COOCH ;, CF; = CFOCF; CF (CF3) O (CF3); 5COOCH ;, CF3 = CFO (CF3); COOCH; , and CF; = CFO (CF;); COOCH ;.

[00541] Examples of the monomers of the third group include

134/803 vinyl compounds with a functional group convertible into an ion exchange group of the sulfone type (sulfonic acid group). As vinyl compounds with a functional group convertible to a sulfonic acid group, for example, monomers represented by CF; = CFO-X-CF; -SO, F are preferred, where X represents a perfluoroalkylene group. Specific examples of these include the monomers represented below: CF; = CFOCFCFSOF, CF; = CFOCFCF (CF3) OCF3CF3SO »xF, CF; = CFOCF: CF (CF3) OCF; CFCF3SO) F, CF3 = CF (CF3); SOF, CF3 = CFO [CF; CF (CF3) O] 1CF.CFE3SOF, and CF. = CFOCF; CF (CF; OCF3) OCF; CFSO »xF.

[00542] Among them, CF = CFOCF; CF (CF3) OCF; CF; CFSO0.F = and CF; = CFOCF; CF (CF3) OCF; CF3SO, F are more preferable.

[00543] The copolymer obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, particularly a general polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, a polymerization reaction can be carried out in the presence of a radical polymerization initiator such as a perfluorocarbon peroxide or an azo compound under the conditions of a temperature of 0 to 200ºC and a pressure of 0, 1 to 20 MPa using an inert solvent such as a perfluorohydrocarbon or a chlorofluorocarbon.

[00544] In the above copolymerization, the type of combination of the above monomers and their proportion are not particularly limited and are selected and determined depending on the type and quantity of the desired functional group to be imparted to the fluorine-containing polymer to be obtained. For example, when a fluorine-containing polymer containing only one carboxylic acid group is formed, at least one monomer must be selected

135/803 of each of the first group and the second group described above and copolymerized. In addition, when a fluorine-containing polymer containing only one sulfonic acid group is formed, at least one monomer must be selected from each of the first group and the third group and copolymerized. In addition, when a fluorine-containing polymer with a carboxylic acid group and a sulfonic acid group is formed, at least one monomer must be selected from each of the first group, the second group and the third group described above and copolymerized. In that case, the target fluorine-containing polymer can also be obtained by separately preparing a copolymer comprising the monomers of the first group and the second group described above and a copolymer comprising the monomers of the first group and the third group described above, and then mixing the copolymers. The mixing ratio of the monomers is not particularly limited, and when the number of functional groups per unit of polymer is increased, the proportion of the selected monomers from the second and third groups described above should be increased.

[00545] The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, more preferably 0.6 to 1.5 mg equivalent / g. The total ion exchange capacity here refers to the exchange group equivalent per unit weight of the dry resin and can be measured by neutralization titration or the like.

[00546] In the membrane body 10 of the ion exchange membrane 1, a layer of sulfonic acid 3 containing a polymer containing fluorine with a group of sulfonic acid and a layer of carboxylic acid 2 containing a polymer containing fluorine with a group of carboxylic acid are laminated. By providing the membrane body 10 with this layer configuration, selective permeability for cations, such as sodium fons, can

136/803 be further improved.

[00547] The ion exchange membrane | it is arranged in an electrolyzer in such a way that, generally, the sulfonic acid layer 3 is located on the anode side of the electrolyzer and the carboxylic acid layer 2 is located on the cathode side of the electrolyzer.

[00548] The sulfonic acid layer 3 is preferably made of a material with low electrical resistance and has a membrane thickness greater than that of the carboxylic acid layer 2 from the point of view of the membrane resistance. The membrane thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, more preferably 3 to 15 times that of the carboxylic acid layer 2.

[00549] The carboxylic acid layer 2 preferably has high anion exclusion properties, even if it has a small membrane thickness. The anion exclusion properties here refer to the property of trying to prevent anion intrusion and permeation into and through the ion exchange membrane 1. In order to increase the anion exclusion properties, it is effective to lay out a layer of carboxylic acid with a small ion exchange capacity to the sulfonic acid layer.

[00550] As the fluorine-containing polymer for use in the sulfonic acid layer 3, a polymer obtained using CF; = CFOCF; CF (CF3) OCF; CF3SO, 3F as the monomer of the third group is preferred.

[00551] As the fluorine-containing polymer for use in the carboxylic acid-2 layer, a polymer obtained using CF; = CFOCF; CF (CF3) O (CF;); COOCH; as the monomer of the second group. (Coating layer)

[00552] The ion exchange membrane has a coating layer on at least one surface of the membrane body. As shown in Figure 23, on the ion exchange membrane 1, the coating layers 11a and

137/803 11b are formed on both surfaces of the membrane body 10.

[00553] The coating layers contain particles of inorganic material and a binder.

[00554] The average particle size of the particles of inorganic material is preferably 0.90 µm or more. When the average particle size of the particles of inorganic material is 0.90 µm or more, the durability to impurities is greatly improved, in addition to the gas display. That is, increasing the average particle size of the particles of inorganic material, as well as satisfying the value of the specific surface area mentioned above, can achieve a particularly remarkable effect. Irregular inorganic material particles are preferable because the average particle size and specific surface area, as above, are satisfied. Particles of inorganic material obtained by melting and particles of inorganic material obtained by grinding ore can be used. Particles of inorganic material obtained by grinding raw ore can preferably be used.

[00555] The average particle size of particles of inorganic material can be 2 µm or less. When the average particle size of the particles of inorganic material is 2 µm or less, it is possible to avoid damage to the membrane due to the particles of inorganic material. The average particle size of the inorganic material particle is more preferably 0.90 to 1.2 µm.

[00556] Here, the average particle size can be measured by a particle size analyzer (“SALD2200”, SHIMADZU CORPORATION).

[00557] Particles of inorganic material preferably have irregular shapes. Such shapes further improve resistance to impurities. Particles of inorganic material preferably have a wide particle size distribution.

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[00558] Particles of inorganic material preferably contain at least one inorganic material selected from the group consisting of oxides of Group IV elements in the Periodic Table, nitrides of Group IV elements in the Periodic Table and carbides of Group IV elements in Periodic table. From the point of view of durability, the zirconium oxide particle is more preferable.

[00559] The particles of inorganic material are preferably particles of inorganic material produced by grinding the raw ore of the particles of inorganic material or particles of inorganic material, such as spherical particles with a uniform diameter, obtained by purification by melting the raw ore of the particles of inorganic material.

[00560] Examples of means for grinding raw ore include, but are not particularly limited to, ball mills, ball mills, colloid mills, taper mills, disc mills, roller mills, grain mills, hammer mills, granules, VSI mills, Wiley mills, laminators and jet mills. After grinding, the particles are preferably washed. As a washing method, the particles are preferably treated with acid. This treatment can reduce impurities, such as iron affixed to the surface of particles of inorganic material.

[00561] The coating layer preferably contains a binder. The binder is a component that forms the coating layers retaining particles of inorganic material on the surface of the ion exchange membrane. The binder preferably contains a polymer containing fluorine from the point of view of durability to the electrolytic solution and electrolysis products.

[00562] As the binder, a fluorine-containing polymer with a carboxylic acid group or a sulfonic acid group is preferred, from the point of view of durability to the electrolyte solution and products of electrolysis and adhesion

139/803 on the surface of the ion exchange membrane. When a coating layer is provided on a layer containing a fluorine-containing polymer with a sulfonic acid group (sulfonic acid layer), a fluorine-containing polymer with a sulfonic acid group is still preferably used as the binder of the coating layer. Alternatively, when a coating layer is provided on a layer containing a fluorine-containing polymer with a carboxylic acid group (carboxylic acid layer), a fluorine-containing polymer with a carboxylic acid group is still preferably used as the binder of the coating layer.

[00563] In the coating layer, the content of the particles of inorganic material is preferably 40 to 90% by weight, more preferably 50 to 90% by weight. The content of the binder is preferably 10 to 60% by weight, more preferably 10 to 50% by weight.

[00564] The density of distribution of the coating layer on the ion exchange membrane is preferably 0.05 to 2 mg per 1 µm. When the ion exchange membrane has roughness on its surface, the distribution density of the coating layer is preferably 0.5 to 2 mg per 1 in °.

[00565] As the method for forming the coating layer, which is not particularly limited, a known method can be used. An example is a method that includes spraying or the like of a coating liquid obtained by dispersing particles of inorganic material in a solution containing a binder. (Reinforcement core materials)

[00566] The ion exchange membrane preferably has reinforcement core materials arranged within the membrane body.

[00567] The reinforcement core materials are members that enhance the resistance and dimensional stability of the ion exchange membrane. When arranging the reinforcement core materials within the body of the

140/803 membrane, particularly the expansion and contraction of the ion exchange membrane can be controlled in the desired range. Such an ion exchange membrane does not expand or contract more than necessary during electrolysis and the like and can maintain excellent dimensional stability in the long run.

[00568] The configuration of the reinforcement core materials is not particularly limited and, for example, the reinforcement core materials can be formed by spinning threads called reinforcement threads. The reinforcement threads here refer to threads that are members that make up the reinforcement core materials, can provide the desired dimensional stability and mechanical resistance to the ion exchange membrane and can be stably present in the ion exchange membrane. By using the reinforcement core materials obtained by spinning such reinforcement threads, better dimensional stability and mechanical resistance to the ion exchange membrane can be provided.

[00569] The material of the reinforcement core materials and the reinforcement yarns used for them is not particularly limited, but is preferably a material resistant to acids, alkalis, etc., and a fiber comprising a fluorine-containing polymer is preferable because the long-term thermal resistance and chemical resistance are required.

[00570] Examples of the fluorine-containing polymer to be used in the reinforcement core materials include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers, tetrafluoroethylene-ethylene (ETFE) copolymers, tetrafluoroethylene copolymers, hexetluoroethylene copolymers, hexetluoroethylene copolymers. trifluorochlorethylene-ethylene and polymers of vinylidene fluoride (PVDF). Among these, fibers comprising polytetrafluoroethylene are preferably used from the point of view of heat resistance and chemical resistance.

[00571] The wire diameter of the reinforcement wires used for the materials

141/803 of the reinforcement core is not particularly limited, but is preferably 20 to 300 deniers, more preferably 50 to 250 deniers. The weave density (tissue count per unit length) is preferably 5 to 50 / inch. The shape of the reinforcement core materials is not particularly limited, for example, a woven fabric, a non-woven fabric and a knitted fabric are used, but it is preferably in the form of a woven fabric. The thickness of the woven fabric to be used is preferably 30 to 250 µm, more preferably 30 to 150 µm.

[00572] As woven fabric or knitted fabric, monofilaments, multifilaments, or yarns thereof, a slit yarn, or the like, and various types of weaving methods, such as single weft, leno weft, knitted weft, weft, can be used cord and sirsaca, can be used.

[00573] The weft and the arrangement of the reinforcement core materials in the membrane body are not particularly limited, and the preferred arrangement can be suitably provided considering the size and shape of the ion exchange membrane, desired physical properties for the membrane of ion exchange, the environment of use and the like.

[00574] For example, the reinforcement core materials can be arranged along a predetermined direction of the membrane body, but from the point of view of dimensional stability, it is preferable that the reinforcement core materials are arranged over a predetermined first direction, and other reinforcement core materials along a second direction substantially perpendicular to the first direction. By arranging the plurality of reinforcement core materials substantially orthogonally within the membrane body, it is possible to provide better dimensional stability and mechanical strength in several directions. For example, the arrangement in which reinforcement core materials arranged along the longitudinal direction (warp yarns) and reinforcement core materials arranged along the transverse direction (weft threads) are woven.

142/803 on the surface side of the membrane body is preferred. The arrangement is most preferably in the form of driven flat weft and woven fabric allowing the warps and wefts to alternately move between themselves and underneath each other, smooth weft in which two warps are woven into wefts while twisted, weft in a driven and woven basket by insertion in two or more warps arranged in parallel, wefts of the same or similar number, from the point of view of dimensional stability, mechanical resistance and ease of production.

[00575] It is preferred that, in particular, the reinforcement core materials are arranged along both directions, the MD (Machine Direction) and TD (Transversal Direction) of the ion exchange membrane. In other words, the reinforcement core materials are preferably single woven in MD and TD. Here, MD refers to the direction in which the membrane body and various core materials (for example, the reinforcement core materials, reinforcement wires and sacrificial wires described below) are transported in a production step of ion exchange membrane described later (flow direction) and TD refers to the direction substantially perpendicular to the MD. The threads woven along the MD are called MD threads, and the threads woven along the TD are called TD threads. Typically, the ion exchange membrane used for electrolysis is rectangular, and in many cases, the longitudinal direction is the MD, and the width direction is the TD. By weaving the reinforcement core materials that are MD yarns and the reinforcement core materials that are TD yarns, it is possible to provide better dimensional stability and mechanical strength in many directions.

[00576] The range of arrangement of the reinforcement core materials is not particularly limited, and the preferred arrangement can be adequately provided considering the desired physical properties for the ion exchange membrane, the environment of use and the like.

[00577] The orifice ratio for reinforcement core materials is not

143/803 is particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The orifice ratio is preferably 30% or more from the point of view of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the point of view of the mechanical strength of the ion exchange membrane.

[00578] The orifice ratio for reinforcement core materials refers to a ratio of a total area of a surface through which substances such as fons (an electrolyte solution and cations contained in it (for example, sodium fons)) they can pass (B) to the area of one of the surfaces of the membrane body (A) (B / A). The total surface area through which substances such as fons can pass (B) can refer to the total areas of regions in which the ion exchange membrane, cations, an electrolyte solution and the like are not blocked by the reinforcement core materials and similar substances contained in the ion exchange membrane.

[00579] Figure 24 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane. Figure 24, in which a portion of the ion exchange membrane is enlarged, shows only the arrangement of the reinforcement core materials 21 and 22 in the regions, omitting the illustration of the other members.

[00580] By subtracting the total area of the reinforcement core materials (C) from the area of the region surrounded by the reinforcement core materials 21 arranged along the longitudinal direction and the reinforcement core materials 22 arranged along the transverse direction, the region including the area of the reinforcement core materials (A), the total area of regions through which substances such as phons can pass (B) in the area of the region described above (A) can be obtained. That is, the orifice ratio can be determined by the following formula (1): Orifice ratio = (B) / (A) = ((A) - (O0)) / (A) ... (D

144/803

[00581] Among the materials of the reinforcement core, a particularly preferred form are stranded yarns or highly oriented monofilaments comprising PTFE from the point of view of chemical resistance and heat resistance. Specifically, reinforcement core materials forming a single web in which 50 to 300 denier ribbon yarns obtained by cutting a high strength porous sheet comprising PTFE into a ribbon form, or highly oriented 50 to 300 denier monofilaments are used comprising PTFE and having a weave density of 10 to 50 threads or monofilaments / inch and having a thickness in the range of 50 to 100 µm are more preferred. The orifice ratio of an ion exchange membrane comprising such reinforcement core materials is still preferably 60% or more.

[00582] Examples of the shape of the reinforcement threads include round threads and ribbon threads. (Continuous holes)

[00583] The ion exchange membrane preferably has continuous holes inside the membrane body.

[00584] Continuous holes refer to holes that can be flow paths for fons generated in electrolysis and an electrolyte solution. The continuous holes, which are tubular holes formed inside the membrane body, are formed by dissolving the sacrificial core materials (or sacrificial threads) described below. The shape, diameter or the like of the continuous holes can be controlled by selecting the shape or diameter of the sacrificial core materials (sacrificial threads).

[00585] Forming the continuous holes inside the ion exchange membrane can guarantee the mobility of an electrolyte solution in electrolysis. The shape of the continuous holes is not particularly limited, but it may be the shape of the sacrificial core materials to be used for forming the continuous holes according to the production method described below.

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[00586] The continuous holes are preferably formed so that they pass alternately through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcement core materials. With this structure, in a portion in which continuous holes are formed on the cathode side of the reinforcement core materials, ions (eg sodium fons) carried by the electrolyte solution with which the continuous holes are filled can also flow on the side of the cathode of the reinforcement core materials. As a result, the flow of cations is not interrupted and, therefore, it is possible to further reduce the electrical resistance of the ion exchange membrane.

[00587] The continuous holes can be formed along only a predetermined direction of the membrane body that constitutes the ion exchange membrane, but are preferably formed both in the longitudinal and in the transversal direction of the membrane body from the point of view of presenting a more stable electrolytic performance. [Production method]

[00588] A suitable example of a method for producing an ion exchange membrane includes a method including the following steps (1) to (6): step (1): the step of producing a fluorine-containing polymer with an exchange group ionic or an ion exchange group precursor capable of forming an ion exchange group by hydrolysis, step (2): the weaving step of at least a plurality of reinforcement core materials, as required, and sacrificial yarns with a proprietary dissolving in an acid or an alkali, and forming continuous holes to obtain a reinforcement material in which the sacrifice wires are arranged between the reinforcement core materials adjacent to each other, step (3): the formation step in a fluorine-containing polymer film above with an ion exchange group or a precursor to the group

146/803 ion exchange capable of forming an ion exchange group by hydrolysis, step (4): the step of embedding the reinforcement materials above, as required, in the above film to obtain a membrane body within which the materials reinforcement are arranged, step (5): the hydrolysis step of the membrane body obtained in step (4) (hydrolysis step), and step (6): the step of providing a coating layer on the obtained membrane body in step (5) (application step).

[00589] Next, each of the steps will be described in detail. Step (1): Fluorine-containing polymer production step

[00590] In step (1), the raw material monomers described in the first group for the third group above are used to produce a fluorine-containing polymer. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the raw material monomers must be adjusted in the production of the fluorine-containing polymer that forms the layers. Step (2): Reinforcement materials production step

[00591] The reinforcement material is a woven fabric obtained by weaving reinforcement threads or the like. The reinforcement material is embedded in the membrane to form reinforcement core materials. When an ion exchange membrane with continuous holes is formed, the sacrificial threads are additionally woven into the reinforcement material. The amount of the sacrificial yarns contained in that case is preferably 10 to 80% by weight, more preferably 30 to 70% by weight based on the entire reinforcement material. Weaving the sacrificial yarns can also prevent the yarn from slipping the reinforcement core materials.

[00592] As sacrificial threads, which have solubility in the membrane production stage or under an electrolysis environment, rayon, polyethylene terephthalate (PET), cellulose, polyamide and the like are used. They are also

147/803 preferred monofilaments or multifilaments having a thickness of 20 to 50 deniers and comprising polyvinyl alcohol and the like.

[00593] In step (2), the orifice ratio, the arrangement of continuous and similar holes can be controlled by adjusting the arrangement of the reinforcement core materials and the sacrifice wires. Step (3): Film forming step

[00594] In step (3), the fluorine-containing polymer obtained in step (1) is formed into a film using an extruder. The film can be a single layer configuration, a two layer configuration of a sulfonic acid layer and a layer of carboxylic acid, as mentioned above, or a multilayer configuration of three layers or more.

[00595] Examples of the film-forming method include the following: a method in which a fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are formed separately in films; and a method in which the fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are coextruded into a composite film.

[00596] The number of each film can be more than one. Coextrusion of different films is preferred because of their contribution to an increase in adhesive strength at the interface. Stage (4): Stage of obtaining the membrane body

[00597] In step (4), the reinforcement material obtained in step (2) is embedded in the film obtained in step (3) to provide a membrane body including the reinforcement material therein.

[00598] Preferable examples of the method for forming a membrane body include (1) a method in which a fluorine-containing polymer with

148/803 a carboxylic acid group precursor (for example, carboxylate functional group) (hereinafter, a layer comprising the same is called the first layer) located on the cathode side and a fluorine-containing polymer with a sulfonic acid group precursor (for example, sulfonyl fluoride functional group) (hereinafter, a layer comprising the same is called a second layer) are formed in a film by a coextrusion method and, using a heat source and a vacuum source as If necessary, a reinforcement material and the second layer / first layer composite film are laminated in that order on heat-resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer is exposed. it melts while the air between each layer is evacuated under reduced pressure; and (11) a method in which, in addition to the composite film of the second layer / first layer, a fluorine-containing polymer with a precursor to the sulfonic acid group is formed separately in a film (the third layer) in advance and, using a heat source and a vacuum source as needed, the third layer film, the reinforcement core materials and the composite film comprising the second layer / first layer are laminated in that order on heat resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated under reduced pressure.

[00599] The coextrusion of the first layer and the second layer contributes to an increase in the adhesive strength at the interface.

[00600] The method including integration under reduced pressure is characterized by making the third layer in the reinforcement material thicker than that of the pressure method of applying pressure. In addition, since the reinforcement material is attached to the internal surface of the

149/803 membrane, the method has a property of sufficiently retaining the mechanical resistance of the ion exchange membrane.

[00601] The lamination variations described here are exemplary, and coextrusion can be performed after a preferred lamination pattern (for example, the combination of layers) is appropriately selected considering the desired layer configuration of the membrane body and physical properties, and the like.

[00602] In order to further improve the electrical properties of the ion exchange membrane, it is also possible to additionally interpose a fourth layer comprising a fluorine-containing polymer with a precursor of the carboxylic acid group and a precursor of the sulfonic acid group between the first layer and the second layer or using a fourth layer comprising a fluorine-containing polymer with a carboxylic acid group precursor and a sulfonic acid group precursor instead of the second layer.

[00603] The method for forming the fourth layer may be a method in which a fluorine-containing polymer with a carboxylic acid group precursor and a fluorine-containing polymer with a sulfonic acid group precursor are separately produced and then mixed or can be a method wherein a monomer with a precursor to the carboxylic acid group and a monomer with a precursor to the sulfonic acid group are copolymerized.

[00604] When the fourth layer is used as a component of the ion exchange membrane, a coextruded film of the first layer and the fourth layer is formed, in addition, the third layer and the second layer are formed separately in films, and the lamination can be performed by the method mentioned above. Alternatively, the three layers of the first layer / fourth layer / second layer can be simultaneously formed into a film by coextrusion.

150/803

[00605] In this case, the direction in which the extruded film flows is the MD. As mentioned above, it is possible to form a membrane body containing a fluorine-containing polymer with an ion exchange group in a reinforcement material.

[00606] Additionally, the ion exchange membrane preferably has protruding portions composed of the fluorine-containing polymer with a sulfonic acid group, that is, projections, on the surface side composed of the sulfonic acid layer. As a method for forming such projections, which is not particularly limited, one can also use a known method including forming projections on a resin surface. A specific example of the method is a method of embossing the surface of the membrane body. For example, the above projections can be formed using release paper embossed in advance when the composite film mentioned above, reinforcement material and the like are integrated. In the case where the projections are formed by embossing, the height and density of arrangement of the projections can be controlled by controlling the form of embossing to be transferred (shape of the release paper). (5) Hydrolysis step

[00607] In step (5), a hydrolysis step of the membrane body obtained in step (4) is carried out to convert the precursor of the ion exchange group into an ion exchange group (hydrolysis step).

[00608] In step (5), it is also possible to form dissolution holes in the membrane body by dissolving and removing the sacrifice wires included in the membrane body with acid or alkali. The sacrifice wires can remain in the continuous holes without being completely dissolved and removed. The sacrifice wires that remain in the continuous holes can be dissolved and removed by the electrolyte solution when the ion exchange membrane is subjected to electrolysis.

151/803

[00609] The sacrifice wire has solubility in acid or alkali in the production stage of an ion exchange membrane or under an electrolysis environment. The sacrifice wires are eluted to form continuous holes at the corresponding locations.

[00610] Step (5) can be carried out by immersing the membrane body obtained in step (4) in a hydrolysis solution containing acid or alkali. An example of the hydrolysis solution that can be used is a mixed solution containing KOH and dimethyl sulfoxide (DMSO). [0061 1] The mixed solution preferably contains 2.5 to 4.0 N KOH and 25 to 35% by weight DMSO.

[00612] The temperature for hydrolysis is preferably 70 to 100 ° C. The higher the temperature, the greater the apparent thickness. The temperature is more preferably 75 to 100 ° C.

[00613] The time for hydrolysis is preferably 10 to 120 minutes. The longer the time, the greater the apparent thickness. The time is most preferably 20 to 120 minutes.

[00614] The step of forming continuous holes eluting the sacrificial wire will now be described in more detail. Figures 25 (a) and (b) are schematic views to explain a method for forming the continuous holes in the ion exchange membrane.

[00615] Figures 25 (a) and (b) show the reinforcement wires 52, the sacrifice wires 504a and the continuous holes 504 formed only by the sacrifice wires 504a, omitting the illustration of the other members, such as a body of membrane.

[00616] Firstly, the reinforcement wires 52 which constitute reinforcement core materials in the ion exchange membrane and the sacrifice wires 504a to form the continuous holes 504 in the ion exchange membrane are used as interlaced reinforcement materials. Then, in step (5), the sacrifice threads 504a are eluted to form continuous holes 504.

152/803

[00617] The above method is simple because the method for interlacing the reinforcement wires 52 and the sacrifice wires 504a can be adjusted depending on the arrangement of the reinforcement core materials and the continuous holes in the membrane body of the ion exchange membrane.

[00618] Figure 25 (a) exemplifies the single fabric reinforcement material in which reinforcement threads 52 and sacrifice threads 504a are interwoven along the longitudinal and lateral direction on the paper, and the arrangement of the reinforcement 52 and the sacrifice wires 504a in the reinforcement material may vary as required. (6) Application stage

[00619] In step (6), a coating layer can be formed by preparing a coating liquid containing particles of inorganic material obtained by grinding raw ore or melting raw ore and a binder, applying the coating liquid on the surface of the ion exchange membrane obtained in step (5), and drying of the coating liquid.

[00620] A preferred binder is a binder obtained by hydrolysis of a fluorine-containing polymer with an ion exchange group precursor with an aqueous solution containing dimethylsulfoxide (DMSO) and potassium hydroxide (KOH) and then immersion of the polymer in hydrochloric acid to replace the counter-ion of the ion exchange group with H + (for example, a fluorine-containing polymer with a carboxyl group or a sulfo group). Thus, the polymer is more likely to dissolve in water or ethanol mentioned below, which is preferable.

[00621] This binder is dissolved in a mixed solution of water and ethanol. The volume ratio between water and ethanol is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 2: 1 to 1: 2. The particles of inorganic material are dispersed with a ball mill in the dissolution liquid thus obtained to provide a liquid of

153/803 coating. In this case, it is also possible to adjust the average particle size and the like of the particles by adjusting the time and speed of rotation during dispersion. The preferable amount of the particles of inorganic material and the binder to be mixed is as mentioned above.

[00622] The concentration of the particles of inorganic material and the binder in the coating liquid is not particularly limited, but a thin-coated liquid is preferable. This allows uniform application to the surface of the ion exchange membrane.

[00623] Additionally, a surfactant can be added to the dispersion when the particles of inorganic material are dispersed. Like the surfactant, nonionic surfactants are preferable and examples of them include HS-210, NS-210, P-210 and E-212 manufactured by NOF CORPORATION.

[00624] The coating liquid obtained is applied on the surface of the ion exchange membrane by spray application or roller coating, thus providing an ion exchange membrane. [Microporous membrane]

[00625] The microporous membrane of the present modality is not particularly limited as long as the membrane can be formed in a laminate with the electrolysis electrode, as mentioned above. Several microporous membranes can be used.

[00626] The porosity of the microporous membrane of the present embodiment is not particularly limited, but it can be from 20 to 90, for example, and is preferably from 30 to 85. The porosity above can be calculated by the following formula: Porosity = (1 - (the weight of the membrane in a dry state) / (the weight calculated from the volume calculated from the thickness, width and length of the membrane and the density of the membrane material)) x 100

[00627] The average pore size of the microporous membrane of the

The present embodiment is not particularly limited, and may be 0.01 µm to 1 µm, for example, preferably 0.05 µm to 5 µm. Regarding the average pore size, for example, the membrane is cut vertically in the direction of thickness, and the section is observed with an FE-SEM. The average pore size can be obtained by measuring the diameter of about 100 observed pores and averaging the measurements.

[00628] The thickness of the microporous membrane of the present embodiment is not particularly limited, and can be from 10 µm to 1000 µm, for example, preferably 50 µm to 600 µm. The above thickness can be measured using a micrometer (manufactured by Mitutoyo Corporation) or similar, for example.

[00629] Specific examples of the microporous membrane as mentioned above include Zirfon Perl UTP 500 manufactured by Agfa (also called Zirfon membrane in the present embodiment) and those described in International Publication No. WO 2013-183584 and International Publication No. WO 2016-203701.

[00630] The reason why the laminate with the membrane of the present modality develops excellent electrolytic performance is presumed below. When the membrane and the electrode adhere firmly to each other by a method such as thermal compression, which is a conventional technique, the electrode sinks into the membrane to physically adhere to it. This adhesion portion inhibits the sodium fons from migrating in the membrane to increase the tension noticeably. However, inhibition of sodium ion migration in the membrane, which has been a problem in the conventional technique, is eliminated by allowing the electrode for electrolysis to be limited to a moderate adhesive force on the membrane or in the supply conductor, as in the present modality. According to the above, when the membrane or the feed conductor touches the electrode for electrolysis with a moderate adhesive force, the membrane or feed conductor and the electrode

155/803 for electrolysis, despite being an integrated part, can develop excellent electrolytic performance. [Wrapped body]

[00631] The rolled body of the present embodiment includes the laminate of the present embodiment. That is, the rolled body of the present embodiment is obtained by rolling the laminate of the present embodiment. The reduction of the laminate of the present embodiment by winding, like the rolled body of the present embodiment, can further improve the handling property. [Electrolyser]

[00632] The electrolyzer of the present modality includes the laminate of the present modality. Hereinafter, the case of conducting common salt electrolysis using an ion exchange membrane as the membrane is taken as an example, and an embodiment of the electrolyzer will be described in detail. [Electrolytic cell]

[00633] Figure 26 illustrates a cross-sectional view of an electrolytic cell 1.

[00634] The electrolytic cell 1 comprises an anodic chamber 10, a cathodic chamber 20, a partition wall 30 placed between the anodic chamber 10 and the cathodic chamber 20, an anode 11 placed in the anodic chamber and a cathode 21 placed in the cathodic chamber 20 As required, the electrolytic cell 1 has a substrate 18a and a reverse current absorbent layer 18b formed on the substrate 18a and can comprise a reverse current absorber 18 placed in the cathode chamber. Anode 11 and cathode 21 belonging to electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 comprises the following cathode structure. Cathode structure 40 comprises cathode chamber 20, cathode 21 placed in cathode chamber 20 and reverse current absorber 18 placed in cathode chamber 20, current absorber

156/803 reverse 18 has substrate 18a and reverse current absorbing layer 18b on substrate 18a, as shown in Figure 30, and cathode 21 and reverse current absorbing layer 18b are electrically connected. The cathodic chamber 20 also has a collector 23, a support 24 supporting the collector and an elastic metal body 22. The elastic metal body 22 is placed between the collector 23 and the cathode 21. The support 24 is placed between the collector 23 and the partition wall 30. The collector 23 is electrically connected to the cathode 21 through the elastic metal body 22. The partition wall 30 is electrically connected to the collector 23 through the support 24. Therefore, the partition wall 30, the support 24, the collector 23, the elastic metal body 22 and cathode 21 are electrically connected. Cathode 21 and reverse current absorbing layer 18b are electrically connected. Cathode 21 and the reverse current absorbing layer can be directly connected or they can be indirectly connected through the collector, the support, the elastic metal body, the partition wall or the like. The entire surface of cathode 21 is preferably covered with a layer of catalyst for the reduction reaction. The electrical connection form can be a form in which the partition wall 30 and the support 24, the support 24 and the collector 23, and the collector 23 and the elastic metal body 22 are each directly attached and the cathode 21 it is laminated to the elastic metal body 22. Examples of a method for directly affixing these constituent components to each other include welding and the like. Alternatively, the reverse current absorber 18, cathode 21 and collector 23 can be collectively called a cathode structure 40.

[00635] Figure 27 illustrates a cross-sectional view of two electrolytic cells 1 that are adjacent to the electrolyzer 4. Figure 28 shows an electrolyzer 4. Figure 29 shows an assembly step for the electrolyzer 4. As shown in Figure 27, an electrolytic cell 1, a cation exchange membrane 2 and an electrolytic cell 1 are arranged in

157/803 series in the order mentioned. An ion exchange membrane 2 is arranged between the anode chamber of an electrolytic cell 1 between the two adjacent electrolytic cells in the electrolyzer and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent to it are separated by the cation exchange membrane 2. As shown in Figure 28, the electrolyzer 4 is composed of a plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer comprising the plurality of electrolytic cells 1 arranged in series and ion exchange membranes 2, each arranged between adjacent electrolytic cells 1. As shown in Figure 29, electrolyzer 4 is assembled arranging the plurality of cells electrolytics 1 in series through the ion exchange membrane 2 and coupling the cells by means of a pressure device 5.

[00636] Electrolyser 4 has an anodic terminal 7 and a cathodic terminal 6 to be connected to a power supply. Anode 11 of electrolytic cell 1 located at the far end between the plurality of electrolytic cells 1 coupled in series in electrolyzer 4 is electrically connected to anode terminal 7. Cathode 21 of the electrolytic cell located at the opposite end to anode terminal 7 between the plurality of electrolytic cells 1 coupled in series in the electrolyzer 4 is electrically connected to the cathodic terminal 6. The electrical current during electrolysis flows from the side of the anodic terminal 7, through the anode and cathode of each electrolytic cell 1, towards the cathodic terminal 6. At the two ends of the coupled electrolytic cells 1, an electrolytic cell with only one anodic chamber (anode terminal cell) and an electrolytic cell with only one cathodic chamber (cathode terminal cell) can be arranged. In this case, anode terminal 7 is connected to the anode terminal cell, arranged at one end, and cathode terminal 6 is

158/803 connected to the cathode terminal cell, arranged at the other end.

[00637] In the case of electrolytic brine, brine is provided for each anodic chamber 10 and pure water or an aqueous solution of low concentration sodium hydroxide is provided for each cathodic chamber 20. Each liquid is supplied from a supply tube of electrolytic solution (not shown in the Figure), through an electrolytic solution supply hose (not shown in the Figure), for each electrolytic cell 1. The electrolyte solution and electrolysis products are recovered from an electrolyte recovery tube (not shown in the figure). During electrolysis, the sodium ions in the brine migrate from the anode chamber 10 of the electrolytic cell 1, through the ion exchange membrane 2, to the cathode chamber 20 of the adjacent electrolytic cell 1. Thus, the electric current during electrolysis flows in the direction wherein electrolytic cells 1 are coupled in series. That is, the electric current flows, through the cation exchange membrane 2, from the anodic chamber 10 towards the cathodic chamber 20. As the brine is electrolyzed, chlorine gas is generated on the anode side 11, and sodium hydroxide (solute ) and hydrogen gas are generated on the cathode side

21. (Anodic chamber)

[00638] The anode chamber 10 has anode 11 or the anode supply conductor 11. When the electrode for electrolysis of the present modality is inserted on the anode side, 11 serves as the anode supply conductor. When the electrode for electrolysis of the present modality is not inserted on the anode side, 11 serves as an anode. The anodic chamber 10 has an electrolytic solution supply unit on the anode side that provides an electrolytic solution to the anodic chamber 10, a baffle plate that is arranged above the anode side electrolytic solution supply unit to be substantially parallel or oblique to the partition wall 30, and a liquid and gas separation unit from the

159/803 anode side arranged above the baffle to separate the gas from the electrolytic solution including the mixed gas. (Anode)

[00639] When the electrode for electrolysis of the present modality is not inserted on the side of the anode, anode 11 is provided in the frame of the anodic chamber 10. As anode 11, a metal electrode such as the so-called DSA (R) can be used . DSA is an electrode that includes a titanium substrate whose surface is covered with an oxide that contains ruthenium, iridium and titanium as components.

[00640] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Anode feed conductor)

[00641] When the electrode for electrolysis of the present modality is inserted on the anode side, the anode 11 feeder conductor is provided in the anode chamber 10 frame. As the anode 11 feeder conductor, a metal electrode can be used , such as the so-called DSA (R), and titanium without catalyst coating can also be used. Alternatively, DSA with a thinner catalyst coating can also be used. In addition, a used anode can also be used.

[00642] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Anode side electrolyte solution supply unit)

[00643] The electrolytic solution supply unit on the anode side, which supplies the electrolytic solution to the anodic chamber 10, is connected to the electrolyte solution supply tube. The unit of

160/803 supply of electrolytic solution on the anode side is preferably arranged below the anode chamber 10. As the supply unit of electrolytic solution on the anode side, for example, a tube can be used on the surface from which orifice portions are formed. (dispersion tube) and the like. Such a tube is most preferably arranged along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell. This tube is connected to an electrolytic solution supply tube (liquid supply nozzle) that supplies the electrolytic solution to the electrolytic cell 1. The electrolyte solution supplied from the liquid supply nozzle is transported with a tube into the electrolytic cell 1 and supplied from the orifice portions provided on the surface of the tube into the anodic chamber 10. The arrangement of the tube along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell is preferable because the electrolyte solution can be uniformly supplied into the anodic chamber

10. (Liquid and gas separation unit on the anode side)

[00644] The liquid and gas separation unit on the anode side is preferably arranged above the baffle. The liquid and gas separation unit on the anode side has the function of separating the produced gas such as chlorine gas from the electrolytic solution during electrolysis. Unless otherwise specified, above means the upper direction in electrolytic cell 1 in Figure 26, and below means the lower direction in electrolytic cell 1 in Figure 26.

[00645] During electrolysis, the produced gas generated in electrolytic cell 1 and the electrolytic solution form a mixed phase (mixed gas-liquid phase), which is then emitted out of the system. Subsequently, pressure fluctuations within the electrolytic cell 1 cause vibration, which can result in physical damage to the ion exchange membrane. In order to avoid this event, the electrolytic cell 1 of the present modality is preferably

161/803 provided with a liquid and gas separation unit on the anode side to separate the gas from the liquid. The liquid and gas separation unit on the anode side is preferably provided with an anti-foam plate to eliminate bubbles. When the flow of the mixed gas-liquid phase passes through the antifoam plate, the bubbles burst, thus allowing the electrolyte solution and the gas to be separated. As a result, vibration during electrolysis can be avoided. (Baffle plate)

[00646] The baffle plate is preferably arranged above the electrolyte solution supply unit on the anode side and arranged substantially in parallel or obliquely to the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. When the deflector plate is provided, it is possible to make the electrolyte solution (brine or similar) circulate internally in the anodic chamber 10 to thus make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged in such a way as to separate the space in the vicinity of anode 11 from the space near the partition wall 30. From such a point of view, the baffle plate is preferably placed so as to be opposite the surface of anode 11 and the surface of the dividing wall 30. In the space next to the anode divided by the deflector plate, as the electrolysis progresses, the concentration of the electrolytic solution (brine concentration) is reduced and the gas produced, such as chlorine gas is generated. This results in a difference in specific gas-liquid gravity between the space near anode 11 and the space near the dividing wall 30 divided by the deflector plate. By using the difference, it is possible to promote the internal circulation of the electrolytic solution in the anodic chamber 10 to thus make the distribution of concentration of the electrolytic solution in the anodic chamber 10 more uniform.

[00647] Although not shown in Figure 26, a collector can be

162/803 additionally provided within the anodic chamber 10. The material and configuration of such a collector can be the same as the collector of the cathodic chamber mentioned below. In anode chamber 10, anode 11 per se can also serve as a collector. (Partition wall)

[00648] The dividing wall 30 is arranged between the anodic chamber 10 and the cathodic chamber 20. The dividing wall 30 can be called a separator, and the anodic chamber 10 and the cathodic chamber 20 are divided by the dividing wall 30. Like the wall partition 30, one known as electrolysis separator can be used, and an example of this includes a partition wall formed by welding a plate comprising nickel next to the cathode and a plate comprising titanium beside the anode. (Cathodic chamber)

[00649] In the cathode chamber 20, when the electrode for electrolysis of the present modality is inserted on the side of the cathode, 21 serves as a supply conductor for the cathode. When the electrode for electrolysis of the present modality is not inserted on the cathode side, 21 serves as a cathode. When a reverse current absorber is included, the cathode or cathode supply conductor 21 is electrically connected to the reverse current absorber. The cathode chamber 20, similarly to the anode chamber 10, preferably has an electrolytic solution supply unit on the cathode side and a liquid and gas separation unit on the cathode side. Among the components that make up the cathodic chamber 20, components similar to those that make up the anode chamber 10 will not be described. (Cathode)

[00650] When the electrode for electrolysis of the present modality is not inserted on the side of the cathode, a cathode 21 is provided in the frame of the cathodic chamber 20. The cathode 21 preferably has a nickel substrate and a

163/803 layer of catalyst covering the nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include metals such as Ru, C, Si, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, alloy galvanizing, composite dispersion / galvanizing, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Cathode 21 can be subjected to a reduction treatment as needed. As the cathode 21 substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[00651] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Cathode supply conductor)

[00652] When the electrode for the electrolysis of the present modality is inserted on the cathode side, a cathode 21 conductor is provided in the cathode chamber 20 frame. The cathode 21 catheter can be covered with a catalytic component. The catalytic component can be a component that is originally used as the cathode and remains. Examples of the catalyst layer components include metals such as Ru, C, S1, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh , Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, I, Gd, Tb, Dy , Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / plating

164/803 composite, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Alternatively, nickel, nickel alloys and nickel or stainless galvanized iron without catalyst coating can be used. As the cathode 21 feed conductor substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[00653] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Reverse current absorbing layer)

[00654] A material with a less noble redox potential than the element's redox potential for the catalyst layer of the cathode mentioned above can be selected as a material for the reverse current absorbing layer. Examples of it include nickel and iron. (Collector)

[00655] The cathodic chamber 20 preferably comprises the collector

23. Collector 23 improves the efficiency of the current collection. In the present embodiment, the collector 23 is a porous plate and is preferably arranged substantially parallel to the surface of the cathode 21.

[00656] The collector 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. Collector 23 can be a mixture, alloy or composite oxide of these metals. The collector 23 can have any shape, as long as the shape allows the function of the collector and can have a plate or network shape. (Elastic metal body)

[00657] Placing the elastic metal body 22 between the collector 23 and the cathode 21 presses each cathode 21 of the plurality of electrolytic cells 1

165/803 connected in series to the ion exchange membrane 2 to reduce the distance between each anode 11 and each cathode 21. Then, it is possible to reduce the voltage to be applied entirely through the plurality of electrolytic cells 1 connected in series. Reducing the voltage reduces energy consumption. With the elastic metal body 22 in place, the pressure caused by the elastic metal body 22 allows the electrolysis electrode to be held steadily in place when the laminate including the electrolysis electrode according to the present embodiment is placed in the electrolytic cell.

[00658] As the elastic metal body 22, spring members such as spiral springs and coils and damping mats can be used. As the elastic metal body 22, a suitable one can be used appropriately, taking into account a tension to pressure the ion exchange membrane and the like. The elastic metal body 22 can be provided on the surface of the collector 23 on the side of the cathode chamber 20 or it can be provided on the surface of the partition wall on the side of the anode chamber 10. Both chambers are normally divided in such a way that the cathode chamber 20 it becomes smaller than the anodic chamber 10. Thus, from the point of view of the strength of the frame and the like, the elastic metal body 22 is preferably provided between the collector 23 and the cathode 21 in the anodic chamber

20. The elastic metal body 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. (Support)

[00659] The cathodic chamber 20 preferably comprises the support 24 that electrically connects the collector 23 to the partition wall 30. This can achieve an efficient current flow.

[00660] The support 24 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. The support 24 can have any shape as long as the support can support the collector 23 and can have a rod, plate or network shape. Support 24 has

166/803 a plate shape, for example. A plurality of supports 24 is arranged between the partition wall 30 and the collector 23. The plurality of supports 24 are aligned in such a way that their surfaces are in parallel with each other. The supports 24 are arranged substantially perpendicular to the partition wall 30 and the collector 23.

(Anode-side gasket and cathode-side gasket)

[00661] The anode-side gasket is preferably arranged on the surface of the structure that constitutes the anode chamber 10. The cathode-side gasket is preferably arranged on the surface of the structure that constitutes the cathodic chamber 20. The electrolytic cells are connected to each other others such that the anode-side gasket included in an electrolytic cell and the cathode-side gasket of an electrolytic cell adjacent to the cell sandwich the ion exchange membrane 2 (see Figures 26 and 27). These gaskets can make the connection points airtight when the plurality of electrolytic cells 1 is connected in series through the ion exchange membrane 2.

[00662] The gaskets form a seal between the ion exchange membrane and the electrolytic cells. Specific examples of gaskets include picture frame rubber sheets, in the center of which a hole portion is formed. Gaskets are required to be resistant to corrosive electrolyte solutions or gas produced and to be usable for a long period. Thus, with regard to chemical resistance and hardness, vulcanized products and products cross-linked with ethylene-propylene-diene rubber peroxide (EPDM rubber) and ethylene-propylene rubber (EPM rubber) are normally used as gaskets. Alternatively, gaskets from which the region to be in contact with liquid (liquid contact portion) with a fluorine-containing resin such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers can be used as needed. These gaskets can have a portion

167/803 orifice so as not to inhibit the flow of the electrolyte solution, and the shape of the orifice portion is not particularly limited. For example, a picture frame gasket is affixed with an adhesive or similar along the peripheral edge of each hole portion of the anodic chamber frame that constitutes the anodic chamber 10 or the cathodic chamber frame that constitutes the cathodic chamber 20. So, for example, in the case where the two electrolytic cells 1 are connected via the ion exchange membrane 2 (see Figure 27), each electrolytic cell 1 to which the gasket is attached must be tightened via the ion exchange membrane 2. This Tightening can prevent the electrolyte solution, alkali metal hydroxide, chlorine gas, hydrogen gas and the like, generated from electrolysis, from escaping from electrolytic cells 1. (Ion exchange membrane)

[00663] The ion exchange membrane 2 is as described in the section of the ion exchange membrane described above. (Water electrolysis)

[00664] The electrolyser of the present modality, as an electrolyser in the case of water electrolysis, has a configuration in which the ion exchange membrane in an electrolyser for use in the case of common salt electrolysis mentioned above is replaced by a microporous membrane. The raw material to be supplied, which is water, is different from that for the electrolyser in the case of electrolysis of the common salt mentioned above. As for the other components, components similar to those of the electrolyser in the case of electrolysis of common salt can also be used in the electrolyser in the case of water electrolysis. Since chlorine gas is generated in the anodic chamber in the case of common salt electrolysis, titanium is used as the material in the anodic chamber, but in the case of water electrolysis, only oxygen gas is generated in the anodic chamber. Thus, a material identical to that of the cathodic chamber can be used. An example of this is nickel. For anode coating, the

168/803 catalyst coating for oxygen generation is suitable. Examples of the catalyst coating include metals, oxides and hydroxides of the metals of the platinum group and metals of the transition metal group. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used.

(Application of laminate)

[00665] The laminate of this modality can improve the work efficiency during the electrode renewal in an electrolyzer and, in addition, it can present an excellent electrolytic performance also after the renovation as mentioned above. In other words, the laminate of the present embodiment can be suitably used as a laminate to replace an electrolyzer member. A laminate to be used in such an application is specifically called a "membrane electrode assembly".

(Packing)

[00666] The laminate of the present modality is preferably transported or similar, while enclosed in a packaging material. That is, the packaging of the present embodiment comprises the laminate of the present embodiment and a packaging material that packs the laminate. The packaging of the present modality, configured as described above, can prevent the adherence of stains and damage that may occur during transport or similar to the laminate of the present modality. When used to replace an electrolyzer member, the laminate is particularly preferably transported or similar as the packaging of the present embodiment. As the packaging material of the present embodiment, which is not particularly limited, various packaging materials can be used. Alternatively, the packaging of the present embodiment can be produced, for example, by a method including packaging

169/803 of the laminate of the present modality with a clean packaging material followed by encapsulation or the like, although not limited to it. <Third modality>

[00667] Here, a third embodiment of the present invention will be described in detail with reference to Figures 43 to 62. [Laminate]

[00668] The laminate of the third modality (hereinafter, in the section of <Third modality>, simply called “the present modality”) has a membrane and an electrolysis electrode attached to at least one region of the “membrane” surface ( hereinafter, simply also called a “fixed region”), and the proportion of the region on the membrane surface is greater than 0% and less than 93%. The laminate of the present modality, as configured as described above, can improve the work efficiency during the electrode renewal in an electrolyzer and, in addition, it can present an excellent electrolytic performance also after the renovation.

[00669] That is, according to the laminate of the present modality, when renewing the electrode, the electrode can be renewed by a job as simple as renewing the membrane, without a complicated job like removing the existing electrode fixed in the electrolytic cell, and thus, work efficiency is noticeably improved.

[00670] In addition, according to the laminate of this modality, it is possible to maintain the electrolytic performance of the existing electrolytic cell comparable to that of a new electrode or to improve the electrolytic performance. Thus, the electrode attached to the existing electrolytic cell and serving as an anode and / or a cathode is only needed to serve as a supply conductor. Thus, it may also be possible to significantly reduce or eliminate the catalyst coating. The supply conductor here means a degraded electrode (that is, the electrode

170/803), an electrode without catalyst coating and the like. [Electrode for electrolysis]

[00671] The electrolysis electrode in the present modality is not particularly limited, as long as the electrode is an electrode to be used for electrolysis and, preferably, has a surface area opposite to the electrolysis electrode membrane (corresponds to an area of the electrolysis surface) conduction S2 mentioned below) of 0.01 m? or more. The "surface opposite the membrane" means the surface on which the membrane is located from the surfaces possessed by the electrolysis electrode. That is, the surface opposite the membrane on the electrolysis electrode can also be the surface that touches the membrane surface. When the surface area opposite the membrane on the electrolysis electrode is 0.01 m? or more, sufficient productivity can be achieved, and especially when industrial electrolysis is carried out, sufficient productivity tends to be achieved. Thus, from the point of view of achieving sufficient productivity and achieving practicality for a laminate to be used in the renewal of the electrolytic cell, is the surface area opposite the membrane on the electrolysis electrode more preferably 0.1 m? or more, even more preferably 1 m? or more. The area can be measured, for example, by a method described in Examples.

[00672] The electrolysis electrode in the present embodiment has a force applied per unit mass-unit area of preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mg: in?), even more preferably less than 1.5 N / (mg: cm?), even more preferably 1.2 N / mg-cm? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a supply conductor (a degraded electrode and an uncoated electrode) catalyst) and the like. The applied force is even more

171/803 preferably 1.1 N / mg-cm? or less, even more preferably 1.10 N / mge? or less, particularly preferably 1.0 N / m? or less, especially preferably 1.00 N / mg-cm? or less.

[00673] From the point of view of further improving electrolytic performance, the strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: in?) Or more, even more preferably 0.1 N / mg: cm? or more, even more preferably 0.14 N / (mg: cm?) or more. By force it is even more preferably 0.2 N / (mg: cm?) Or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 m x 2.5 m).

[00674] The applied force described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness, arithmetic mean surface roughness and the like, for example. More specifically, for example, a higher opening ratio tends to lead to a lower applied force, and a lower opening ratio tends to lead to a higher applied force.

[00675] Is the mass per unit preferably 48 mg / cm? or less, more preferably 30 mg / cm? or less, even more preferably 20 mg / cm? or less from the point of view of allowing a good manipulation property, having a good adhesive force for a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a conductive conductor without catalyst coating, and economy , and in addition it is 15 mg / cm? or less from a comprehensive point of view including handling, grip and economy properties. The lower limit value is not particularly limited, but is in the order of 1 mg / em ?, for example.

[00676] The mass per unit area described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness and the like, for example. More

172/803 specifically, for example, when the thickness is constant, a larger opening ratio tends to lead to a smaller mass per unit area, and a smaller opening ratio tends to lead to a mass per unit area greater.

[00677] The applied force can be measured by the following method (1) or (11). The value obtained by measuring method (i) (also called “applied force (1)”) and the value obtained by measuring method (11) (also called “applied force (2)”) can be equal or different, and any of the values is preferably less than 1.5 N / (mg: ecm?). [Method (i)]

[00678] A nickel plate obtained by stripping processing with grain size 320 alumina (1.2 mm thickness, 200 square mm), an ion exchange membrane that is obtained by the application of particles of inorganic material and a binder on both surfaces of a perfluorocarbon polymer membrane in which an ion exchange group (170 square mm) and an electrode sample (130 square mm) are introduced are laminated in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. The arithmetic mean roughness of the surface (Ra) of the nickel plate after blasting treatment is 0.5 to 0.8 µm. The specific method for calculating the arithmetic mean surface roughness (Ra) is as described in the Examples.

[00679] Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the charge when the electrode sample is raised by 10 mm in a vertical direction is measured. This measurement is repeated three times and the average value is calculated.

[00680] This average value is divided by the area of the overlapping portion of the

173/803 electrode sample and ion exchange membrane and mass of the portion that overlaps the ion exchange membrane in the electrode sample to calculate the applied force per unit mass-unit area (1) (N / mg- ecm?).

[00681] The force applied per unit mass-unit area (1) obtained by method (i) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg: -em? or less. The strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg: cm?) Or more than the point view of further improving electrolytic performance, and furthermore, it is even more preferably 0.14 N / (mgcm?), even more preferably 0.2 N / (mg: cm?) or more from the point of view of facilitating further manipulation in a large size (for example, a size of 1.5 mx2.5 Mm). [Method (ii)]

[00682] A nickel plate obtained by stripping processing with alumina of grain size 320 (thickness 1.2 mm, 200 mm square, a nickel plate similar to the method (1) above) and an electrode sample ( 130 mm square) is laminated in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. Under

174/803 temperature conditions of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the charge when the electrode sample is raised by 10 mm in a vertical direction is measured. This measurement is repeated three times and the average value is calculated.

[00683] This average value is divided by the area of the overlapping portion of the electrode sample and the nickel plate and the mass of the electrode sample in the portion that overlaps the nickel plate to calculate the adhesive force per unit mass-unit of area (2) (N / mg: -cm?).

[00684] The force applied per unit mass-unit area (2) obtained by method (ii) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg: cm? or less. In addition, the strength is preferably greater than 0.005 N / (mg: cm?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg-in?) Or more from the point of view of further improving electrolytic performance, and it is even more preferably 0.14 N / (mg: cm?) or more from the point of view of further facilitating handling in a large size (for example, a 1.5 m x 2.5 m).

[00685] The electrolyte electrode in the present modality

175/803 preferably includes an electrode substrate for electrolysis and a layer of catalyst. The substrate thickness for the electrolysis electrode (gauge thickness) is, but is not particularly limited to, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less , even more preferably 125 µm or less, even more preferably 120 µm or less, even more preferably 100 µm or less from the point of view of enabling a good handling property to be provided, having a good adhesive strength to a membrane, such as a ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, be able to be properly laminated on a roll and folded satisfactorily, facilitating handling in one size large (for example, a size of 1.5 mx 2.5 Mm), and is even more preferably 50 µm or less from the point of view of a handling and economy property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[00686] The proportion measured by the following method (2) of the electrode for electrolysis in the present embodiment is not particularly limited, but is preferably 90% or more, more preferably 92% or more from the point of view of allowing a good handling property is provided and has a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and more preferably 95% or more from the point of view of facilitating further handling at a large size (for example, a size of 1.5 mx 2.5 m) The upper limit value is 100%. [Method (2)]

176/803

[00687] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 280 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[00688] The proportion measured by the following method (3) of the electrode for electrolysis in the present embodiment is not particularly limited, but is preferably 75% or more, more preferably 80% or more from the point of view of allowing a good handling property be provided, have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating and can be properly laminated in a roll is satisfactorily folded, and is more preferably 90% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (3)]

[00689] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 145 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are

177/803 sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of an area of a portion in which the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[00690] The electrolysis electrode in the present modality has a porous structure and an opening ratio or void ratio of 5 to 90% or less from the point of view of enabling a good handling property, having a good adhesive force to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and to prevent gas buildup from being generated during electrolysis, although not particularly limited . The opening ratio is more preferably 10 to 80% or less, more preferably 20 to 75%.

[00691] The opening ratio is a proportion of the opening portions per unit volume. The calculation method may differ depending on whether the opening portions in submicron size are considered or that only visible openings are considered. In the present embodiment, a volume V was calculated from the values of the thickness of the gauge, width and length of the electrode and, in addition, a weight W was measured to thereby calculate an aperture ratio A using the following formula.

A = (1- (W / (YV xp)) x 100

[00692] p is the density of the electrode material (g / cm?). For example, p nickel is 8.908 g / cm ”, and p titanium is 4.506 g / cm ?. The opening ratio is appropriately adjusted by changing the area of metal to be drilled per unit area in the case of perforated metal, changing the SW (short diameter), LW (long diameter) and feed values in the case of expanded metal, changing the metal fiber line diameter and mesh number in the case of mesh, changing the pattern of a photoresist to be used

178/803 in the case of electroforming, changing the diameter of the metal fiber and fiber density in the case of non-woven fabric, changing the mold to form voids in the case of foamed metal or similar.

[00693] Hereinafter, an aspect of the electrode for electrolysis in the present modality will be described.

[00694] The electrolysis electrode according to the present embodiment preferably includes a substrate for electrolysis electrode and a catalyst layer. The catalyst layer can be composed of a plurality of layers, as shown below, or it can be a single layer configuration.

[00695] As shown in Figure 43, an electrolysis electrode 100 according to the present embodiment includes an electrode substrate for electrolysis 10 and a pair of first layers 20 with which both surfaces of the electrode substrate for electrolysis 10 are covered. . The entire electrolyte electrode substrate 10 is preferably covered with the first 20 layers. This coating is likely to improve the activity of the catalyst and the durability of the electrolysis electrode. A first layer 20 can be laminated only on one surface of the electrode substrate for electrolysis 10.

[00696] Also as shown in Figure 43, the surfaces of the first layers 20 can be covered with the second layers 30. The first entire layers 20 are preferably covered by the second layers 30. Alternatively, a second layer 30 can be laminated to only one surface of the first layer 20. (Electrode substrate for electrolysis)

[00697] As an electrode substrate for electrolysis 10, for example, nickel, nickel alloys, stainless steel or valve metals including titanium can be used, although not limited to them. The substrate 10 preferably contains at least one element selected from nickel (Ni) and

179/803 titanium (Ti).

[00698] When stainless steel is used in a high-concentration aqueous alkaline solution, iron and chromium are eluted and the electrical conductivity of stainless steel is about one tenth that of nickel. In view of the above, a substrate containing nickel (Ni) is preferable as a substrate for the electrolysis electrode.

[00699] Alternatively, when the electrode substrate for electrolysis 10 is used in a high concentration saline solution close to saturation under an atmosphere in which chlorine gas is generated, the substrate material for electrode 10 is also preferably titanium with high corrosion resistance.

[00700] The shape of the electrode substrate for electrolysis 10 is not particularly limited, and a shape suitable for the purpose can be selected. As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. Among these, a perforated metal or expanded metal is preferable. Electroforming is a technique for producing a thin metal film with a precise pattern using photolithography and electroplating in combination. It is a method that includes the formation of a pattern on a substrate with a photoresist and electroplating of the portion not protected by the resistance to provide a thin metal film.

[00701] Regarding the shape of the substrate for the electrolysis electrode, an appropriate specification depends on the distance between the anode and the cathode in the electrolyzer. In the case where the distance between the anode and the cathode is finite, a form of expanded metal or perforated metal can be used, and in the case of a so-called zero-interstitial electrolyzer, in which the ion exchange membrane is in contact with the electrode, a woven mesh produced by fine knitted threads, wire mesh, foamy metal,

180/803 non-woven metallic fabric, expanded metal, perforated metal, porous metal foil and the like, although not limited to it.

[00702] Examples of the electrode substrate for electrolysis 10 include a porous metallic foil, a wire mesh, a nonwoven metal fabric, a perforated metal, an expanded metal and a foamy metal.

[00703] As plate material before being processed into a perforated metal or expanded metal, laminated plate materials and electrolytic sheets are preferred. An electrolytic sheet is preferably still subjected to a galvanizing treatment using the same element as its base material, such as after-treatment, to thereby form roughness and one or both surfaces.

[00704] The thickness of the electrode substrate for electrolysis 10 is, as mentioned above, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less, even more preferably 125 one or less, even more preferably 120 µm or less, even more preferably 100 µm or less, and even more preferably 50 µm or less from the point of view of a handling and economical property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[00705] In the electrode substrate for electrolysis, the residual stress during processing is preferably relaxed by annealing the electrode substrate for electrolysis in an oxidizing atmosphere. It is preferable to form roughness using a steel grid, alumina powder or similar on the surface of the electrode substrate for electrolysis followed by an acid treatment to increase the surface area of the electrode, in order to improve the adhesion to a catalyst layer with which the surface is covered. Alternatively, it is preferable to give a galvanizing treatment using the same element as the substrate to increase the surface area.

181/803

[00706] In order to place the first layer 20 in close contact with the surface of the electrode electrode substrate 10, the electrode electrode substrate 10 is preferably subjected to a treatment to increase the surface area. Examples of the treatment of increasing the surface area include a pickling treatment using a cut wire, steel grid, alumina grid or similar, an acid treatment using sulfuric acid or hydrochloric acid, and a galvanizing treatment using the same element as the of the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 µm to 50 µm, more preferably 0.1 to 10 µm, even more preferably 0.1 to 8 µm.

[00707] Next, a case will be described in which the electrode for electrolysis in the present modality is used as an anode for electrolysis of common salt. (First layer)

[00708] In Figure 43, a first layer 20 as a catalyst layer contains at least one of the ruthenium oxides, iridium oxides and titanium oxides. Examples of ruthenium oxide include RuO; Examples of iridium oxide include IrO ,. Examples of titanium oxide include TiO,; The first layer 20 preferably contains two oxides: a ruthenium oxide and a titanium oxide or three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide. This makes the first layer 20 more stable and further improves adhesion with the second layer 30.

[00709] When the first layer 20 contains two oxides: a ruthenium oxide and a titanium oxide, the first layer 20 preferably contains 1 to 9 mol, more preferably 1 to 4 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition ratio of the two oxides in this range, the electrode for electrolysis 100 has excellent durability.

182/803

[00710] When the first layer 20 contains three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide, the first layer 20 preferably contains 0.2 to 3 mol, more preferably 0.3 to 2.5 mol of iridium oxide based on 1 mol of ruthenium oxide contained in the first layer 20. The first layer 20 preferably contains 0.3 to 8 mol, more preferably 1 to 7 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition of the three oxides in this range, the electrode for electrolysis 100 has excellent durability.

[00711] When the first layer 20 contains at least two of a ruthenium oxide, an iridium oxide and a titanium oxide, these oxides preferably form a solid solution. The formation of the solid oxide solution allows the electrolysis electrode 100 to have excellent durability.

[00712] In addition to the compositions described above, oxides of various compositions may be used provided that at least one oxide of a ruthenium oxide, an iridium oxide and titanium oxide is contained. For example, an oxide coating called DSA (R), which contains ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum and the like, can be used as a first layer 20.

[00713] The first layer 20 need not be a single layer and can include a plurality of layers. For example, the first layer 20 can include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 µm, more preferably 0.1 to 8 µm. (Second layer)

[00714] The second layer 30 preferably contains ruthenium and titanium. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

183/803

[00715] The second layer 30 preferably contains a palladium oxide, a solid solution of a palladium and platinum oxide, or an alloy of palladium and platinum. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[00716] A second thicker layer 30 can maintain the electrolytic performance for a longer period, but from an economic point of view, the thickness is preferably 0.05 to 3 µm.

[00717] Next, a case will be described in which the electrode for electrolysis in the present modality is used as a cathode for electrolysis of common salt. (First layer)

[00718] Examples of components of the first layer 20 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[00719] The first layer 20 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal.

[00720] When the first layer 20 contains at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides, and alloys containing a platinum group metal, the metals of the platinum group platinum, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal preferably contain at least one platinum group metal of platinum, palladium, rhodium, ruthenium and iridium.

[00721] Like the platinum group metal, platinum is preferably contained.

[00722] Like the metal oxide of the platinum group, an oxide of

184/803 ruthenium is preferably contained.

[00723] Like the metal hydroxide of the platinum group, a ruthenium hydroxide is preferably contained.

[00724] Like the platinum group metal alloy, a platinum alloy with nickel, iron and cobalt is preferably contained.

[00725] In addition, as needed, an oxide or hydroxide of a lanthanide element is preferably contained as a second component. This allows the electrolysis electrode 100 to have excellent durability.

[00726] As the oxide or hydroxide of a lanthanide element, at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium and dysprosium is preferably contained.

[00727] Furthermore, as needed, an oxide or hydroxide of a transition metal is preferably contained as a third component.

[00728] The addition of the third component allows the electrolysis electrode 100 to have greater durability and the electrolysis voltage to be reduced.

[00729] Examples of a preferable combination include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + Platinum + Palladium, Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + samarium + cobalt, ruthenium + samarium + zinc, ruthenium +

185/803 samarium + gallium, ruthenium + samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium , platinum + iridium + palladium, platinum + nickel + palladium, platinum + nickel + ruthenium, platinum and nickel alloys, platinum and cobalt alloys, and platinum and iron alloys.

[00730] When platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal are not contained, the main component of the catalyst is preferably the nickel element.

[00731] At least one of the nickel metals, oxides and hydroxides is preferably contained.

[00732] As the second component, a transition metal can be added. As the second component to be added, at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper and carbon is preferably contained.

[00733] Examples of a preferable combination include nickel + tin, nickel + titanium, nickel + molybdenum and nickel + cobalt.

[00734] As required, an intermediate layer can be placed between the first layer 20 and the electrode substrate for electrolysis

10. The durability of the electrolysis electrode 100 can be improved by placing the intermediate layer.

[00735] As the intermediate layer, those that have affinity for both the first layer 20 and the electrode substrate for electrolysis 10 are preferred. As the intermediate layer, nickel oxides, platinum group metals, metal oxides are preferable of the platinum group and metal hydroxides of the platinum group. The intermediate layer can be formed by applying and cooking a solution containing a component that forms the intermediate layer. Alternatively, a surface oxide layer can also be formed by subjecting a

186/803 substrate to a heat treatment at a temperature of 300 to 600ºC in an air atmosphere. In addition, the layer can be formed by a known method, such as a thermal spray method and an ion galvanizing method. (Second layer)

[00736] Examples of components of the first layer 30 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[00737] The first layer 30 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal. Examples of a preferable combination of elements contained in the second layer include the combinations listed for the first layer. The combination of the first layer and the second layer can be a combination in which the compositions are the same and the composition reasons are different or can be a combination of different compositions.

[00738] As the thickness of the catalyst layer, the total thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 µm to 20 µm. With a thickness of 0.01 µm or more, the catalyst layer can sufficiently serve as the catalyst. With a thickness of 20 µm or less, it is possible to form a robust catalyst layer that is unlikely to fall off the substrate. The thickness is more preferably 0.05 µm to 15 µm. The thickness is more preferably 0.1 µm to 10 µm. The thickness is even more preferably 0.2 µm to 8 µm.

[00739] The thickness of the electrode, that is, the total thickness of the electrode substrate for electrolysis and the catalyst layer is preferably 315

187/803 One or less, more preferably 220 one or less, more preferably 170 One or less, even more preferably 150 one or less, particularly - preferably 145 one or less, even more preferably 140 one or less, even more preferably 138 one or less, even more preferably 135 µm or less with respect to the handling property of the electrode. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably one or more. The thickness of the electrode can be determined by measurement with a digital thickness gauge (Mitutoyo Corporation, minimum scale 0.001 mm). The thickness of the electrode substrate for electrolysis is measured in the same way as the thickness of the electrode. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.

[00740] In the present embodiment, the electrolysis electrode preferably contains at least one catalytic component selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B / C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy from the point of view of achieving sufficient electrolytic performance.

[00741] In the present modality, from the point of view that the electrolysis electrode, if it is an electrode with a wide region of elastic deformation, can provide a better handling property and has a better adhesive strength to a membrane such as an exchange membrane ion and a microporous membrane, a degraded electrode, a supply conductor

188/803 with no catalyst coating, and the like, the electrode thickness for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, even more preferably 150 µm or less, particularly preferably 145 one or less, even more preferably 140 one or less, even more preferably 138 one or less, even more preferably 135 one or less. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably 20 µm or more. In the present modality, “having a wide region of elastic deformation” means that when an electrolysis electrode is wound to form a wound body, it is unlikely that distortion derived from the winding will occur after the wound state is released. The thickness of the electrolysis electrode refers, when a catalyst layer mentioned below is included, to the total thickness of both the electrolysis electrode substrate and the catalyst layer. (Method to produce electrode for electrolysis)

[00742] Next, an embodiment of the method for producing the electrolysis electrode 100 will be described in detail.

[00743] In the present embodiment, the electrolysis electrode 100 can be produced by forming the first layer 20, preferably the second layer 30, on the electrode electrode substrate by a method such as cooking a coating film under an oxygen atmosphere ( pyrolysis) or ion galvanizing, galvanizing or thermal spraying. The production method of the present modality as mentioned can reach

189/803 a high productivity of electrode for electrolysis 100. Specifically, a layer of catalyst is formed on the electrode substrate for electrolysis by an application step to apply a coating liquid containing a catalyst, a drying step to dry the liquid from coating and a pyrolysis step to perform pyrolysis. Pyrolysis here means that a metal salt that is to be a precursor is decomposed by heating into a metal or metal oxide and a gaseous substance. The decomposition product depends on the metal species to be used, the type of salt and the atmosphere under which pyrolysis is carried out, and many metals tend to form oxides in an oxidizing atmosphere. In an industrial electrode production process, pyrolysis is usually carried out in air, and a metal oxide or metal hydroxide is formed in many cases. (Formation of the first anode layer) (Application stage)

[00744] The first layer 20 is obtained by applying a solution in which at least one metallic salt of ruthenium, iridium and titanium is dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the liquid of coating in the presence of oxygen. The ruthenium, iridium and titanium content in the first coating liquid is substantially equivalent to that of the first layer 20.

[00745] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

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[00746] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersion bathing of the electrode substrate for electrolysis 10 in the first coating liquid, a method of brushing the first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[00747] After being applied to the electrode substrate for electrolysis 100, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[00748] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the second layer)

[00749] The second layer 30, which is formed as needed, is

191/803 obtained, for example, by applying a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second coating liquid) in the first layer 20 and then pyrolyzing the coating in the presence of oxygen. (Formation of the first cathode layer by the pyrolysis method) (Application stage)

[00750] The first layer 20 is obtained by applying a solution in which metal salts of various combinations are dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the coating liquid in the presence of oxygen. The metal content in the first coating liquid is substantially equivalent to that of the first layer 20.

[00751] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[00752] Examples of a method used as the method for applying the first coating liquid to the electrode electrode substrate 10 include a bathing method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10

192/803 and the first coating liquid are loaded in the opposite way and spraying is carried out. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[00753] After being applied to the electrode substrate for electrolysis 10, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[00754] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the intermediate layer)

[00755] The intermediate layer, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound or a platinum compound (second coating liquid) to the substrate and then pyrolyzing the coating liquid in the presence of oxygen. Alternatively, an intermediate layer of nickel oxide can be formed on the surface of the substrate just by heating the substrate, without applying a solution on it. (Formation of the first cathode layer by ion galvanizing)

193/803

[00756] The first layer 20 can also be formed by ion plating.

[00757] An example includes a method in which the substrate is fixed in a chamber and the metal ruthenium target is irradiated with an electron beam. Evaporated metallic ruthenium particles are positively charged to the plasma in the chamber to deposit on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and deposits of ruthenium as ruthenium oxide in the substrate. (Formation of the first cathode layer by galvanizing)

[00758] The first layer 20 can also be formed by a method of galvanization.

[00759] For example, when the substrate is used as a cathode and subjected to electrolytic galvanization in an electrolytic solution containing nickel and tin, nickel and tin alloy galvanizing can be formed. (Formation of the first cathode layer by thermal spray)

[00760] The first layer 20 can also be formed by thermal spraying.

[00761] As an example, the nickel oxide particles sprayed by plasma on the substrate can form a catalyst layer in which the metal nickel and nickel oxide are mixed.

[00762] The electrolysis electrode in the present modality can be integrated with a membrane, such as an ion exchange membrane and a microporous membrane, and used. Thus, the laminate of the present embodiment can be used as an electrode integrated into the membrane. Then, the work of replacing the cathode and anode in electrode renewal is eliminated, and the work efficiency is noticeably improved.

[00763] The electrode integrated into the membrane, such as an ion exchange membrane and a microporous membrane, can make the electrolytic performance comparable or superior to that of a new electrode.

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[00764] In the following, the ion exchange membrane will be described in detail. [Ion exchange membrane]

[00765] The ion exchange membrane is not particularly limited as long as the membrane can be laminated with the electrolysis electrode, and several ion exchange membranes can be used. In the present embodiment, an ion exchange membrane is preferably used which has a membrane body containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and a coating layer provided on at least one surface of the membrane body. It is preferable that the coating layer contains particles of inorganic material and a binder, and the specific surface area of the coating layer is 0.1 to 10 µm / g. The ion exchange membrane that has such a structure has a small influence of the gas generated during electrolysis on electrolytic performance and tends to exert stable electrolytic performance.

[00766] The membrane of a perfluorocarbon polymer into which an ion exchange group is introduced described above includes a layer of sulfonic acid with an ion exchange group derived from a sulfo group (a group represented by -SO3 ', here also called a "sulfonic acid group") or a layer of carboxylic acid with an ion exchange group derived from a carboxyl group (a group represented by -CO ;, here also called a "carboxylic acid group"). From the point of view of strength and dimensional stability, reinforcement core materials are preferably included.

[00767] The particles of inorganic material and binder will be described in detail in the coating layer description section below.

[00768] Figure 44 illustrates a schematic cross-sectional view showing an ion exchange membrane modality. An ion exchange membrane | has a membrane body 10 containing a hydrocarbon polymer or fluorine-containing polymer with a group of

195/803 ion exchange and coating layers 11a and 11b formed on both surfaces of the membrane body 10.

[00769] In the ion exchange membrane 1, the membrane body 10 comprises a layer of sulfonic acid 3 with an ion exchange group derived from a sulfo group (a group represented by -SO3 ', here also called an “acid group sulfonic ”) and a layer of carboxylic acid 2 with an ion exchange group derived from a carboxyl group (a group represented by -CO,; here also called a“ carboxylic acid group ”), and the core materials of reinforcement 4 intensifies strength and dimensional stability. The ion exchange membrane 1, comprising the sulfonic acid layer 3 and the carboxylic acid layer 2, is suitably used as an anion exchange membrane.

[00770] The ion exchange membrane can include the sulfonic acid layer or the carboxylic acid layer. The ion exchange membrane may not necessarily be reinforced by reinforcement core materials, and the arrangement of the reinforcement core materials is not limited to the example in Figure 44. (Membrane body)

[00771] First, the membrane body 10 which constitutes the ion exchange membrane 1 will be described.

[00772] The membrane body 10 must be one that has the function of selectively allowing cations to permeate and comprises a hydrocarbon polymer or a fluorine-containing polymer with an ion exchange group. Its configuration and material are not particularly limited, and the preferred ones can be selected appropriately.

[00773] The hydrocarbon polymer or fluorine-containing polymer with an ion exchange group in the membrane body 10 can be obtained from a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group precursor capable of forming a group of ion exchange

196/803 by hydrolysis or similar. Specifically, for example, after a polymer comprising a fluorinated hydrocarbon backbone that has, as a pendant side chain, a group convertible into an ion exchange group by hydrolysis or similar (precursor to the ion exchange group), and is processable by melting (hereinafter called "fluorine-containing polymer (a)" in some cases), be used to prepare a precursor to the membrane body 10, the membrane body 10 can be obtained by converting the precursor to the ion exchange group in an ion exchange group.

[00774] The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. The fluorine-containing polymer (a) can also be produced by homopolymerizing a monomer selected from any of the following first group, the following second group and the following third group.

[00775] Examples of the monomers of the first group include vinyl fluoride compounds. Examples of the vinyl fluoride compounds include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and perfluoralkyl vinyl ethers. Particularly when the ion exchange membrane is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoro monomer, and a perfluoro monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and perfluoralkylvinyl ethers is preferable.

[00776] Examples of the monomers of the second group include vinyl compounds with a functional group convertible into an ion exchange group of the carboxylic acid type (carboxylic acid group). Examples of vinyl compounds with a functional group convertible to a carboxylic acid group include monomers represented by CF; = CF (OCF; CYF); -

197/803 O (CZF) .- COOR, where s represents an integer from 0 to 2, t represents an integer from 1 to 12, Y and Z each independently represent F or CF; 3, and R represents a lower alkyl group (a lower alkyl group is an alkyl group with 1 to 3 carbon atoms, for example).

[00777] Among them, compounds represented by CF; = CF (OCF; CYF), - O (CF2) n-COOR are preferable. Where n represents an integer from 0 to 2, m represents an integer from 1 to 4, Y represents F or CF; 3, and R represents CH3, CoHs, or C3H ;.

[00778] When the ion exchange membrane is used as a cation exchange membrane for alkaline electrolysis, a perfluoro compound is preferably at least used as the monomer, but the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis and, therefore, the alkyl group (R) need not be a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[00779] Of the monomers above, the monomers shown below are more preferable than the monomers of the second group: CF; = CFOCF; -CF (CF;) OCF; COOCH ;, CF; = CFOCF; CF (CF3) O (CF3) -COOCH ;, CF; = CF [OCF3-CF (CF3) 12O (CF>) - COOCH ;, CF; = CFOCF; CF (CF3) O (CF3); 5COOCH ;, CF3 = CFO (CF3); COOCH; , and CF; = CFO (CF;); COOCH ;.

[00780] Examples of the monomers of the third group include vinyl compounds with a functional group convertible into an ion exchange group of the sulfone type (sulfonic acid group). As vinyl compounds with a functional group convertible to a sulfonic acid group, for example, monomers represented by CF; = CFO-X-CF; -SO, F are preferred, where X represents a perfluoroalkylene group. Specific examples of these include the monomers represented below:

198/803 CF; = CFOCFCFSOF, CF3 = CFOCF; CF (CF3) OCF; CF3SO, F, CF3 = CFOCF; CF (CF3) OCF; CF; CF3SOF, CF3 = CF (CF3); SOF, CF3 = CFO [CF ; CF (CF3) O] 1CF.CFE3SOF, and CF. = CFOCF; CF (CF; OCF3) OCF; CFSO »xF.

[00781] Among them, CF = CFOCF; CF (CF3) OCF; CF; CFSO0.F = and CF; = CFOCF; CF (CF3) OCF; CF3SO, F are more preferable.

[00782] The copolymer obtained from these monomers can be produced by a polymerization method developed for homopolymerization and copolymerization of ethylene fluoride, particularly a general polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, a polymerization reaction can be carried out in the presence of a radical polymerization initiator such as a perfluorocarbon peroxide or an azo compound under the conditions of a temperature of 0 to 200ºC and a pressure of 0, 1 to 20 MPa using an inert solvent such as a perfluorohydrocarbon or a chlorofluorocarbon.

[00783] In the above copolymerization, the type of combination of the above monomers and their proportion are not particularly limited and are selected and determined depending on the type and quantity of the desired functional group to be imparted to the fluorine-containing polymer to be obtained. For example, when a fluorine-containing polymer containing only one carboxylic acid group is formed, at least one monomer must be selected from each of the first group and the second group described above and copolymerized. In addition, when a fluorine-containing polymer containing only one sulfonic acid group is formed, at least one monomer must be selected from each of the first group and the third group and copolymerized. In addition, when a fluorine-containing polymer with a carboxylic acid group and a sulfonic acid group is formed, at least

199/803 a monomer must be selected from each of the first group, the second group and the third group described above and copolymerized. In that case, the target fluorine-containing polymer can also be obtained by separately preparing a copolymer comprising the monomers of the first group and the second group described above and a copolymer comprising the monomers of the first group and the third group described above, and then mixing the copolymers. The mixing ratio of the monomers is not particularly limited, and when the number of functional groups per unit of polymer is increased, the proportion of the selected monomers from the second and third groups described above should be increased.

[00784] The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, more preferably 0.6 to 1.5 mg equivalent / g. The total ion exchange capacity here refers to the exchange group equivalent per unit weight of the dry resin and can be measured by neutralization titration or the like.

[00785] In the membrane body 10 of the ion exchange membrane 1, a layer of sulfonic acid 3 containing a polymer containing fluorine with a group of sulfonic acid and a layer of carboxylic acid 2 containing a polymer containing fluorine with a group of carboxylic acid are laminated. By providing the membrane body 10 with this layer configuration, the selective permeability for cations, such as sodium fons, can be further improved.

[00786] The ion exchange membrane | it is arranged in an electrolyzer in such a way that, generally, the sulfonic acid layer 3 is located on the anode side of the electrolyzer and the carboxylic acid layer 2 is located on the cathode side of the electrolyzer.

[00787] The sulfonic acid layer 3 is preferably constituted

200/803 by a material with low electrical resistance and has a membrane thickness greater than that of the carboxylic acid layer 2 from the point of view of the membrane resistance. The membrane thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, more preferably 3 to 15 times that of the carboxylic acid layer 2.

[00788] The carboxylic acid layer 2 preferably has high anion exclusion properties, even if it has a small membrane thickness. The anion exclusion properties here refer to the property of trying to prevent anion intrusion and permeation into and through the ion exchange membrane 1. In order to increase the anion exclusion properties, it is effective to lay out a layer of carboxylic acid with a small ion exchange capacity to the sulfonic acid layer.

[00789] As the fluorine-containing polymer for use in the sulfonic acid layer 3, a polymer obtained using CF; = CFOCF; CF (CF3) OCF; CF3SO, 3F as the monomer of the third group is preferred.

[00790] As the fluorine-containing polymer for use in the carboxyl acid-2 layer, a polymer obtained using CF; = CFOCF; CF (CF3) O (CF;); COOCH; as the monomer of the second group. (Coating layer)

[00791] The ion exchange membrane preferably has a coating layer on at least one surface of the membrane body. As shown in Figure 44, on the ion exchange membrane 1, the coating layers 11a and 11b are formed on both surfaces of the membrane body 10.

[00792] The coating layers contain particles of inorganic material and a binder.

[00793] The average particle size of the particles of inorganic material is preferably 0.90 µm or more. When the average size of

201/803 particle of inorganic material particles is 0.90 μm or more, the durability to impurities is greatly improved, in addition to gas display. That is, increasing the average particle size of the particles of inorganic material, as well as satisfying the value of the specific surface area mentioned above, can achieve a particularly remarkable effect. Irregular inorganic material particles are preferable because the average particle size and specific surface area, as above, are satisfied. Particles of inorganic material obtained by melting and particles of inorganic material obtained by grinding ore can be used. Particles of inorganic material obtained by grinding raw ore can preferably be used.

[00794] The average particle size of inorganic material particles can be 2 µm or less. When the average particle size of the particles of inorganic material is 2 µm or less, it is possible to avoid damage to the membrane due to the particles of inorganic material. The average particle size of the inorganic material particle is more preferably 0.90 to 1.2 µm.

[00795] Here, the average particle size can be measured by a particle size analyzer (“SALD2200”, SHIMADZU CORPORATION).

[00796] Particles of inorganic material preferably have irregular shapes. Such shapes further improve resistance to impurities. Particles of inorganic material preferably have a wide particle size distribution.

[00797] Particles of inorganic material preferably contain at least one inorganic material selected from the group consisting of oxides of Group IV elements in the Periodic Table, nitrides of Group IV elements in the Periodic Table and carbides of Group IV elements in Periodic table. From the point of view of durability, the particle

202/803 zirconium oxide is more preferable.

[00798] The particles of inorganic material are preferably particles of inorganic material produced by grinding the raw ore of the particles of inorganic material or particles of inorganic material, such as spherical particles with a uniform diameter, obtained by purification by melting the raw ore of the particles of inorganic material.

[00799] Examples of means for grinding raw ore include, but are not particularly limited to, ball mills, ball mills, colloid mills, conical mills, disc mills, roller mills, grain mills, hammer mills, granules, VSI mills, Wiley mills, laminators and jet mills. After grinding, the particles are preferably washed. As a washing method, the particles are preferably treated with acid. This treatment can reduce impurities, such as iron affixed to the surface of particles of inorganic material.

[00800] The coating layer preferably contains a binder. The binder is a component that forms the coating layers retaining particles of inorganic material on the surface of the ion exchange membrane. The binder preferably contains a polymer containing fluorine from the point of view of durability to the electrolytic solution and electrolysis products.

[00801] As the binder, it is preferable a polymer containing fluorine with a carboxylic acid group or a sulfonic acid group, from the point of view of durability to the electrolytic solution and products of electrolysis and adhesion to the surface of the ion exchange membrane. When a coating layer is provided on a layer containing a fluorine-containing polymer with a sulfonic acid group (sulfonic acid layer), a fluorine-containing polymer with a sulfonic acid group is still preferably used as the binder of the coating layer. Alternatively, when

203/803 a coating layer is provided in a layer containing a fluorine-containing polymer with a carboxylic acid group (carboxylic acid layer), a fluorine-containing polymer with a carboxylic acid group is still preferably used as the binder of the coating layer.

[00802] In the coating layer, the content of the particles of inorganic material is preferably 40 to 90% by weight, more preferably 50 to 90% by weight. The content of the binder is preferably 10 to 60% by weight, more preferably 10 to 50% by weight.

[00803] The distribution density of the coating layer on the ion exchange membrane is preferably 0.05 to 2 mg per 1 µm. When the ion exchange membrane has roughness on its surface, the distribution density of the coating layer is preferably 0.5 to 2 mg per 1 in °.

[00804] As the method for forming the coating layer, which is not particularly limited, a known method can be used. An example is a method that includes spraying or the like of a coating liquid obtained by dispersing particles of inorganic material in a solution containing a binder. (Reinforcement core materials)

[00805] The ion exchange membrane preferably has reinforcement core materials arranged within the membrane body.

[00806] The reinforcement core materials are members that enhance the resistance and dimensional stability of the ion exchange membrane. By arranging the reinforcement core materials within the membrane body, particularly the expansion and contraction of the ion exchange membrane can be controlled in the desired range. Such an ion exchange membrane does not expand or contract more than necessary during electrolysis and the like and can maintain excellent dimensional stability in the long run.

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[00807] The configuration of the reinforcement core materials is not particularly limited and, for example, the reinforcement core materials can be formed by spinning threads called reinforcement threads. The reinforcement threads here refer to threads that are members that make up the reinforcement core materials, can provide the desired dimensional stability and mechanical resistance to the ion exchange membrane and can be stably present in the ion exchange membrane. By using the reinforcement core materials obtained by spinning such reinforcement threads, better dimensional stability and mechanical resistance to the ion exchange membrane can be provided.

[00808] The material of the reinforcement core materials and the reinforcement yarns used for them is not particularly limited, but is preferably a material resistant to acids, alkalis, etc., and a fiber comprising a fluorine-containing polymer is preferable because the long-term thermal resistance and chemical resistance are required.

[00809] Examples of the fluorine-containing polymer to be used in the reinforcement core materials include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroethyl vinyl ether (PFA) copolymers, tetrafluoroethylene-ethylene (ETFE) copolymers, tetrafluoroethylene-copolymers, hexetrafluoroethylene-copolymers, tetrafluoroethylene-copolymers. trifluorochlorethylene-ethylene and polymers of vinylidene fluoride (PVDF). Among these, fibers comprising polytetrafluoroethylene are preferably used from the point of view of heat resistance and chemical resistance.

[00810] The wire diameter of the reinforcement threads used for the reinforcement core materials is not particularly limited, but is preferably 20 to 300 deniers, more preferably 50 to 250 deniers. The weave density (tissue count per unit length) is preferably 5 to 50 / inch. The shape of the reinforcement core materials is not particularly limited, for example, a woven fabric, a

205/803 non-woven fabric and a knitted fabric are used, but it is preferably in the form of a woven fabric. The thickness of the woven fabric to be used is preferably 30 to 250 µm, more preferably 30 to 150 µm.

[00811] As woven fabric or knitted fabric, monofilaments, multifilaments, or yarns thereof, a slit yarn, or the like, and various types of weaving methods, such as single weft, leno weft, knitted weft, weft, can be used cord and sirsaca, can be used.

[00812] The weft and arrangement of the reinforcement core materials in the membrane body are not particularly limited, and the preferred arrangement can be adequately provided considering the size and shape of the ion exchange membrane, desired physical properties for the membrane of ion exchange, the environment of use and the like.

[00813] For example, the reinforcement core materials can be arranged along a predetermined direction of the membrane body, but from the point of view of dimensional stability, it is preferable that the reinforcement core materials are arranged over a predetermined first direction, and other reinforcement core materials along a second direction substantially perpendicular to the first direction. By arranging the plurality of reinforcement core materials substantially orthogonally within the membrane body, it is possible to provide better dimensional stability and mechanical strength in several directions. For example, the arrangement in which reinforcement core materials arranged along the longitudinal direction (warp yarns) and reinforcement core materials arranged along the transverse direction (weft threads) are woven on the surface side of the body membrane is preferred. The arrangement is more preferably in the form of driven flat weft and woven fabric allowing the warps and wefts to alternately move between themselves and underneath each other, smooth weft in which two warps are woven into wefts while twisted, weft in driven and woven basket by insertion into two or more

206/803 warps arranged in parallel, wefts of the same or similar number, from the point of view of dimensional stability, mechanical resistance and ease of production.

[00814] It is preferred that, in particular, the reinforcement core materials are arranged along both directions, the MD (Machine Direction) and TD (Transversal Direction) of the ion exchange membrane. In other words, the reinforcement core materials are preferably single woven in MD and TD. Here, MD refers to the direction in which the membrane body and various core materials (for example, the reinforcement core materials, reinforcement wires and sacrificial wires described below) are transported in a production step of ion exchange membrane described later (flow direction) and TD refers to the direction substantially perpendicular to the MD. The threads woven along the MD are called MD threads, and the threads woven along the TD are called TD threads. Typically, the ion exchange membrane used for electrolysis is rectangular, and in many cases, the longitudinal direction is the MD, and the width direction is the TD. By weaving the reinforcement core materials that are MD yarns and the reinforcement core materials that are TD yarns, it is possible to provide better dimensional stability and mechanical strength in many directions.

[00815] The range of arrangement of the reinforcement core materials is not particularly limited, and the preferred arrangement can be adequately provided considering the desired physical properties for the ion exchange membrane, the environment of use and the like.

[00816] The orifice ratio for the reinforcement core materials is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The orifice ratio is preferably 30% or more from the point of view of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the point of view of the mechanical strength of the exchange membrane.

207/803 ionic.

[00817] The orifice ratio for reinforcement core materials refers to a ratio of a total area of a surface through which substances such as fons (an electrolyte solution and cations contained in it (for example, sodium fons)) they can pass (B) to the area of one of the surfaces of the membrane body (A) (B / A). The total surface area through which substances such as fons can pass (B) can refer to the total areas of regions in which the ion exchange membrane, cations, an electrolyte solution and the like are not blocked by the reinforcement core materials and similar substances contained in the ion exchange membrane.

[00818] Figure 45 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane. Figure 45, in which a portion of the ion exchange membrane is enlarged, shows only the arrangement of the reinforcement core materials 21 and 22 in the regions, omitting the illustration of the other members.

[00819] By subtracting the total area of the reinforcement core materials (C) from the area of the region surrounded by the reinforcement core materials 21 arranged along the longitudinal direction and the reinforcement core materials 22 arranged along the transverse direction, the region including the area of the reinforcement core materials (A), the total area of regions through which substances such as phons can pass (B) in the area of the region described above (A) can be obtained. That is, the orifice ratio can be determined by the following formula (1): Orifice ratio = (B) / (A) = ((A) - (C)) / (A) ... (D

[00820] Among the materials of the reinforcement core, a particularly preferred form are highly oriented tape yarns or monofilaments comprising PTFE from the point of view of chemical resistance and heat resistance. Specifically, reinforcement core materials forming a single web in which 50 to 300 tape yarns are used

208/803 denier obtained by cutting a high strength porous sheet comprising PTFE in a tape form, or highly oriented 50 to 300 denier monofilaments comprising PTFE and having a weave density of 10 to 50 threads or monofilaments / inch and have a thickness in the range of 50 to 100 µm are more preferred. The orifice ratio of an ion exchange membrane comprising such reinforcement core materials is still preferably 60% or more.

[00821] Examples of the shape of the reinforcement threads include round threads and ribbon threads. (Continuous holes)

[00822] The ion exchange membrane preferably has continuous holes inside the membrane body.

[00823] Continuous holes refer to holes that can be flow paths for fons generated in electrolysis and an electrolyte solution. The continuous holes, which are tubular holes formed inside the membrane body, are formed by dissolving the sacrificial core materials (or sacrificial threads) described below. The shape, diameter or the like of the continuous holes can be controlled by selecting the shape or diameter of the sacrificial core materials (sacrificial threads).

[00824] Forming the continuous holes inside the ion exchange membrane can guarantee the mobility of an electrolyte solution in electrolysis. The shape of the continuous holes is not particularly limited, but it may be the shape of the sacrificial core materials to be used for forming the continuous holes according to the production method described below.

[00825] The continuous holes are preferably formed so as to pass alternately on the anode side (sulfonic acid layer side) and on the cathode side (carboxylic acid layer side) of the reinforcement core materials. With this structure, in a portion in which continuous holes are formed on the cathode side of the reinforcement core materials, ions

209/803 (eg sodium fons) carried by the electrolyte solution with which the continuous holes are filled can also flow on the cathode side of the reinforcement core materials. As a result, the flow of cations is not interrupted and, therefore, it is possible to further reduce the electrical resistance of the ion exchange membrane.

[00826] The continuous holes can be formed along only a predetermined direction of the membrane body that constitutes the ion exchange membrane, but are preferably formed both in the longitudinal and in the transversal direction of the membrane body from the point of view of presenting a more stable electrolytic performance. [Production method]

[00827] A suitable example of a method for producing an ion exchange membrane includes a method including the following steps (1) to (6): Step (1): the step of producing a fluorine-containing polymer with an exchange group ionic or an ion exchange group precursor capable of forming an ion exchange group by hydrolysis, Step (2): the step of weaving at least a plurality of reinforcement core materials, as required, and sacrificial yarns with a proprietary dissolving in an acid or an alkali, and forming continuous holes to obtain a reinforcement material in which the sacrifice wires are arranged between the reinforcement core materials adjacent to each other, Step (3): the formation step in a fluorine-containing polymer film above with an ion exchange group or a precursor to the ion exchange group capable of forming an ion exchange group by hydrolysis, Step (4): the step of embedding the reinforcement materials above, as required, in the film above to obtain a membrane body within which the reinforcement materials are arranged, Step (5): the hydrolysis step of the membrane body obtained

210/803 in step (4) (hydrolysis step), and Step (6): the step of providing a coating layer on the membrane body obtained in step (5) (application step).

[00828] Next, each of the steps will be described in detail. Step (1): Fluorine-containing polymer production step

[00829] In step (1), the raw material monomers described in the first group for the third group above are used to produce a fluorine-containing polymer. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the raw material monomers must be adjusted in the production of the fluorine-containing polymer that forms the layers. Step (2): Reinforcement materials production step

[00830] The reinforcement material is a woven fabric obtained by weaving reinforcement threads or the like. The reinforcement material is embedded in the membrane to form reinforcement core materials. When an ion exchange membrane with continuous holes is formed, the sacrificial threads are additionally woven into the reinforcement material. The amount of the sacrificial yarns contained in that case is preferably 10 to 80% by weight, more preferably 30 to 70% by weight based on the entire reinforcement material. Weaving the sacrificial yarns can also prevent the yarn from slipping the reinforcement core materials.

[00831] As sacrificial threads, which have solubility in the membrane production stage or under an electrolysis environment, rayon, polyethylene terephthalate (PET), cellulose, polyamide and the like are used. Also preferred are monofilaments or multifilaments having a thickness of 20 to 50 deniers and comprising polyvinyl alcohol and the like.

[00832] In step (2), the orifice ratio, the arrangement of continuous and similar holes can be controlled by adjusting the arrangement of the reinforcement core materials and the sacrifice wires.

Step (3): Film forming step

[00833] In step (3), the fluorine-containing polymer obtained in step (1) is formed into a film using an extruder. The film can be a single layer configuration, a two layer configuration of a sulfonic acid layer and a layer of carboxylic acid, as mentioned above, or a multilayer configuration of three layers or more.

[00834] Examples of the film-forming method include the following: a method in which a fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are formed separately in films; and a method in which the fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are coextruded into a composite film.

[00835] The number of each film can be more than one. Coextrusion of different films is preferred because of their contribution to an increase in adhesive strength at the interface. Stage (4): Stage of obtaining the membrane body

[00836] In step (4), the reinforcement material obtained in step (2) is embedded in the film obtained in step (3) to provide a membrane body including the reinforcement material therein.

[00837] Preferable examples of the method for forming a membrane body include (1) a method in which a fluorine-containing polymer with a precursor to the carboxylic acid group (e.g., carboxylate functional group) (hereinafter, a layer comprising the same called the first layer) located on the cathode side and a fluorine-containing polymer with a precursor to the sulfonic acid group (for example, the sulfonyl fluoride functional group) (hereinafter, a layer

212/803 comprising the same is called the second layer) are formed into a film by a coextrusion method and, using a heat source and a vacuum source as needed, a reinforcement material and the second layer / first composite film layers are laminated in that order on heat-resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated under reduced pressure; and (11) a method in which, in addition to the composite film of the second layer / first layer, a fluorine-containing polymer with a precursor to the sulfonic acid group is formed separately in a film (the third layer) in advance and, using a heat source and a vacuum source as needed, the third layer film, the reinforcement core materials and the composite film comprising the second layer / first layer are laminated in that order on heat resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated under reduced pressure.

[00838] The coextrusion of the first layer and the second layer contributes to an increase in the adhesive strength at the interface.

[00839] The method including integration under reduced pressure is characterized by making the third layer in the reinforcement material thicker than that of the pressure method of applying pressure. In addition, since the reinforcement material is fixed on the inner surface of the membrane body, the method has a property of sufficiently retaining the mechanical resistance of the ion exchange membrane.

[00840] The lamination variations described here are exemplary, and coextrusion can be performed after a preferred lamination pattern (for example, the combination of layers) is appropriately selected

213/803 considering the desired layer configuration of the membrane body and physical properties, and the like.

[00841] In order to further improve the electrical properties of the ion exchange membrane, it is also possible to additionally interpose a fourth layer comprising a fluorine-containing polymer with a precursor of the carboxylic acid group and a precursor of the sulfonic acid group between the first layer and the second layer or using a fourth layer comprising a fluorine-containing polymer with a carboxylic acid group precursor and a sulfonic acid group precursor instead of the second layer.

[00842] The method for forming the fourth layer can be a method in which a fluorine-containing polymer with a carboxylic acid group precursor and a fluorine-containing polymer with a sulfonic acid group precursor are separately produced and then mixed or can be a method wherein a monomer with a precursor to the carboxylic acid group and a monomer with a precursor to the sulfonic acid group are copolymerized.

[00843] When the fourth layer is used as a component of the ion exchange membrane, a coextruded film of the first layer and the fourth layer is formed, in addition, the third layer and the second layer are formed separately in films, and the lamination can be performed by the method mentioned above. Alternatively, the three layers of the first layer / fourth layer / second layer can be simultaneously formed into a film by coextrusion.

[00844] In this case, the direction in which the extruded film flows is the MD. As mentioned above, it is possible to form a membrane body containing a fluorine-containing polymer with an ion exchange group in a reinforcement material.

[00845] Additionally, the ion exchange membrane has

214/803 preferably protruding portions composed of the fluorine-containing polymer with a sulfonic acid group, that is, projections, on the side of the surface composed of the layer of sulfonic acid. As a method for forming such projections, which is not particularly limited, one can also use a known method including forming projections on a resin surface. A specific example of the method is a method of embossing the surface of the membrane body. For example, the above projections can be formed using release paper embossed in advance when the composite film mentioned above, reinforcement material and the like are integrated. In the case where the projections are formed by embossing, the height and density of arrangement of the projections can be controlled by controlling the form of embossing to be transferred (shape of the release paper). (5) Hydrolysis step

[00846] In step (5), a step of hydrolysis of the membrane body obtained in step (4) is performed to convert the precursor of the ion exchange group into an ion exchange group (hydrolysis step).

[00847] In step (5), it is also possible to form dissolution holes in the membrane body by dissolving and removing the sacrifice wires included in the membrane body with acid or alkali. The sacrifice wires can remain in the continuous holes without being completely dissolved and removed. The sacrifice wires that remain in the continuous holes can be dissolved and removed by the electrolyte solution when the ion exchange membrane is subjected to electrolysis.

[00848] The sacrifice wire has solubility in acid or alkali in the production stage of an ion exchange membrane or under an electrolysis environment. The sacrifice wires are eluted to form continuous holes at the corresponding locations.

[00849] Step (5) can be performed by immersing the membrane body

215/803 obtained in step (4) in a hydrolysis solution containing acid or alkali. An example of the hydrolysis solution that can be used is a mixed solution containing KOH and dimethyl sulfoxide (DMSO).

[00850] The mixed solution preferably contains KOH of 2.5 to 4.0 Ne and DMSO of 25 to 35% by weight.

[00851] The temperature for hydrolysis is preferably 70 to 100 ° C. The higher the temperature, the greater the apparent thickness. The temperature is more preferably 75 to 100 ° C.

[00852] The time for hydrolysis is preferably 10 to 120 minutes. The longer the time, the greater the apparent thickness. The time is most preferably 20 to 120 minutes.

[00853] The step of forming continuous holes eluting the sacrificial wire will now be described in more detail. Figures 46 (a) and (b) are schematic views to explain a method for forming the continuous holes in the ion exchange membrane.

[00854] Figures 46 (a) and (b) show the reinforcement threads 52, the sacrifice threads 504a and the continuous holes 504 formed only by the sacrifice threads 504a, omitting the illustration of the other members, such as a body of membrane.

[00855] Firstly, the reinforcement wires 52 constituting reinforcement core materials in the ion exchange membrane and the sacrifice wires 504a to form the continuous holes 504 in the ion exchange membrane are used as interlaced reinforcement materials. Then, in step (5), the sacrifice threads 504a are eluted to form continuous holes 504.

[00856] The above method is simple because the method for interweaving reinforcement wires 52 and sacrifice wires 504a can be adjusted depending on the arrangement of the reinforcement core materials and the continuous holes in the membrane body of the ion exchange membrane.

[00857] Figure 46 (a) exemplifies the fabric reinforcing material

216/803 simple in which the reinforcement threads 52 and the sacrifice threads 504a are interwoven along the longitudinal and lateral direction on the paper, and the arrangement of the reinforcement threads 52 and the sacrifice threads 504a in the reinforcement material can vary as required. (6) Application stage

[00858] In step (6), a coating layer can be formed by preparing a coating liquid containing particles of inorganic material obtained by grinding raw ore or melting raw ore and a binder, applying the coating liquid on the surface of the ion exchange membrane obtained in step (5), and drying of the coating liquid.

[00859] A preferred binder is a binder obtained by hydrolysis of a fluorine-containing polymer with an ion exchange group precursor with an aqueous solution containing dimethylsulfoxide (DMSO) and potassium hydroxide (KOH) and then immersion of the polymer in hydrochloric acid to replace the counter-ion of the ion exchange group with H + (for example, a fluorine-containing polymer with a carboxyl group or a sulfo group). Thus, the polymer is more likely to dissolve in water or ethanol mentioned below, which is preferable.

[00860] This binder is dissolved in a mixed solution of water and ethanol. The volume ratio between water and ethanol is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 2: 1 to 1: 2. The particles of inorganic material are dispersed with a ball mill in the dissolution liquid thus obtained to provide a coating liquid. In this case, it is also possible to adjust the average particle size and the like of the particles by adjusting the time and speed of rotation during dispersion. The preferable amount of the particles of inorganic material and the binder to be mixed is as mentioned above.

[00861] The concentration of particles of inorganic material and the

217/803 binder in the coating liquid is not particularly limited, but a thin-coated liquid is preferable. This allows uniform application to the surface of the ion exchange membrane.

[00862] Additionally, a surfactant can be added to the dispersion when the particles of inorganic material are dispersed. Like the surfactant, nonionic surfactants are preferable and examples of them include HS-210, NS-210, P-210 and E-212 manufactured by NOF CORPORATION.

[00863] The coating liquid obtained is applied on the surface of the ion exchange membrane by spray application or roller coating, thus providing an ion exchange membrane. [Microporous membrane]

[00864] The microporous membrane of the present modality is not particularly limited as long as the membrane can be formed in a laminate with the electrolysis electrode, as mentioned above. Several microporous membranes can be used.

[00865] The porosity of the microporous membrane of the present embodiment is not particularly limited, but it can be from 20 to 90, for example, and is preferably from 30 to 85. The porosity above can be calculated by the following formula: Porosity = (1 - (the weight of the membrane in a dry state) / (the weight calculated from the volume calculated from the thickness, width and length of the membrane and the density of the membrane material)) x 100

[00866] The average pore size of the microporous membrane of the present embodiment is not particularly limited, and can be 0.01 µm to 1 µm, for example, preferably 0.05 µm to 5 µm. Regarding the average pore size, for example, the membrane is cut vertically in the direction of thickness, and the section is observed with an FE-SEM. The average pore size can be obtained by measuring the diameter of about 100 pores

218/803 observed and averaging the measurements.

[00867] The thickness of the microporous membrane of the present embodiment is not particularly limited, and can be from 10 µm to 1000 µm, for example, preferably 50 µm to 600 µm. The above thickness can be measured using a micrometer (manufactured by Mitutoyo Corporation) or similar, for example.

[00868] Specific examples of the microporous membrane as mentioned above include Zirfon Perl UTP 500 manufactured by Agfa (also called Zirfon membrane in the present embodiment) and those described in International Publication No. WO 2013-183584 and International Publication No. WO 2016-203701.

[00869] In the present embodiment, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different EW (ion exchange capacity) than that of the first layer of ion exchange resin. In addition, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different functional group than that of the first layer of ion exchange resin. The ion exchange capacity can be adjusted by the functional group to be introduced, and functional groups that can be introduced are as mentioned above. [Fixed region]

[00870] In the present modality, the electrolysis electrode is fixed in at least one region of a membrane surface, and in the section of <Third modality>, the one or two or more regions are also called fixed regions. The fixed region in the present modality is not particularly limited as long as the region is a portion that has a function of preventing the separation of the electrode for electrolysis from the membrane and fixing the membrane on the electrode for electrolysis. For example, the electrode for

219/803 electrolysis per se can serve as a fixation means to constitute the fixed region, or a fixation member, which is separate from the electrolysis electrode, can serve as a fixation means to constitute the fixed region. The region fixed in this modality can be present only in the position corresponding to the conductive surface during electrolysis or it can extend to the position corresponding to the non-conductive surface. The "conductive surface" corresponds to a portion designed to allow the electrolytes to migrate between the anodic chamber and the cathodic chamber. The "non-conductive surface" means a different portion of the conductive surface.

[00871] In addition, in the present modality, the proportion of the region fixed on the membrane surface (hereinafter, simply also called “proportion 0º”) will be greater than 0% and less than 93%. The ratio above can be determined as the ratio of the area of the fixed region (here below, simply also called "area S3") to the area of the membrane surface (here below, simply also called "area S1" *). In the present embodiment, the membrane surface means the surface on the side where the electrolysis electrode is present between the surfaces possessed by the membrane. The area not covered with the electrolysis electrode on the membrane surface mentioned above is also included in area S1.

[00872] From the point of view of improving stability as a membrane laminate and electrode for electrolysis, the ratio a. (= 100 x S3 / S1) is preferably 0.00000001% or more, more preferably 0.0000001% or more. In contrast, as in the conventional technique, in the case of the membrane and the electrode firmly adhering to each other over the entire contact surface between them by a method such as thermal compression (that is, the case where the proportion is 100%), all the electrode contact surface sinks into the membrane to physically adhere to it. Such a portion of adherence inhibits the sodium fons from migrating in the membrane, thereby significantly increasing the tension. In the present modality, from the point of

220/803 In view of providing sufficient space for the fons to migrate freely, the above ratio is less than 93%, preferably 90% or less, more preferably 70% or less, even more preferably less than 60%.

[00873] In the present modality, from the point of view of achieving a better electrolytic performance, it is preferable to adjust the area of the corresponding portion only to the conductive surface (hereinafter, simply also called “area S3”) of the area of the fixed region ( area S3). That is, it is preferable to adjust the proportion of the area S3 '(hereinafter, simply also called "proportion to") to the area of the conductive surface (hereinafter, simply also called "area S2"). The S2 area can be identified as the electrode surface area for electrolysis (details will be mentioned below). Specifically, in the present embodiment, the B8 ratio (= 100 x S3 '/ S2) is preferably greater than 0% and less than 100%, more preferably 0.0000001% or more and less than 83%, even more preferably 0.000001 % or more and 70% or less, even more preferably 0.00001% or more and 25% or less.

[00874] The proportions a and a described above can be measured, for example, as follows.

[00875] First, the surface area of the S1 membrane is calculated. Then, the electrode area for electrolysis S2 is calculated. The areas S1 and S2 here can be identified as the area when the membrane laminate and the electrolysis electrode is viewed from the side of the electrolysis electrode (see Figure 57).

[00876] The shape of the electrolysis electrode is not particularly limited, and the electrode may have openings. In the case where the form is liquid or similar, which has openings, and the opening ratio is less than 90% (1), as for S2, its opening portions are included in the S2 area. In contrast, in the case where the opening ratio is 90% or more (ii), the area excluding the opening portions is used to calculate S2 in order to obtain a

221/803 sufficient electrolytic performance. The opening ratio referred to here is a numerical value (%; 100 x S / S ”) obtained by dividing the total area of the opening portions S 'in the electrolysis electrode by the area in the electrolysis electrode S”', which is obtained when the opening portions are included in the area.

[00877] The area of the fixed region (area S3 and area S3 ') will be mentioned below.

[00878] As described above, the proportion of the O (%) region on the membrane surface can be determined by calculating 100 x (S3 / S1). Additionally, the proportion of the portion area that corresponds only to the conductive surface of the fixed region B (%) in relation to the area of the conductive surface can be determined by calculating 100 x (S3 ”/ S2).

[00879] More specifically, the measurement can be performed by a method described in the Example mentioned below.

[00880] The surface area of the S1 membrane to be identified as mentioned above is not particularly limited, but is preferably 1 time or more and 5 times or less, more preferably | once or more and 4 times or less, even more preferably | times or more and 3 times or less the area of the conductive surface S2.

[00881] In the present modality, a fixation configuration in the fixed region is not intended to be limited, but, for example, a fixation configuration exemplified below can be used. Only one fixture configuration can be used, or two or more fixture configurations can be used in combination.

[00882] In the present embodiment, at least a portion of the electrolysis electrode preferably penetrates the membrane and, therefore, is fixed in the fixed region. The appearance will be described using Figure 47A.

[00883] In Figure 47A, at least a portion of the electrolysis electrode 2 penetrates the membrane 3 and is thus fixed. As shown in Figure 47A, the electrolysis electrode portion 2 is penetrating the

222/803 membrane 3. Figure 47A shows an example where electrode for electrolysis 2 is a porous metallic electrode. That is, in Figure 47A, a plurality of electrode electrode portions 2 are shown separately, but these portions are continuous. Thus, the cross section of an integral porous metallic electrode is shown (the same applies to Figures 48 to 51 below).

[00884] In the electrode configuration, when the membrane 3 in the predetermined position (position to be the fixed region), for example, is pressed in the electrode for electrolysis 2, a portion of the membrane 3 penetrates the roughness geometry or the opening geometry on the electrode surface for electrolysis 2. Then, recesses on the electrode surface and the projections around the openings penetrate the membrane 3 and preferably penetrate through the outer surface 3b of the membrane 3, as shown in Figure 47A.

[00885] As described above, the fixation configuration in Figure 47A can be produced by pressing membrane 3 on the electrolysis electrode 2. In this case, membrane 3 is softened by heating and then subjected to thermal compression and thermal suction. Then, electrolyte electrode 2 penetrates membrane 3. Alternatively, membrane 3 can be used in a melting state. In that case, the membrane 3 is preferably aspirated from the outer surface side 2b (rear surface side) of the electrolysis electrode 2 in the state shown in Figure 47B. The region in which membrane 3 is pressed on electrode for electrolysis 2 constitutes the “fixed region”.

[00886] The fixation configuration shown in Figure 47A can be seen by an magnifier (magnifying glass), an optical microscope or an electron microscope. Once the electrolysis electrode 2 has penetrated the membrane 3, it is possible to estimate the fixation configuration in Figure 47A by a conduction test between the outer surface 3b of the membrane 3 and the

223/803 external surface 2b of the electrode for electrolysis 2 using a tester or similar.

[00887] In Figure 47A, no electrolyte solution in the anodic chamber and the cathodic chamber divided by the membrane preferably permeate the penetration portion. Thus, the pore size in the penetration portion is preferably small enough not to allow the electrolyte solution to permeate the portion. Specifically, characteristics comparable to those of a membrane without a penetrating portion are preferably exercised when conducting an electrolytic test. Alternatively, the penetration portion is preferably subjected to processing to prevent permeation of the electrolyte solution. It is preferable to use, in the penetration portion, a material that is not eluted or decomposed by the electrolytic solution of the anodic chamber, products to be generated in the anodic chamber, the electrolytic solution of the cathodic chamber and products to be generated in the cathodic chamber. For example, EPDM and fluorine-containing resins are preferable. A fluorine resin with an ion exchange group is more preferable.

[00888] In the present embodiment, at least a portion of the electrolysis electrode is preferably located within the membrane and, therefore, fixed in the fixed region. The appearance will be described using Figure 48A.

[00889] As described above, the electrode surface for electrolysis 2 has a roughness geometry or opening geometry. In the embodiment shown in Figure 48A, a portion of the electrode surface enters the membrane 3 at the predetermined position (position to be the fixed region) and is attached to it. The fixation configuration shown in Figure 48A can be produced by pressing the membrane 3 on the electrolysis electrode 2. In that case, the fixation configuration in Figure 48A is preferably formed by softening the membrane 3 by heating and then by thermal compression and thermal aspiration of the membrane 3. Alternatively, the configuration

224/803 of attachment in Figure 48A can be formed by melting the membrane 3. In that case, the membrane 3 is preferably aspirated from the side of the outer surface 2b (side of the rear surface) of the electrode for electrolysis 2.

[00890] The fixation configuration shown in Figure 48A can be observed by an magnifier (magnifying glass), an optical microscope or an electron microscope. Particularly preferable is a method that includes subjecting the sample to an inlay treatment, then forming a cross section by a microtome and observing the cross section. In the fixation configuration shown in Figure 48A, the electrolysis electrode 2 does not penetrate the membrane 3. Thus, no conduction between the outer surface 3b of the membrane 3 and the outer surface 2b of the electrolysis electrode 2 is identified by the conduction test.

[00891] In the present embodiment, it is preferable to additionally have a fixing member to fix the membrane and electrode for electrolysis. The appearance will be described using Figures 49A to C.

[00892] The fixation configuration shown in Figure 49A is a configuration in which a fixation member 7, which is separated from the electrolyte electrode 2 and the membrane 3, is used and the fixation member 7 penetrates and thereby fixes the electrode for electrolysis 2 and the membrane 3. The electrolysis electrode 2 is not necessarily penetrated by the fixing member 7, and must be fixed by the fixing member 7 so as not to be separated from the membrane 2. The material for the fixing member 7 it is not particularly limited, and materials consisting of metal, resin or the like, for example, can be used as the fixing member 7. Examples of the metal include nickel, nichrome, titanium and stainless steel (SUS). Oxides of the same can be used. Examples of the resin that can be used include fluorine resins (eg, polytetrafluoroethylene (PTFE), tetrafluoroethylene and perfluoroalkoxyethylene (PFA) copolymers, tetrafluoroethylene and ethylene (ETFE) copolymers, membrane materials 3 described below, fluoride fluoride

225/803 polyvinylidene (PVDF), ethylene-propylene-diene rubber (EPDM), polyethylene (PP), polypropylene (PE), nylon and aramid.

[00893] In the present embodiment, for example, a wire-type fixing member (metal or wire-type resin) is used to sew the predetermined position (position to be the fixed region) between the outer surface 2b of the electrode for electrolysis 2 and the outer surface 3b of membrane 3, as shown in Figures 49B and C. The yarn-like resin is not particularly limited, but examples of it include PTFE yarns. It is also possible to fix the electrolysis electrode 2 to the membrane 3, using a fixation mechanism, such as a fixation device.

[00894] In Figures 49A to C, no electrolyte solution in the anodic chamber and the cathodic chamber divided by the membrane preferably permeate the penetration portion. Thus, the pore size in the penetration portion is preferably small enough not to allow the electrolyte solution to permeate the portion. Specifically, characteristics comparable to those of a membrane without a penetrating portion are preferably exercised when conducting an electrolytic test. Alternatively, the penetration portion is preferably subjected to processing to prevent permeation of the electrolyte solution. It is preferable to use, in the penetration portion, a material that is not eluted or decomposed by the electrolytic solution of the anodic chamber, products to be generated in the anodic chamber, the electrolytic solution of the cathodic chamber and products to be generated in the cathodic chamber. For example, EPDM and fluorine-containing resins are preferable. A fluorine resin with an ion exchange group is more preferable.

[00895] The fixation configuration shown in Figure 50 is a configuration in which the fixation is made by an organic resin (adhesion layer) interposed between the electrolyte electrode 2 and the membrane 3. That is, in Figure 50, it is shown a configuration in which an organic resin

226/803 as the fixing member 7 is arranged in the predetermined position (position to be the fixed region) between the electrolysis electrode 2 and the membrane 3 to thus fix by adhesion. For example, the organic resin applied to the inner surface 2a of the electrolysis electrode 2, the inner surface 3a of the membrane 3, or one or both of the inner surface 2a of the electrode for electrolysis 2 and the inner surface 3a of the membrane 3. So, the fixation configuration shown in Figure 50 can be formed by laminating the electrolyte electrode 2 to the membrane 3. The materials for the organic resin are not particularly limited, but examples of the same that can be used include fluorine resins (for example, PTFE, PFA and ETFE) and resins similar to the materials that make up membrane 3 as mentioned above. Commercially available fluoride-containing adhesives and PTFE dispersions can also be used as appropriate. In addition, multipurpose vinyl acetate adhesives, ethylene-vinyl acetate copolymer adhesives, acrylic resin adhesives, a-olefin adhesives, styrene-butadiene rubber latex adhesives, vinyl chloride resin adhesives, adhesives chloroprene, nitrile rubber adhesives, urethane rubber adhesives, epoxy adhesives, silicone resin adhesives, modified silicone adhesives, epoxy modified silicone resin adhesives, silylated urethane resin adhesives, cyanoacrylate adhesives and the like can be used.

[00896] In the present modality, organic resins that dissolve in an electrolyte solution or dissolve or decompose during electrolysis can be used. Examples of organic resins that dissolve in an electrolyte solution or dissolve or decompose during electrolysis include, but are not limited to, vinyl acetate adhesives, ethylene vinyl acetate copolymer adhesives, acrylic resin adhesives, air-olefin, styrene-butadiene rubber latex adhesives, vinyl chloride resin adhesives, chloroprene adhesives,

227/803 nitrile adhesives, urethane rubber adhesives, epoxy adhesives, silicone resin adhesives, modified silicone adhesives, epoxy modified silicone resin adhesives, silylated urethane resin adhesives and cyanoacrylate adhesives.

[00897] The fixation configuration shown in Figure 50 can be observed by an optical microscope or electron microscope. Particularly preferable is a method that includes subjecting the sample to an inlay treatment, then forming a cross section by a microtome and observing the cross section.

[00898] In the present embodiment, at least a portion of the fixation member preferably externally holds the membrane and electrode for electrolysis. The aspect will be described using the Figure SIA.

[00899] The fixation configuration shown in Figure SIA is a configuration in which the electrolysis electrode 2 and the membrane 3 are attached and fixed externally. That is, the outer surface 2b of the electrolysis electrode 2 and the outer surface 3b of the membrane 3 are sandwiched and fixed by a gripping member such as the fixation member 7. In the fixation configuration shown in Figure SIA, a state in which the gripping member is engaging the electrolysis electrode 2 and the membrane 3 is also included. Examples of the gripping member include tape and clips.

[00900] In the present modality, a gripping member that dissolves in an electrolyte solution can be used. Examples of the gripping member that dissolves in an electrolyte solution include PET tape and clips and PVA tapes and clips.

[00901] In the fixation configuration shown in Figure SIA, unlike Figures 47 to 50, the electrolysis electrode 2 and the membrane 3 are not joined at the interface between them, but the inner surface 2a of the electrolysis electrode 2 and the inner surface 3a of membrane 3 are

228/803 just touching or opposite each other. Removing the gripping member can release the fixed state of the electrolysis electrode 2 and the membrane 3 and separate the electrolysis electrode 2 from the membrane 3.

[00902] Although not shown in Figure SIA, it is also possible to fix the electrode for electrolysis 2 and the membrane 3 using a gripping member in an electrolytic cell.

[00903] For example, it is possible to fold the PTFE tape back to fix the membrane and the electrode in a sandwiched manner.

[00904] Also in the present embodiment, at least a portion of the fixation member preferably fixes the membrane and the electrode for electrolysis by magnetic force. The aspect will be described using Figure S1B.

[00905] The fixation configuration shown in Figure SIB is a configuration in which the electrolyte electrode 2 and the membrane 3 are attached and fixed externally. The difference from Figure S1A is that a pair of magnets is used as the gripping member, which is the fixing member. In the aspect of the fastening configuration shown in Figure S1B, a laminate | is attached to the electrolyser. Thereafter, during the operation of the electrolyser, the gripping member can be left as is or removed from the laminate |.

[00906] Although not shown in Figure S1B, it is also possible to fix the electrode for electrolysis 2 and the membrane 3 using a gripping member in an electrolytic cell. When a magnetic material that adheres to magnets is used as part of the material for the electrolytic cell, a gripping material is placed on the surface side of the membrane. Then, the gripping material and the electrolytic cell can sandwich and fix the electrolyte electrode 2 and the membrane 3 between them.

[00907] A plurality of fixed region lines can be provided. That is, 1, 2,3, ... n fixed region lines can be arranged on the contour side

229/803 towards the inner side of laminate 1. n is an integer of 1 or more. The mth fixed region line (m <n) and the Lth fixed region line (m <L <n) can be formed to have a different fixation pattern.

[00908] A fixed region line to be formed in the electroconductive portion preferably has a symmetrical line shape. This tends to allow the stress concentration to be controlled. For example, when two orthogonally intersecting directions are called the X direction and the Y direction, it is possible to configure the fixed region by arranging a fixed region line, each in the X direction and in the Y direction, or arranging a plurality of region lines fixed at equal intervals, each in the X direction and in the Y direction. The number of fixed region lines in the X direction and in the Y direction is not limited, but is preferably 100 or less each in the X direction and the Y direction. From the point of view of achieving the flatness of the electroconductive portion, the number of lines in the fixed region is preferably 50 or less, each, in the X and Y directions.

[00909] When the fixed region in the present embodiment has the fixation configuration shown in Figure 47A or Figure 49, a sealing material is preferably applied to the membrane surface of the fixed region in order to prevent a short circuit caused by a contact between the anode and the cathode. As a sealing material, the materials described for the adhesives above can be used.

[00910] When a fixation member is used, when determining area S3 and area S3 ', as for the portion on which the fixation member overlaps, the overlapping part is not included in area S3 and area S3'. For example, when fixing is done using the PTIFE wires mentioned above as the fixing members, the portion in which the PTFE wires cross each other is not included as an overlapping part in the area. When fixing is done using the PTFE tapes mentioned above as the fixing members, the portion in which the PTFE tapes cross each other is not included

230/803 as an overlapping part in the area.

[00911] When the fixation is done using the PTFE wire or adhesive mentioned above as the fixing member, the area present on the rear side of the electrolysis electrode and / or the membrane is also included in area S3 and area S3 '.

[00912] The laminate in the present embodiment may have several fixed regions in various positions as mentioned above, but the electrolysis electrode preferably satisfies the "applied force" mentioned above particularly in a portion in which no fixed region is present (non-fixed region) . That is, the force applied per unit of mass-unit area of the electrode for electrolysis in the non-fixed region is preferably less than 1.5 N / mg: -em ?. [Electrolyser]

[00913] The electrolyzer of the present modality includes the laminate of the present modality. Hereinafter, the case of conducting common salt electrolysis using an ion exchange membrane as the membrane is taken as an example, and an embodiment of the electrolyzer will be described in detail. [Electrolytic cell]

[00914] Figure 52 illustrates a cross-sectional view of an electrolytic cell 1.

[00915] The electrolytic cell 1 comprises an anodic chamber 10, a cathodic chamber 20, a partition wall 30 placed between the anodic chamber 10 and the cathodic chamber 20, an anode 11 placed in the anodic chamber and a cathode 21 placed in the cathodic chamber 20 As required, the electrolytic cell 1 has a substrate 18a and a reverse current absorbent layer 18b formed on the substrate 18a and can comprise a reverse current absorber 18 placed in the cathode chamber. Anode 11 and cathode 21 belonging to electrolytic cell 1 are electrically connected

231/803 each other. In other words, the electrolytic cell 1 comprises the following cathode structure. The cathode structure 40 comprises the cathode chamber 20, the cathode 21 placed in the cathode chamber 20 and the reverse current absorber 18 placed in the cathode chamber 20, the reverse current absorber 18 has the substrate 18a and the reverse current absorbent layer 18b on substrate 18a, as shown in Figure 56, and cathode 21 and reverse current absorbing layer 18b are electrically connected. The cathodic chamber 20 also has a collector 23, a support 24 supporting the collector and an elastic metal body 22. The elastic metal body 22 is placed between the collector 23 and the cathode 21. The support 24 is placed between the collector 23 and the partition wall 30. The collector 23 is electrically connected to the cathode 21 through the elastic metal body 22. The partition wall 30 is electrically connected to the collector 23 through the support 24. Therefore, the partition wall 30, the support 24, the collector 23, the elastic metal body 22 and the cathode 21 are electrically connected. Cathode 21 and reverse current absorbing layer 18b are electrically connected. Cathode 21 and the reverse current absorbing layer can be directly connected or they can be indirectly connected through the collector, the support, the elastic metal body, the partition wall or the like. The entire surface of cathode 21 is preferably covered with a layer of catalyst for the reduction reaction. The electrical connection form can be a form in which the partition wall 30 and the support 24, the support 24 and the collector 23, and the collector 23 and the elastic metal body 22 are each directly attached and the cathode 21 it is laminated to the elastic metal body 22. Examples of a method for directly affixing these constituent components to each other include welding and the like. Alternatively, the reverse current absorber 18, cathode 21 and collector 23 can be collectively called a cathode structure 40.

[00916] Figure 53 illustrates a cross-sectional view of two

232/803 electrolytic cells 1 that are adjacent in the electrolyzer 4. Figure 54 shows an electrolyzer 4. Figure 55 shows an electrolyzer assembly step 4. As shown in Figure 53, an electrolytic cell 1, a cation exchange membrane 2 and an electrolytic cell 1 are arranged in series in the order mentioned. An ion exchange membrane 2 is arranged between the anode chamber of an electrolytic cell 1 between the two adjacent electrolytic cells in the electrolyzer and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent to it are separated by the cation exchange membrane 2. As shown in Figure 54, the electrolyzer 4 is composed of a plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer comprising the plurality of electrolytic cells 1 arranged in series and ion exchange membranes 2, each arranged between adjacent electrolytic cells 1. As shown in Figure 55, electrolyzer 4 is assembled arranging the plurality of cells electrolytics 1 in series through the ion exchange membrane 2 and coupling the cells by means of a pressure device 5.

[00917] Electrolyser 4 has an anodic terminal 7 and a cathodic terminal 6 to be connected to a power source. Anode 11 of electrolytic cell 1 located at the far end between the plurality of electrolytic cells 1 coupled in series in electrolyzer 4 is electrically connected to anode terminal 7. Cathode 21 of the electrolytic cell located at the opposite end to anode terminal 7 between the plurality of electrolytic cells 1 coupled in series in the electrolyzer 4 is electrically connected to the cathodic terminal 6. The electrical current during electrolysis flows from the side of the anodic terminal 7, through the anode and cathode of each electrolytic cell 1, towards the cathodic terminal 6. At the two ends of the coupled electrolytic cells 1, an electrolytic cell with

233/803 only an anodic chamber (anodic terminal cell) and an electrolytic cell with only one cathodic chamber (cathodic terminal cell) can be arranged. In that case, anode terminal 7 is connected to the cell of the anode terminal, arranged at one end, and cathode terminal 6 is connected to the cell of the cathode terminal, arranged at the other end.

[00918] In the case of electrolytic brine, brine is provided for each anodic chamber 10 and pure water or an aqueous solution of low concentration sodium hydroxide is provided for each cathodic chamber 20. Each liquid is supplied from a supply tube of electrolytic solution (not shown in the Figure), through an electrolytic solution supply hose (not shown in the Figure), for each electrolytic cell 1. The electrolyte solution and electrolysis products are recovered from an electrolyte recovery tube (not shown in the figure). During electrolysis, the sodium ions in the brine migrate from the anode chamber 10 of the electrolytic cell 1, through the ion exchange membrane 2, to the cathode chamber 20 of the adjacent electrolytic cell 1. Thus, the electric current during electrolysis flows in the direction wherein electrolytic cells 1 are coupled in series. That is, the electric current flows, through the cation exchange membrane 2, from the anodic chamber 10 towards the cathodic chamber 20. As the brine is electrolyzed, chlorine gas is generated on the anode side 11, and sodium hydroxide (solute ) and hydrogen gas are generated on the cathode side

21. (Anodic chamber)

[00919] The anodic chamber 10 has anode 11 or the anode supply conductor 11. When the electrode for electrolysis in the present mode is inserted on the anode side, 11 serves as the anode supply conductor. When the electrode for electrolysis in the present modality is not inserted on the anode side, 11 serves as the anode. Anodic chamber 10 has an electrolyte solution supply unit

234/803 on the anode side that provides an electrolytic solution for the anode chamber 10, a deflector plate that is arranged above the anode side electrolyte solution supply unit so as to be substantially parallel or oblique to the partition wall 30, and a liquid and gas separation unit on the anode side arranged above the baffle to separate the gas from the electrolytic solution including the mixed gas. (Anode)

[00920] When the electrode for electrolysis in the present mode is not inserted on the anode side, anode 11 is provided in the anode chamber 10 frame. As anode 11, a metal electrode such as the so-called DSA (R) can be used . DSA is an electrode that includes a titanium substrate whose surface is covered with an oxide that contains ruthenium, iridium and titanium as components.

[00921] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Anode feed conductor)

[00922] When the electrode for electrolysis in this mode is inserted on the anode side, the anode 11 feeder conductor is provided in the anode chamber 10 frame. As the anode 11 feeder conductor, a metal electrode can be used , such as the so-called DSA (R), and titanium without catalyst coating can also be used. Alternatively, DSA with a thinner catalyst coating can also be used. In addition, a used anode can also be used.

[00923] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used.

235/803 (Anode side electrolyte solution supply unit)

[00924] The electrode solution supply unit on the anode side, which supplies the electrolyte solution to the anodic chamber 10, is connected to the electrolyte solution supply tube. The electrolytic solution supply unit on the anode side is preferably arranged below the anode chamber 10. As the electrolytic solution supply unit on the anode side, for example, a tube can be used on the surface from which orifice portions are formed. (dispersion tube) and the like. Such a tube is most preferably arranged along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell. This tube is connected to an electrolytic solution supply tube (liquid supply nozzle) that supplies the electrolytic solution to the electrolytic cell 1. The electrolyte solution supplied from the liquid supply nozzle is transported with a tube into the electrolytic cell 1 and supplied from the orifice portions provided on the surface of the tube into the anodic chamber 10. The arrangement of the tube along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell is preferable because the electrolyte solution can be uniformly supplied into the anodic chamber

10. (Liquid and gas separation unit on the anode side)

[00925] The liquid and gas separation unit on the anode side is preferably arranged above the baffle plate. The liquid and gas separation unit on the anode side has the function of separating the produced gas such as chlorine gas from the electrolytic solution during electrolysis. Unless otherwise specified, above means the upper direction in electrolytic cell 1 in Figure 52, and below means the lower direction in electrolytic cell 1 in Figure 52.

[00926] During electrolysis, the produced gas generated in electrolytic cell 1 and the electrolytic solution form a mixed phase (gas-gas mixed phase)

236/803 liquid), which is then emitted out of the system. Subsequently, pressure fluctuations within the electrolytic cell 1 cause vibration, which can result in physical damage to the ion exchange membrane. In order to avoid this event, the electrolytic cell 1 in the present embodiment is preferably provided with a liquid and gas separation unit on the anode side to separate the gas from the liquid. The liquid and gas separation unit on the anode side is preferably provided with an anti-foam plate to eliminate bubbles. When the flow of the mixed gas-liquid phase passes through the antifoam plate, the bubbles burst, thus allowing the electrolyte solution and the gas to be separated. As a result, vibration during electrolysis can be avoided.

(Baffle plate)

[00927] The baffle plate is preferably arranged above the electrolyte solution supply unit on the anode side and arranged substantially in parallel or obliquely to the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. When the deflector plate is provided, it is possible to make the electrolyte solution (brine or similar) circulate internally in the anodic chamber 10 to thus make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged in such a way as to separate the space in the vicinity of anode 11 from the space near the partition wall 30. From such a point of view, the baffle plate is preferably placed so as to be opposite the surface of anode 11 and the surface of the dividing wall 30. In the space next to the anode divided by the deflector plate, as the electrolysis progresses, the concentration of the electrolytic solution (brine concentration) is reduced and the gas produced, such as chlorine gas is generated. This results in a difference in specific gas-liquid gravity between the space near anode 11 and the space near the dividing wall 30 divided by the deflector plate. By using difference, it is

237/803 it is possible to promote the internal circulation of the electrolytic solution in the anodic chamber 10 to thus make the distribution of concentration of the electrolytic solution in the anodic chamber 10 more uniform.

[00928] Although not shown in Figure 52, a collector can be additionally provided inside the anodic chamber 10. The material and configuration of such a collector can be the same as the cathode chamber collector mentioned below. In anode chamber 10, anode 11 per se can also serve as a collector. (Partition wall)

[00929] The partition wall 30 is arranged between the anodic chamber 10 and the cathodic chamber 20. The partition wall 30 can be called a separator, and the anodic chamber 10 and the cathodic chamber 20 are divided by the partition wall 30. Like the wall partition 30, one known as electrolysis separator can be used, and an example of this includes a partition wall formed by welding a plate comprising nickel next to the cathode and a plate comprising titanium beside the anode. (Cathodic chamber)

[00930] In the cathodic chamber 20, when the electrode for electrolysis in the present modality is inserted on the cathode side, 21 serves as a cathode supply conductor. When the electrolysis electrode in the present embodiment is not inserted on the cathode side, 21 it serves as a cathode. When a reverse current absorber is included, the cathode or cathode supply conductor 21 is electrically connected to the reverse current absorber. The cathode chamber 20, similarly to the anode chamber 10, preferably has an electrolytic solution supply unit on the cathode side and a liquid and gas separation unit on the cathode side. Among the components that make up the cathodic chamber 20, components similar to those that make up the anode chamber 10 will not be described.

238/803 (Cathode)

[00931] When the electrode for electrolysis in the present embodiment is not inserted on the side of the cathode, a cathode 21 is provided in the frame of the cathodic chamber 20. The cathode 21 preferably has a nickel substrate and a catalyst layer that covers the substrate of nickel. Examples of the components of the catalyst layer on the nickel substrate include metals such as Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, alloy galvanizing, composite dispersion / galvanizing, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Cathode 21 can be subjected to a reduction treatment as needed. As the cathode 21 substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[00932] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Cathode supply conductor)

[00933] When the electrolysis electrode in the present embodiment is inserted on the side of the cathode, a cathode 21 conductor is provided in the cathode chamber 20 frame. The cathode 21 catheter can be covered with a catalytic component. The catalytic component can be a component that is originally used as the cathode and remains. Examples of the catalyst layer components include metals such as Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr,

239/803 Nb, Mo, Rh, Pd, Ag, Cd, Tn, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm , Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, alloy galvanizing, composite dispersion / galvanizing, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Nickel, nickel alloys and nickel or stainless galvanized iron without catalyst coating can be used. As the cathode 21 feed conductor substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[00934] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Reverse current absorbing layer)

[00935] A material with a less noble redox potential than the element's redox potential for the catalyst layer of the cathode mentioned above can be selected as a material for the reverse current absorbing layer. Examples of it include nickel and iron. (Collector)

[00936] The cathodic chamber 20 preferably comprises the collector

23. Collector 23 improves the efficiency of the current collection. In the present embodiment, the collector 23 is a porous plate and is preferably arranged substantially parallel to the surface of the cathode 21.

[00937] The collector 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. Collector 23 can be a mixture, alloy or composite oxide of these metals. Collector 23 can have any shape, as long as the shape allows the function of the collector and

240/803 may have a plate or network shape. (Elastic metal body)

[00938] Placing the elastic metal body 22 between the collector 23 and the cathode 21 presses each cathode 21 of the plurality of electrolytic cells 1 connected in series to the ion exchange membrane 2 to reduce the distance between each anode 11 and each cathode 21. Then, it is possible to reduce the voltage to be applied entirely through the plurality of electrolytic cells 1 connected in series. Reducing the voltage reduces energy consumption. With the elastic metal body 22 in place, the pressure caused by the elastic metal body 22 allows the electrolysis electrode to be held steadily in place when the laminate including the electrolysis electrode according to the present embodiment is placed in the electrolytic cell.

[00939] As the elastic metal body 22, spring members such as spiral springs and coils and damping mats can be used. As the elastic metal body 22, a suitable one can be used appropriately, taking into account a tension to pressure the ion exchange membrane and the like. The elastic metal body 22 can be provided on the surface of the collector 23 on the side of the cathode chamber 20 or it can be provided on the surface of the partition wall on the side of the anode chamber 10. Both chambers are normally divided in such a way that the cathode chamber 20 it becomes smaller than the anodic chamber 10. Thus, from the point of view of the strength of the frame and the like, the elastic metal body 22 is preferably provided between the collector 23 and the cathode 21 in the anodic chamber

20. The elastic metal body 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. (Support)

[00940] The cathodic chamber 20 preferably comprises the support 24 that electrically connects the collector 23 to the partition wall 30. This can achieve an efficient current flow.

241/803

[00941] The support 24 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. The support 24 can have any shape as long as the support can support the collector 23 and can have a rod, plate or network shape. The support 24 has a plate shape, for example. A plurality of supports 24 is arranged between the partition wall 30 and the collector 23. The plurality of supports 24 are aligned in such a way that their surfaces are in parallel with each other. The supports 24 are arranged substantially perpendicular to the partition wall 30 and the collector 23.

(Anode-side gasket and cathode-side gasket)

[00942] The anode-side gasket is preferably arranged on the surface of the structure that constitutes the anode chamber 10. The cathode-side gasket is preferably arranged on the surface of the structure that constitutes the cathodic chamber 20. The electrolytic cells are connected to each other others such that the anode-side gasket included in an electrolytic cell and the cathode-side gasket of an electrolytic cell adjacent to the cell sandwich the ion exchange membrane 2 (see Figures 52 and 53). These gaskets can make the connection points airtight when the plurality of electrolytic cells 1 is connected in series through the ion exchange membrane 2.

[00943] The gaskets form a seal between the ion exchange membrane and the electrolytic cells. Specific examples of gaskets include picture frame rubber sheets, in the center of which a hole portion is formed. Gaskets are required to be resistant to corrosive electrolyte solutions or gas produced and to be usable for a long period. Thus, with regard to chemical resistance and hardness, vulcanized products and products cross-linked with ethylene-propylene-diene rubber peroxide (EPDM rubber) and ethylene-propylene rubber (EPM rubber) are normally used as gaskets. Alternatively,

242/803 gaskets from which the region to be in contact with liquid (liquid contact portion) with a fluorine-containing resin such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers can be used as needed. Such gaskets may have an orifice portion so as not to inhibit the flow of the electrolyte solution, and the shape of the orifice portion is not particularly limited. For example, a picture frame gasket is affixed with an adhesive or similar along the peripheral edge of each hole portion of the anodic chamber frame that constitutes the anodic chamber 10 or the cathodic chamber frame that constitutes the cathodic chamber 20. So, for example, in the case where the two electrolytic cells 1 are connected via the ion exchange membrane 2 (see Figure 53), each electrolytic cell 1 to which the gasket is attached must be tightened via the ion exchange membrane 2. This Tightening can prevent the electrolyte solution, alkali metal hydroxide, chlorine gas, hydrogen gas and the like, generated from electrolysis, from escaping from electrolytic cells 1. (Ion exchange membrane 2)

[00944] The ion exchange membrane 2 is as described in the section of the ion exchange membrane described above. (Water electrolysis)

[00945] The electrolyzer of the present modality, like an electrolyzer in the case of water electrolysis, has a configuration in which the ion exchange membrane in an electrolyzer for use in the case of common salt electrolysis mentioned above is replaced by a microporous membrane. The raw material to be supplied, which is water, is different from that for the electrolyser in the case of electrolysis of the common salt mentioned above. As for the other components, components similar to those of the electrolyser in the case of electrolysis of common salt can also be used in the electrolyser in the case of water electrolysis. Since chlorine gas is generated in the anodic chamber in the case

243/803 of common salt electrolysis, titanium is used as the material of the anodic chamber, but in the case of water electrolysis, only oxygen gas is generated in the anodic chamber. Thus, a material identical to that of the cathodic chamber can be used. An example of this is nickel. For the anode coating, the catalyst coating for oxygen generation is suitable. Examples of the catalyst coating include metals, oxides and hydroxides of the metals of the platinum group and metals of the transition metal group. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used. <Fourth modality>

[00946] Here, a fourth embodiment of the present invention will be described in detail with reference to Figures 63 to 90. [Electrolyzer]

[00947] The electrolyzer according to the fourth modality (hereinafter, in the section of <Fourth modality>, simply called “the present modality”) comprises an anode, an anode frame that supports the anode, a gasket on the side the anode that is arranged in the anodic frame, a cathode that opposes the anode, a cathode frame that supports the cathode, a gasket on the side of the cathode that is arranged in the cathode frame and is opposite the gasket on the anode side, and a membrane laminate and an electrolysis electrode, the laminate being arranged between the anode-side gasket and the cathode-side gasket, where at least a portion of the laminate is sandwiched between the anode-side gasket and the gasket on the cathode side and the ventilation resistance is 24 kPa-s / m or less when the electrolysis electrode is 50 mm x 50 mm in size, the ventilation resistance being measured under temperature conditions of 24ºC, a relative humidity of 32%, piston speed of 0.2 in / s, and volu ventilation of 0.4 cc / in? / s. According to the configuration described above, the electrolyzer of this modality has an excellent performance

244/803 electrolytic, as well as can prevent damage to the membrane.

[00948] The electrolyzer of the present embodiment comprises the constituent members mentioned above, in other words, comprises an electrolytic cell. Hereinafter, a case of conducting common salt electrolysis using an ion exchange membrane as the membrane is taken as an example, and an embodiment of the electrolyzer will be described in detail. [Electrolytic cell]

[00949] First, the electrolytic cell will be described, which can be used as a constituent unit of the electrolyzer of the present modality. Figure 63 illustrates a cross-sectional view of an electrolytic cell 1.

[00950] The electrolytic cell 1 comprises an anodic chamber 10, a cathodic chamber 20, a partition wall 30 placed between the anodic chamber 10 and the cathodic chamber 20, an anode 11 placed in the anodic chamber and a cathode 21 placed in the cathodic chamber 20 As required, the electrolytic cell 1 has a substrate 18a and a reverse current absorbent layer 18b formed on the substrate 18a and can comprise a reverse current absorber 18 placed in the cathode chamber. Anode 11 and cathode 21 belonging to electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 comprises the following cathode structure. The cathode structure 40 comprises the cathode chamber 20, the cathode 21 placed in the cathode chamber 20 and the reverse current absorber 18 placed in the cathode chamber 20, the reverse current absorber 18 has the substrate 18a and the reverse current absorbent layer 18b on substrate 18a, as shown in Figure 67, and cathode 21 and reverse current absorbing layer 18b are electrically connected. The cathodic chamber 20 also has a collector 23, a support 24 supporting the collector and an elastic metal body 22. The elastic metal body 22 is placed between the collector 23 and the cathode 21. The support 24 is placed between the collector 23 and the

245/803 partition wall 30. Collector 23 is electrically connected to cathode 21 via elastic metal body 22. Partition wall 30 is electrically connected to collector 23 via support 24. Consequently, partition wall 30, support 24 , the collector 23, the elastic metal body 22 and the cathode 21 are electrically connected. Cathode 21 and reverse current absorbing layer 18b are electrically connected. Cathode 21 and the reverse current absorbing layer can be directly connected or they can be indirectly connected through the collector, the support, the elastic metal body, the partition wall or the like. The entire surface of cathode 21 is preferably covered with a layer of catalyst for the reduction reaction. The electrical connection form can be a form in which the partition wall 30 and the support 24, the support 24 and the collector 23, and the collector 23 and the elastic metal body 22 are each directly attached and the cathode 21 it is laminated to the elastic metal body 22. Examples of a method for directly affixing these constituent components to each other include welding and the like. Alternatively, the reverse current absorber 18, cathode 21 and collector 23 can be collectively called a cathode structure 40.

[00951] Figure 64 illustrates a cross-sectional view of two electrolytic cells 1 that are adjacent to the electrolyzer 4. Figure 65 shows an electrolyzer 4. Figure 66 shows an assembly step for the electrolyzer 4.

[00952] In the conventional electrolyser, as shown in Figure 64A, an electrolytic cell 1, a membrane (here, a cation exchange membrane) 2 and an electrolytic cell 1 are arranged in series in the order mentioned. The ion exchange membrane 2 is arranged between the anode chamber of an electrolytic cell 1 of the two adjacent electrolytic cells in the electrolyzer and the cathode chamber of the other electrolytic cell 1. That is, in the electrolyzer, the anode chamber 10 of the electrolytic cell 1 and the cathodic chamber

246/803 of the electrolytic cell 1 adjacent to it are generally separated by the cation exchange membrane 2.

[00953] Meanwhile, in the present embodiment, as shown in Figure 64B, an electrolytic cell 1, a laminate 25 with a membrane (here, a cation exchange membrane) 2 and an electrolysis electrode (here, a cathode for renewal) 21a, and an electrolytic cell 1 are arranged in series in the order mentioned. The laminate 25, in the portion thereof (in Figure 64B, the upper end portion), is sandwiched between an anode gasket 12 and a cathode gasket 13.

[00954] As shown in Figure 65, electrolyzer 4 is composed of a plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2. That is, electrolyzer 4 is a bipolar electrolyzer that comprises the plurality of electrolytic cells 1 arranged in series and ion exchange membranes 2, each arranged between adjacent electrolytic cells 1. As shown in Figure 66, electrolyzer 4 is assembled by arranging the plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2 and coupling the cells by means of a pressure device 5.

[00955] Electrolyser 4 has an anodic terminal 7 and a cathodic terminal 6 to be connected to a power supply. Anode 11 of electrolytic cell 1 located at the far end between the plurality of electrolytic cells 1 coupled in series in electrolyzer 4 is electrically connected to anode terminal 7. Cathode 21 of the electrolytic cell located at the opposite end to anode terminal 7 between the plurality of electrolytic cells 1 coupled in series in the electrolyzer 4 is electrically connected to the cathodic terminal 6. The electrical current during electrolysis flows from the side of the anodic terminal 7, through the anode and cathode of each electrolytic cell 1, towards the cathodic terminal 6. At the two ends of the coupled electrolytic cells 1, an electrolytic cell with

247/803 only an anodic chamber (anodic terminal cell) and an electrolytic cell with only one cathodic chamber (cathodic terminal cell) can be arranged. In that case, anode terminal 7 is connected to the cell of the anode terminal, arranged at one end, and cathode terminal 6 is connected to the cell of the cathode terminal, arranged at the other end.

[00956] In the case of electrolytic brine, brine is provided for each anodic chamber 10 and pure water or an aqueous solution of low concentration sodium hydroxide is provided for each cathodic chamber 20. Each liquid is supplied from a supply tube of electrolytic solution (not shown in the Figure), through an electrolytic solution supply hose (not shown in the Figure), for each electrolytic cell 1. The electrolyte solution and electrolysis products are recovered from an electrolyte recovery tube (not shown in the figure). During electrolysis, the sodium ions in the brine migrate from the anode chamber 10 of the electrolytic cell 1, through the ion exchange membrane 2, to the cathode chamber 20 of the adjacent electrolytic cell 1. Thus, the electric current during electrolysis flows in the direction wherein electrolytic cells 1 are coupled in series. That is, the electric current flows, through the cation exchange membrane 2, from the anodic chamber 10 towards the cathodic chamber 20. As the brine is electrolyzed, chlorine gas is generated on the anode side 11, and sodium hydroxide (solute ) and hydrogen gas are generated on the cathode side

21.

[00957] As mentioned above, the characteristics of the membrane, cathode and anode in the electrolyzer generally deteriorate in association with the operation of the electrolyzer and replacement with new ones becomes necessary in a short time. In the case of replacing only the membrane, renewal can easily be accomplished by extracting the existing membrane between the electrolytic cells and inserting a new membrane between them, but replacing the anode or cathode by means of welding is complicated because a

248/803 specialized installation is required.

[00958] Meanwhile, in the present embodiment, laminate 25, in the portion thereof (in Figure 64B, the upper end portion), is sandwiched between an anode gasket 12 and cathode gasket 13, as described above. Particularly in the example shown in Figure 64B, the membrane (here, the cation exchange membrane) 2 and the electrolysis electrode (here, the renovation cathode) 21a can be fixed at least in the upper end portion of the laminate by pressing in the direction of the anode gasket 12 towards laminate 25 and pressing in the direction of cathode gasket 13 towards laminate 25. This case is preferable because it is not necessary to fix laminate 25 (in particular, the electrolyte electrode) to the existing member (for example, existing cathode) by welding. That is, the case in which both the electrolysis electrode and the membrane are sandwiched between the anode-side gasket and the cathode-side gasket is preferable because the work efficiency during the electrode renewal in the electrolyzer tends to be improved.

[00959] Furthermore, according to the configuration of the electrolyzer of the present modality, the membrane and electrode for electrolysis are sufficiently fixed like the laminate and, thus, an excellent electrolytic performance can be achieved. (Anodic chamber)

[00960] The anodic chamber 10 has anode 11 or the supply conductor of anode 11. The supply conductor referred to here means a degraded electrode (i.e., the existing electrode), an electrode without catalyst coating and the like. When the electrode for electrolysis in the present embodiment is inserted on the anode side, 11 serves as a feed conductor for the anode. When the electrode for electrolysis in the present embodiment is not inserted on the anode side, 11 serves as an anode. The anodic chamber 10 preferably has a unit for supplying

249/803 electrolyte solution on the anode side that provides an electrolyte solution for the anode chamber 10, a baffle plate that is arranged above the anode side electrolyte solution supply unit so as to be substantially parallel or oblique to a partition wall 30, and a liquid and gas separation unit on the anode side which is arranged above the baffle to separate the gas from the electrolytic solution including the mixed gas. (Anode)

[00961] When the electrode for electrolysis in the present modality is not inserted on the side of the anode, an anode 11 is provided in the frame of the anodic chamber 10 (that is, the anodic frame). Like anode 11, a metal electrode such as the so-called DSA (R) can be used. DSA is an electrode that includes a titanium substrate whose surface is covered with an oxide that contains ruthenium, iridium and titanium as components.

[00962] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Anode feed conductor)

[00963] When the electrolysis electrode in the present mode is inserted on the anode side, the anode 11 feeder conductor is provided in the anode chamber 10 frame. As the anode 11 feeder conductor, a metal electrode can be used , such as the so-called DSA (R), and titanium without catalyst coating can also be used. Alternatively, DSA with a thinner catalyst coating can also be used. In addition, a used anode can also be used.

[00964] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by

250/803 knitted metal and the like. (Anode side electrolyte solution supply unit)

[00965] The electrolyte solution supply unit on the anode side, which supplies the electrolyte solution to the anodic chamber 10, is connected to the electrolyte solution supply tube. The electrolytic solution supply unit on the anode side is preferably arranged below the anode chamber 10. As the electrolytic solution supply unit on the anode side, for example, a tube can be used on the surface from which orifice portions are formed. (dispersion tube) and the like. Such a tube is most preferably arranged along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell. This tube is connected to an electrolytic solution supply tube (liquid supply nozzle) that supplies the electrolytic solution to the electrolytic cell 1. The electrolyte solution supplied from the liquid supply nozzle is transported with a tube into the electrolytic cell 1 and supplied from the orifice portions provided on the surface of the tube into the anodic chamber 10. The arrangement of the tube along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell is preferable because the electrolyte solution can be uniformly supplied into the anodic chamber

10. (Liquid and gas separation unit on the anode side)

[00966] The liquid and gas separation unit on the anode side is preferably arranged above the baffle. The liquid and gas separation unit on the anode side has the function of separating the produced gas such as chlorine gas from the electrolytic solution during electrolysis. Unless otherwise specified, above means the upper direction in electrolytic cell 1 in Figure 63, and below means the lower direction in electrolytic cell 1 in Figure 63.

[00967] During electrolysis, the produced gas generated in the cell

251/803 electrolytic 1 and the electrolytic solution form a mixed phase (mixed gas-liquid phase), which is then emitted out of the system. Subsequently, pressure fluctuations within the electrolytic cell 1 cause vibration, which can result in physical damage to the ion exchange membrane. In order to avoid this event, the electrolytic cell 1 in the present embodiment is preferably provided with a liquid and gas separation unit on the anode side to separate the gas from the liquid. The liquid and gas separation unit on the anode side is preferably provided with an anti-foam plate to eliminate bubbles. When the flow of the mixed gas-liquid phase passes through the antifoam plate, the bubbles burst, thus allowing the electrolyte solution and the gas to be separated. As a result, vibration during electrolysis can be avoided.

(Baffle plate)

[00968] The baffle plate is preferably arranged above the electrolyte solution supply unit on the anode side and arranged substantially in parallel or obliquely to the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. When the deflector plate is provided, it is possible to make the electrolyte solution (brine or similar) circulate internally in the anodic chamber 10 to thus make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged in such a way as to separate the space in the vicinity of anode 11 from the space near the partition wall 30. From such a point of view, the baffle plate is preferably placed so as to be opposite the surface of anode 11 and the surface of the dividing wall 30. In the space next to the anode divided by the deflector plate, as the electrolysis progresses, the concentration of the electrolytic solution (brine concentration) is reduced and the gas produced, such as chlorine gas is generated. This results in a difference in specific gas-liquid gravity between the space near anode 11 and the space near the

252/803 partition wall 30 divided by the baffle plate. By using the difference, it is possible to promote the internal circulation of the electrolytic solution in the anodic chamber 10 to thus make the distribution of concentration of the electrolytic solution in the anodic chamber 10 more uniform.

[00969] Although not shown in Figure 63, a collector can be additionally provided inside the anodic chamber 10. The material and configuration of such a collector can be the same as the cathode chamber collector mentioned below. In anode chamber 10, anode 11 per se can also serve as a collector. (Partition wall)

[00970] The dividing wall 30 is arranged between the anodic chamber 10 and the cathodic chamber 20. The dividing wall 30 can be called a separator, and the anodic chamber 10 and the cathodic chamber 20 are divided by the dividing wall 30. Like the wall partition 30, one known as electrolysis separator can be used, and an example of this includes a partition wall formed by welding a plate comprising nickel next to the cathode and a plate comprising titanium beside the anode. (Cathodic chamber)

[00971] In the cathodic chamber 20, when the electrode for electrolysis in the present modality is inserted on the side of the cathode, 21 serves as a cathode supply conductor. When the electrolysis electrode in the present embodiment is not inserted on the cathode side, 21 it serves as a cathode. When a reverse current absorber is included, the cathode or cathode supply conductor 21 is electrically connected to the reverse current absorber. The cathodic chamber 20, similarly to the anodic chamber 10, preferably has an electrolytic solution supply unit on the cathode side and a liquid and gas separation unit on the cathode side. Among the components that make up the cathodic chamber 20, components similar to those that make up the anodic chamber 10

253/803 will not be described. (Cathode)

[00972] When the electrode for electrolysis in the present embodiment is not inserted on the side of the cathode, a cathode 21 is provided in the frame of the cathode chamber 20 (i.e., the cathode frame). Cathode 21 preferably has a nickel substrate and a catalyst layer that covers the nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include metals such as Ru, C, Si, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, y-alloying, composite dispersion / galvanization, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Cathode 21 can be subjected to a reduction treatment as needed. As the cathode 21 substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[00973] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Cathode supply conductor)

[00974] When the electrode for electrolysis in the present embodiment is inserted on the side of the cathode, a cathode 21 supply conductor is provided in the cathode chamber 20 frame. The cathode 21 supply conductor can be covered with a catalytic component. The catalytic component can be a component that is originally used as the cathode and remains. Examples of the catalyst layer components include

254/803 metals such as Ru, C, S1, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, alloy galvanizing, composite dispersion / galvanizing, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Nickel, nickel alloys and nickel or stainless galvanized iron without catalyst coating can be used. As the cathode 21 feed conductor substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[00975] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Reverse current absorbing layer)

[00976] A material with a less noble redox potential than the element's redox potential for the catalyst layer of the cathode mentioned above can be selected as a material for the reverse current absorbing layer. Examples of it include nickel and iron. (Collector)

[00977] The cathodic chamber 20 preferably comprises the collector

23. Collector 23 improves the efficiency of the current collection. In the present embodiment, the collector 23 is a porous plate and is preferably arranged substantially parallel to the surface of the cathode 21.

[00978] The collector 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. Collector 23 can be a mixture, alloy or composite oxide of these metals. The collector 23

255/803 can have any shape, as long as the shape allows the collector to function and can have a plate or network shape. (Elastic metal body)

[00979] Placing the elastic metal body 22 between the collector 23 and the cathode 21 presses each cathode 21 of the plurality of electrolytic cells 1 connected in series to the ion exchange membrane 2 to reduce the distance between each anode 11 and each cathode 21. Then, it is possible to reduce the voltage to be applied entirely through the plurality of electrolytic cells 1 connected in series. Reducing the voltage reduces energy consumption. With the elastic metal body 22 in place, the pressure caused by the elastic metal body 22 allows the electrolysis electrode to be held steadily in place when the laminate including the electrolysis electrode in the present embodiment is placed in the electrolytic cell.

[00980] As the elastic metal body 22, spring members such as spiral springs and coils and damping mats can be used. As the elastic metal body 22, a suitable one can be used appropriately, taking into account a tension to pressure the ion exchange membrane and the like. The elastic metal body 22 can be provided on the surface of the collector 23 on the side of the cathode chamber 20 or it can be provided on the surface of the partition wall on the side of the anode chamber 10. Both chambers are normally divided in such a way that the cathode chamber 20 it becomes smaller than the anodic chamber 10. Thus, from the point of view of the strength of the frame and the like, the elastic metal body 22 is preferably provided between the collector 23 and the cathode 21 in the anodic chamber

20. The elastic metal body 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. (Support)

[00981] The cathodic chamber 20 preferably comprises the support 24 that electrically connects the collector 23 to the partition wall 30. This can

256/803 achieve an efficient current flow.

[00982] The support 24 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. The support 24 can have any shape as long as the support can support the collector 23 and can have a rod, plate or network shape. The support 24 has a plate shape, for example. A plurality of supports 24 is arranged between the partition wall 30 and the collector 23. The plurality of supports 24 are aligned in such a way that their surfaces are in parallel with each other. The supports 24 are arranged substantially perpendicular to the partition wall 30 and the collector 23. (Gasket on the anode side and gasket on the cathode side)

[00983] The anode-side gasket is preferably arranged on the surface of the structure that constitutes the anodic chamber 10. The cathode-side gasket is preferably arranged on the surface of the structure that constitutes the cathodic chamber 20. The electrolytic cells are connected to each other others such that the anode-side gasket included in an electrolytic cell and the cathode-side gasket of an electrolytic cell adjacent to the cell sandwich the laminate 25 (see Figure 64B). These gaskets can make the connection points airtight when the plurality of electrolytic cells 1 is connected in series through the laminate 25.

[00984] The gaskets form a seal between the ion exchange membrane and the electrolytic cells. Specific examples of gaskets include picture frame rubber sheets, in the center of which a hole portion is formed. Gaskets are required to be resistant to corrosive electrolyte solutions or gas produced and to be usable for a long period. Thus, with regard to chemical resistance and hardness, vulcanized products and products cross-linked with ethylene-propylene-diene rubber peroxide (EPDM rubber) and ethylene-propylene rubber (EPM rubber) are normally used as gaskets. Alternatively,

257/803 gaskets from which the region to be in contact with liquid (liquid contact portion) with a fluorine-containing resin such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers can be used as needed. Such gaskets may have an orifice portion so as not to inhibit the flow of the electrolyte solution, and the shape of the orifice portion is not particularly limited. For example, a picture frame gasket is affixed with an adhesive or similar along the peripheral edge of each hole portion of the anodic chamber frame that constitutes the anodic chamber 10 or the cathodic chamber frame that constitutes the cathodic chamber 20. Sandwiching laminate 25 with anode gasket and cathode gasket can prevent the electrolyte solution, alkali metal hydroxide, chlorine gas, hydrogen gas and the like, generated from electrolysis, from escaping electrolytic cells 1. [Laminate]

[00985] The laminate in the present modality comprises a membrane and electrode for electrolysis. The laminate in this modality can improve the work efficiency during the electrode renewal in an electrolyzer and, in addition, it can present excellent electrolytic performance also after the renovation. That is, according to the laminate in the present modality, when renewing the electrode, the electrode can be renewed by a job as simple as renewing the membrane, without a complicated job like removing the existing electrode fixed in the electrolytic cell, and thus, the work efficiency is noticeably improved.

[00986] Furthermore, according to the laminate in this modality, it is possible to maintain the electrolytic performance of the existing electrolytic cell comparable to that of a new electrode or to improve the electrolytic performance. Thus, the electrode attached to the existing electrolytic cell and serving as the anode or cathode is only needed to serve as a supply conductor. Thus, it is also possible to remarkably reduce or eliminate the

258/803 catalyst coating. [Electrode for electrolysis]

[00987] In the electrolyte electrode in this mode, the ventilation resistance is 24 kPa-s / m or less when the electrolysis electrode is 50 mm x 50 mm in size, the ventilation resistance being measured under temperature conditions 24ºC, a relative humidity of 32%, a piston speed of 0.2 cm / s and a ventilation volume of 0.4 celem? / s (hereinafter, also called “measurement condition 1”) (hereinafter onwards, also called “ventilation resistance 1”). Higher ventilation resistance means that air is unlikely to flow and refers to a state of high density. In this state, the electrolysis product remains on the electrode and it is more unlikely that a substrate for the reaction will diffuse inside the electrode, and thus the electrolytic performance (such as voltage) deteriorates. The concentration on the membrane surface increases. Specifically, the caustic concentration increases on the cathode surface, and the supply of brine decreases on the anode surface. As a result, the product accumulates in high concentration at the interface at which the membrane is in contact with the electrode. This build-up causes damage to the membrane and leads to increased tension and damage to the membrane on the cathode surface and damage to the membrane on the anode surface. In the present modality, in order to avoid these defects, the ventilation resistance is set at 24 kPa-s / m or less.

[00988] In the present modality, when the ventilation resistance is greater than a certain value, the NaOH generated in the electrode tends to accumulate at the interface between the electrode and the membrane to result in a high concentration in the case of the cathode, and the supply brine tends to decrease to make the brine concentration lower in the case of the anode. In order to avoid damage to the membrane that could be caused by such an accumulation, the ventilation resistance is preferably less than 0.19

259/803 kPa-s / m, more preferably 0.15 kPas / m or less, even more preferably 0.07 kPa-s / m or less.

[00989] In contrast, when the ventilation resistance is low, the electrode area becomes smaller and the electroconductive area is reduced. Thus, electrolytic performance (such as voltage) deteriorates. When the ventilation resistance is zero, the supply conductor functions as the electrode, as no electrolysis electrode is provided and the electrolytic performance (like the voltage) deteriorates noticeably. From that point of view, a preferable lower limit value identified as ventilation resistance 1 is not particularly limited, but is preferably greater than 0 kPa-s / m, more preferably 0.0001 kPa-s / m or more, even more preferably 0.001 kPa-s / m or more.

[00990] When ventilation resistance 1 is 0.07 kKPa-s / m or less, sufficient measurement accuracy may not be achieved because of the measurement method for it. From this point of view, it is also possible to evaluate an electrolysis electrode with ventilation resistance 1 of 0.07 kPa-s / m or less by means of a ventilation resistance (hereinafter, also called “ventilation resistance 2 ”) obtained by the following measurement method (hereinafter, also called“ measurement condition 2 ”). That is, ventilation resistance 2 is a measured ventilation resistance, when the electrolysis electrode has a size of 50 mm x 50 mm, under conditions of temperature of 24ºC, the relative humidity of 32%, a piston speed of 2 cm / s and a ventilation volume of 4 cc / in? / s.

[00991] Specific methods for measuring ventilation resistances | and 2 are described in the Examples.

[00992] Ventilation resistors | and 2 may be within the range described above, appropriately adjusting an aperture ratio, electrode thickness and the like, for example. More specifically, for example,

260/803 when the thickness is constant, a higher opening ratio tends to lead to smaller ventilation resistances 1 and 2, and a smaller opening ratio tends to lead to higher ventilation resistances 1 and 2.

[00993] The electrolysis electrode in the present embodiment has a force applied per unit mass-unit area of preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mg: in?), even more preferably less than 1.5 N / (mg: cm?), even more preferably 1.2 N / mg-cm? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a supply conductor (a degraded electrode and an uncoated electrode) catalyst) and the like. Is the applied force even more preferably 1.1 N / mg-cm? or less, even more preferably 1.10 N / mge? or less, particularly preferably 1.0 N / m? or less, especially preferably 1.00 N / mg-cm? or less.

[00994] From the point of view of further improving electrolytic performance, the strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: in?) Or more, even more preferably 0.1 N / mg: cm? or more, even more preferably 0.14 N / (mg: cm?) or more. By force it is even more preferably 0.2 N / (mg: cm?) Or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 m x 2.5 m).

[00995] The applied force described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness, arithmetic mean surface roughness and the like, for example. More specifically, for example, a higher opening ratio tends to lead to a lower applied force, and a lower opening ratio tends to lead to a higher applied force.

261/803

[00996] Is the mass per unit preferably 48 mg / cm? or less, more preferably 30 mg / cm? or less, even more preferably 20 mg / cm? or less from the point of view of allowing a good manipulation property, having a good adhesive force for a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a conductive conductor without catalyst coating, and economy , and in addition it is preferably 15 mg / hundred? or less from a comprehensive point of view including handling, grip and economy properties. The lower limit value is not particularly limited, but is in the order of 1 mg / hundred?, For example.

[00997] The mass per unit area described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness and the like, for example. More specifically, for example, when the thickness is constant, a larger opening ratio tends to lead to a smaller mass per unit area, and a smaller opening ratio tends to lead to a mass per unit area greater.

[00998] The applied force can be measured by the methods (1) or (11) described below, which are as detailed in the Examples. As for the applied force, the value obtained by measuring the method (1) (also called “the applied force (1)”) and the value obtained by measuring the method (ii) (also called “the applied force (2) ”) Can be the same or different, and any of the values is preferably less than 1.5 N / (mg: -ecm?). [Method (i)]

[00999] A nickel plate obtained by stripping processing with grain size 320 alumina (1.2 mm thickness, 200 square mm), an ion exchange membrane that is obtained by the application of particles of inorganic material and a binder on both surfaces of a perfluorocarbon polymer membrane in which an ion exchange group is introduced (170 mm square, the membrane detail of

262/803 ion exchange referred to here is as described in the Examples) and an electrode sample (130 mm square) is laminated in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. The arithmetic mean roughness of the surface (Ra) of the nickel plate after blasting treatment is 0.5 to 0.8 µm. The specific method for calculating the arithmetic mean surface roughness (Ra) is as described in the Examples.

[001000] Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the charge when the electrode sample is raised by 10 mm in a vertical direction is measured. This measurement is repeated three times and the average value is calculated.

[001001] This average value is divided by the area of the overlapping portion of the electrode sample and the ion exchange membrane and the mass of the portion that overlaps the ion exchange membrane in the electrode sample to calculate the applied force per unit of mass- area unit (1) (N / mg-ecm?).

[001002] The force applied per unit mass-unit area (1) obtained by method (i) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. Is the applied force even more preferably 1.1 N / mg-cm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg: -cm? or

263/803 less, especially preferably 1.00 N / mg: -em? or less. The strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg: cm?) Or more than the point view of further improving electrolytic performance, and furthermore, it is even more preferably 0.14 N / (mgcm?), even more preferably 0.2 N / (mg: cm?) or more from the point of view of facilitating further manipulation in a large size (for example, a size of 1.5 mx2.5 Mm). [Method (ii)]

[001003] A nickel plate obtained by blasting processing with grain size 320 alumina (1.2 mm thickness, 200 mm square, a nickel plate similar to the method (1) above) and an electrode sample ( 130 mm square) is laminated in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the load when the electrode sample is raised by 10 mm in a vertical direction it is measured. This measurement is repeated three times and the average value is calculated.

[001004] This average value is divided by the area of the overlapping portion of the electrode sample and the nickel plate and the mass of the electrode sample in the portion that overlaps the nickel plate to calculate the adhesive force per unit mass-unit of area (2) (N / mg: -cm?).

[001005] The force applied per unit mass-unit area (2) obtained by method (ii) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or

264/803 less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg: cm? or less. In addition, the strength is preferably greater than 0.005 N / (mg: cm?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg-in?) Or more from the point of view of further improving electrolytic performance, and it is even more preferably 0.14 N / (mg: cm?) or more from the point of view of further facilitating handling in a large size (for example, a 1.5 m x 2.5 m).

[001006] The electrolyte electrode in the present embodiment preferably includes an electrode electrode substrate and a catalyst layer. The substrate thickness for the electrolysis electrode (gauge thickness) is, but is not particularly limited to, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less , even more preferably 125 µm or less, even more preferably 120 µm or less, even more preferably 100 µm or less from the point of view of enabling a good handling property to be provided, having a good adhesive strength to a membrane, such as a ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, be able to be properly laminated on a roll and folded satisfactorily, facilitating handling in one size large (for example, a size of 1.5 mx

265/803 2.5 mM), and it is even more preferably 50 µm or less from the point of view of manipulation and economy property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001007] The proportion measured by the following method (2) of the electrode for electrolysis in the present embodiment is not particularly limited, but is preferably 90% or more, more preferably 92% or more from the point of view of allowing a good handling property is provided and has a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and more preferably 95% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (2)]

[001008] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 280 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001009] The proportion measured by the following method (3) of the electrode for electrolysis in the present embodiment is not particularly limited, but is preferably 75% or more, more preferably 80% or more of the

266/803 seen to allow a good handling property to be provided, to have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (conductor conductor) without catalyst coating and can be properly rolled on a roll and satisfactorily folded, and is more preferably 90% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (3)]

[001010] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 145 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001011] The value obtained by measuring by the following method (A) of the electrolyte for electrolysis in the present embodiment is preferably 40 mm or less, more preferably 29 mm or less, more preferably 19 mm or less from the point of view of the handling property. [Method (A)]

[001012] Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, a sample obtained by lamination of an ion exchange membrane that is obtained by applying particles of inorganic material and a binder to both surfaces of an membrane of a polymer of

267/803 perfluorocarbon in which an ion exchange group is introduced (170 mm square, the details of the ion exchange membrane referred to here are described in the Examples) and the electrolysis electrode is rolled up and fixed to a curved surface of a core material made of polyvinyl chloride and with an external diameter of 32 mm and left to stand for 6 hours; thereafter, when the electrolysis electrode is separated from the sample and placed on a flat plate, heights in a vertical direction on both edges of the electrolysis electrode L1 and L2 are measured, and an average value is used as a measurement value .

[001013] The electrolysis electrode in the present modality has a porous structure and an opening ratio or void ratio of 5 to 90% or less from the point of view of enabling a good handling property, having a good adhesive force to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and to prevent gas buildup from being generated during electrolysis, although not particularly limited . The opening ratio is more preferably 10 to 80% or less, more preferably 20 to 75%.

[001014] The opening ratio is a proportion of the opening portions per volume unit. The calculation method may differ depending on whether the opening portions in submicron size are considered or that only visible openings are considered. In the present embodiment, a volume V was calculated from the values of the thickness of the gauge, width and length of the electrode and, in addition, a weight W was measured to thereby calculate an aperture ratio A using the following formula.

A = (1- (W / (Y xp)) x 100

[001015] p is the density of the electrode material (g / cm?). For example, nickel p is 8.908 g / em ”, and titanium p is 4.506 g / em ?. The aperture ratio can be appropriately adjusted by changing the area of metal to be drilled

268/803 per unit area in the case of perforated metal, changing the SW (short diameter), LW (long diameter) and feed values in the case of expanded metal, changing the metal fiber line diameter and mesh number in the mesh case, changing the pattern of a photoresist to be used in the case of electroforming, changing the diameter of the metal fiber and fiber density in the case of non-woven fabric, changing the mold to form voids in the case of foamy metal or similar.

[001016] Hereinafter, an aspect of the electrode for electrolysis in the present modality will be described.

[001017] The electrolysis electrode according to the present embodiment preferably includes a substrate for electrolysis electrode and a layer of catalyst. The catalyst layer can be composed of a plurality of layers, as shown below, or it can be a single layer configuration.

[001018] As shown in Figure 68, an electrolysis electrode 100 according to the present embodiment includes an electrode electrode substrate 10 and a pair of first layers 20 with which both surfaces of the electrode substrate for electrolysis 10 are covered. . The entire electrolyte electrode substrate 10 is preferably covered with the first 20 layers. This coating is likely to improve the activity of the catalyst and the durability of the electrolysis electrode. A first layer 20 can be laminated only on one surface of the electrode substrate for electrolysis 10.

[001019] Also shown in Figure 68, the surfaces of the first layers 20 can be covered with the second layers 30. The first entire layers 20 are preferably covered by the second layers 30. Alternatively, a second layer 30 can be laminated only one surface of the first layer 20. (Electrode substrate for electrolysis)

269/803

[001020] As an electrode substrate for electrolysis 10, for example, nickel, nickel alloys, stainless steel or valve metals including titanium can be used, although not limited to them. The substrate 10 preferably contains at least one element selected from nickel (Ni) and titanium (Ti).

[001021] When stainless steel is used in a high-concentration aqueous alkaline solution, iron and chromium are eluted and the electrical conductivity of stainless steel is about one tenth that of nickel. In view of the above, a substrate containing nickel (Ni) is preferable as a substrate for the electrolysis electrode.

[001022] Alternatively, when the electrode substrate for electrolysis 10 is used in a high concentration saline solution close to saturation under an atmosphere in which chlorine gas is generated, the substrate material for electrode 10 is also preferably titanium with high corrosion resistance.

[001023] The shape of the electrode substrate for electrolysis 10 is not particularly limited, and a shape suitable for the purpose can be selected. As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. Among these, a perforated metal or expanded metal is preferable. Electroforming is a technique for producing a thin metal film with a precise pattern using photolithography and electroplating in combination. It is a method that includes the formation of a pattern on a substrate with a photoresist and electroplating of the portion not protected by the resistance to provide a thin metal film.

[001024] As for the shape of the substrate for the electrolysis electrode, an appropriate specification depends on the distance between the anode and the cathode in the electrolyzer. In the event that the distance between the anode and the cathode is finite,

270/803 a form of expanded metal or perforated metal can be used, and in the case of a so-called zero-interstitial electrolyzer, in which the ion exchange membrane is in contact with the electrode, a woven mesh produced by fine knitted threads, wire mesh, foamy metal, metallic non-woven fabric, expanded metal, perforated metal, porous metal foil and the like, although not limited to it.

[001025] Examples of the electrode substrate for electrolysis 10 include a porous metallic foil, a wire mesh, a nonwoven metal fabric, a perforated metal, an expanded metal and a foamy metal.

[001026] As plate material before being processed into a perforated metal or expanded metal, laminated plate materials and electrolytic sheets are preferred. An electrolytic sheet is preferably still subjected to a galvanizing treatment using the same element as its base material, such as after-treatment, to thereby form roughness and one or both surfaces.

[001027] The thickness of the electrode substrate for electrolysis 10 is, as mentioned above, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less, even more preferably 125 one or less, even more preferably 120 µm or less, even more preferably 100 µm or less, and even more preferably 50 µm or less from the point of view of a handling and economical property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001028] In the electrode substrate for electrolysis, the residual stress during processing is preferably relaxed by annealing the electrode substrate for electrolysis in an oxidizing atmosphere. It is preferable to form roughness using a steel grid, alumina powder or similar on the surface of the electrode substrate for electrolysis followed by a

271/803 acid treatment to increase its surface area, in order to improve adhesion to a catalyst layer with which the surface is covered. Alternatively, it is preferable to give a galvanizing treatment using the same element as the substrate to increase the surface area.

[001029] In order to place the first layer 20 in close contact with the surface of the electrode electrode substrate 10, the electrode electrode substrate 10 is preferably subjected to a treatment of increasing the surface area. Examples of the treatment of increasing the surface area include a pickling treatment using a cut wire, steel grid, alumina grid or similar, an acid treatment using sulfuric acid or hydrochloric acid, and a galvanizing treatment using the same element as the of the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 µm to 50 µm, more preferably 0.1 to 10 µm, even more preferably 0.1 to 8 µm.

[001030] Next, a case will be described in which the electrode for electrolysis in the present modality is used as an anode for electrolysis of common salt. (First layer)

[001031] In Figure 68, a first layer 20 as a catalyst layer contains at least one of the ruthenium oxides, iridium oxides and titanium oxides. Examples of ruthenium oxide include RuO; Examples of iridium oxide include IrO ,. Examples of titanium oxide include TiO,; The first layer 20 preferably contains two oxides: a ruthenium oxide and a titanium oxide or three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide. This makes the first layer 20 more stable and further improves adhesion with the second layer 30.

[001032] When the first layer 20 contains two oxides: a ruthenium oxide and a titanium oxide, the first layer 20 contains

272/803 preferably 1 to 9 mol, more preferably 1 to 4 mol of titanium oxide based on 1 mol of ruthenium oxide contained in the first layer 20. With the ratio of composition of the two oxides in this range, the electrolyte for electrolysis 100 excellent durability.

[001033] When the first layer 20 contains three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide, the first layer 20 preferably contains 0.2 to 3 mol, more preferably 0.3 to 2.5 mol of iridium oxide based on 1 mol of ruthenium oxide contained in the first layer 20. The first layer 20 preferably contains 0.3 to 8 mol, more preferably 1 to 7 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition of the three oxides in this range, the electrode for electrolysis 100 has excellent durability.

[001034] When the first layer 20 contains at least two of a ruthenium oxide, an iridium oxide and a titanium oxide, these oxides preferably form a solid solution. The formation of the solid oxide solution allows the electrolysis electrode 100 to have excellent durability.

[001035] In addition to the compositions described above, oxides of various compositions can be used provided that at least one oxide of a ruthenium oxide, an iridium oxide and titanium oxide is contained. For example, an oxide coating called DSA (R), which contains ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum and the like, can be used as a first layer 20.

[001036] The first layer 20 need not be a single layer and can include a plurality of layers. For example, the first layer 20 can include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 µm, more preferably 0.1 to 8 µm.

273/803 (Second layer)

[001037] The second layer 30 preferably contains ruthenium and titanium. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001038] The second layer 30 preferably contains a palladium oxide, a solid solution of a palladium and platinum oxide, or an alloy of palladium and platinum. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001039] A second thicker layer 30 can maintain the electrolytic performance for a longer period, but from an economic point of view, the thickness is preferably 0.05 to 3 µm.

[001040] Next, a case will be described in which the electrode for electrolysis in the present modality is used as a cathode for electrolysis of common salt. (First layer)

[001041] Examples of components of the first layer 20 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[001042] The first layer 20 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal.

[001043] When the first layer 20 contains at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides, and alloys containing a platinum group metal, the metals of the platinum group platinum, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal preferably contain at least one platinum group metal

274/803 of platinum, palladium, rhodium, ruthenium and iridium.

[001044] Like the platinum group metal, platinum is preferably contained.

[001045] Like the metal oxide of the platinum group, a ruthenium oxide is preferably contained.

[001046] Like the metal hydroxide of the platinum group, a ruthenium hydroxide is preferably contained.

[001047] Like the platinum group metal alloy, a platinum alloy with nickel, iron and cobalt is preferably contained.

[001048] In addition, as needed, an oxide or hydroxide of a lanthanide element is preferably contained as a second component. This allows the electrolysis electrode 100 to have excellent durability.

[001049] As the oxide or hydroxide of a lanthanide element, at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium and dysprosium is preferably contained.

[001050] Furthermore, as needed, an oxide or hydroxide of a transition metal is preferably contained as a third component.

[001051] The addition of the third component allows the electrolysis electrode 100 to have greater durability and the electrolysis voltage to be reduced.

[001052] Examples of a preferable combination include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + platinum + palladium, ruthenium + neodymium, ruthenium + neodymium + platinum, ruthenium + neodymium + manganese, ruthenium + neodymium + iron, ruthenium + neodymium + cobalt, ruthenium + neodymium

275/803 + zinc, ruthenium + neodymium + gallium, ruthenium + neodymium + sulfur, ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + samarium + cobalt, ruthenium + samarium + zinc, ruthenium + samarium + gallium, ruthenium + samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + nickel + palladium, platinum + nickel + ruthenium, platinum and nickel alloys, platinum and cobalt alloys, and platinum and iron alloys .

[001053] When platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal are not contained, the main component of the catalyst is preferably the nickel element.

[001054] At least one of the nickel metals, oxides and hydroxides is preferably contained.

[001055] As the second component, a transition metal can be added. As the second component to be added, at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper and carbon is preferably contained.

[001056] Examples of a preferable combination include nickel + tin, nickel + titanium, nickel + molybdenum and nickel + cobalt.

[001057] As required, an intermediate layer can be placed between the first layer 20 and the electrode substrate for electrolysis

10. The durability of the electrolysis electrode 100 can be improved by placing the intermediate layer.

[001058] As the intermediate layer, those having affinity for both the first layer 20 and the electrode substrate for electrolysis 10 are preferred. As the intermediate layer, nickel oxides, platinum group metals, metal oxides are preferable of the group

276/803 platinum and platinum group metal hydroxides. The intermediate layer can be formed by applying and cooking a solution containing a component that forms the intermediate layer. Alternatively, a surface oxide layer can also be formed by subjecting a substrate to a heat treatment at a temperature of 300 to 600ºC in an air atmosphere. In addition, the layer can be formed by a known method, such as a thermal spray method and an ion galvanizing method. (Second layer)

[001059] Examples of components of the first layer 30 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[001060] The first layer 30 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal. Examples of a preferable combination of elements contained in the second layer include the combinations listed for the first layer. The combination of the first layer and the second layer can be a combination in which the compositions are the same and the composition reasons are different or can be a combination of different compositions.

[001061] As the thickness of the catalyst layer, the total thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 µm to 20 µm. With a thickness of 0.01 µm or more, the catalyst layer can sufficiently serve as the catalyst. With a thickness of 20 µm or less, it is possible to form a robust catalyst layer that is unlikely to fall off the substrate. The thickness is more preferably 0.05 µm to 15 µm. The thickness is more preferably 0.1 µm to 10 µm. The thickness is even more preferably 0.2 µm to 8 µm.

[001062] The thickness of the electrode, i.e. the total thickness of the electrode substrate for electrolysis and the catalyst layer is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, even more preferably 150 one or less, particularly - preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less with respect to the electrode handling property. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably one or more. The thickness of the electrode can be determined by measurement with a digital thickness gauge (Mitutoyo Corporation, minimum scale 0.001 mm). The thickness of the electrode substrate for electrolysis is measured in the same way as the thickness of the electrode. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.

[001063] In the present embodiment, the electrolysis electrode preferably contains at least one catalytic component selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B / C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy from the point of view of achieving sufficient electrolytic performance.

[001064] In the present modality, from the point of view that the electrode for

278/803 electrolysis, if it is an electrode with a wide region of elastic deformation, can provide a better handling property and has a better adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a conductor feed without any catalyst coating, and the like, the electrode thickness for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, even more preferably 150 µm or less, particularly preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably 20 µm or more. In the present modality, “having a wide region of elastic deformation” means that when an electrolysis electrode is wound to form a wound body, it is unlikely that distortion derived from the winding will occur after the wound state is released. The thickness of the electrolysis electrode refers, when a catalyst layer mentioned below is included, to the total thickness of both the electrolysis electrode substrate and the catalyst layer. (Method to produce electrode for electrolysis)

[001065] Next, an embodiment of the method for producing the electrolysis electrode 100 will be described in detail.

[001066] In the present embodiment, the electrolysis electrode 100 can be produced by forming the first layer 20, preferably the second

279/803 layer 30, on the electrode substrate for electrolysis by a method such as cooking a coating film under an oxygen atmosphere (pyrolysis) or ion galvanizing, galvanizing or thermal spraying. The production method of the present embodiment as mentioned can achieve a high productivity of the electrode for electrolysis 100. Specifically, a catalyst layer is formed on the electrode substrate for electrolysis by an application step to apply a coating liquid containing a catalyst, a drying step to dry the coating liquid and a pyrolysis step to perform pyrolysis. Pyrolysis here means that a metal salt that is to be a precursor is decomposed by heating into a metal or metal oxide and a gaseous substance. The decomposition product depends on the metal species to be used, the type of salt and the atmosphere under which pyrolysis is carried out, and many metals tend to form oxides in an oxidizing atmosphere. In an industrial electrode production process, pyrolysis is usually carried out in air, and a metal oxide or metal hydroxide is formed in many cases. (Formation of the first anode layer) (Application stage)

[001067] The first layer 20 is obtained by applying a solution in which at least one metallic salt of ruthenium, iridium and titanium is dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the liquid coating in the presence of oxygen. The ruthenium, iridium and titanium content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001068] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The concentration

280/803 total metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating.

[001069] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a bathing method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[001070] After being applied to the electrode substrate for electrolysis 100, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolysed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001071] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then

281/803 additionally post-cooked for a long period, as needed, can further improve the stability of the first layer 20. (Formation of the second layer)

[001072] The second layer 30, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second liquid of first layer 20 and then pyrolyzing the coating liquid in the presence of oxygen. (Formation of the first cathode layer by the pyrolysis method) (Application stage)

[001073] The first layer 20 is obtained by applying a solution in which metal salts of various combinations are dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the coating liquid in the presence of oxygen. The metal content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001074] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[001075] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersion bath of the substrate for electrode for

282/803 electrolysis 10 in the first coating liquid, a brushing method of the first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in the opposite way and spraying is carried out. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[001076] After being applied to the electrode substrate for electrolysis 10, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001077] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the intermediate layer)

[001078] The intermediate layer, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound or a platinum compound (second coating liquid) to the substrate and then pyrolyzing the coating liquid in the presence of

283/803 oxygen. Alternatively, an intermediate layer of nickel oxide can be formed on the surface of the substrate just by heating the substrate, without applying a solution on it. (Formation of the first cathode layer by ion galvanizing)

[001079] The first layer 20 can also be formed by ion plating.

[001080] An example includes a method in which the substrate is fixed in a chamber and the metal ruthenium target is irradiated with an electron beam. Evaporated metallic ruthenium particles are positively charged to the plasma in the chamber to deposit on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and deposits of ruthenium as ruthenium oxide in the substrate. (Formation of the first cathode layer by galvanizing)

[001081] The first layer 20 can also be formed by a method of galvanization.

[001082] For example, when the substrate is used as a cathode and subjected to electrolytic galvanization in an electrolytic solution containing nickel and tin, nickel and tin alloy galvanization can be formed. (Formation of the first cathode layer by thermal spray)

[001083] The first layer 20 can also be formed by thermal spraying.

[001084] As an example, the nickel oxide particles sprayed by plasma on the substrate can form a catalyst layer in which the metallic nickel and the nickel oxide are mixed.

[001085] The electrolysis electrode in the present modality can be integrated with a membrane, such as an ion exchange membrane and a microporous membrane, and used. Thus, the laminate in the present embodiment can be used as an electrode integrated into the membrane. So, the job of replacing the cathode and anode in renewing the electrode is

284/803 eliminated, and work efficiency is noticeably improved.

[001086] The electrode integrated into the membrane, such as an ion exchange membrane and a microporous membrane, can make the electrolytic performance comparable or superior to that of a new electrode.

[001087] In the following, the ion exchange membrane will be described in detail. [Ion exchange membrane]

[001088] The ion exchange membrane is not particularly limited as long as the membrane can be laminated with the electrolysis electrode, and several ion exchange membranes can be used. In the present embodiment, an ion exchange membrane is preferably used which has a membrane body containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and a coating layer provided on at least one surface of the membrane body. It is preferable that the coating layer contains particles of inorganic material and a binder, and the specific surface area of the coating layer is 0.1 to 10 µm / g. The ion exchange membrane that has such a structure has a small influence of the gas generated during electrolysis on electrolytic performance and tends to exert stable electrolytic performance.

[001089] The membrane of a perfluorocarbon polymer into which an ion exchange group is introduced described above includes a layer of sulfonic acid with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called a "sulfonic acid group") or a layer of carboxylic acid with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a "carboxylic acid group"). From the point of view of strength and dimensional stability, reinforcement core materials are preferably included.

[001090] The particles of inorganic material and binder will be described in detail in the coating layer description section below.

285/803

[001091] Figure 69 illustrates a schematic cross-sectional view showing an ion exchange membrane modality. An ion exchange membrane | it has a membrane body 10 containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and coating layers 11a and 11b formed on both surfaces of the membrane body 10.

[001092] In the ion exchange membrane 1, the membrane body 10 comprises a layer of sulfonic acid 3 with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called an “acid group sulfonic ”) and a layer of carboxylic acid 2 with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a“ carboxylic acid group ”), and the core materials of reinforcement 4 intensifies strength and dimensional stability. The ion exchange membrane 1, comprising the sulfonic acid layer 3 and the carboxylic acid layer 2, is suitably used as an anion exchange membrane.

[001093] The ion exchange membrane may include the sulfonic acid layer or the carboxylic acid layer. The ion exchange membrane may not necessarily be reinforced by reinforcement core materials, and the arrangement of the reinforcement core materials is not limited to the example in Figure 69. (Membrane body)

[001094] First, the membrane body 10 which constitutes the ion exchange membrane 1 will be described.

[001095] The membrane body 10 must be one that has the function of selectively allowing cations to permeate and comprises a hydrocarbon polymer or a fluorine-containing polymer with an ion exchange group. Its configuration and material are not particularly limited, and the preferred ones can be selected appropriately.

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[001096] The hydrocarbon polymer or fluorine-containing polymer with an ion exchange group in the membrane body 10 can be obtained from a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group precursor capable of forming a group of ion exchange by hydrolysis or similar. Specifically, for example, after a polymer comprising a fluorinated hydrocarbon backbone that has, as a pendant side chain, a group convertible into an ion exchange group by hydrolysis or similar (precursor to the ion exchange group), and is processable by melting (hereinafter called "fluorine-containing polymer (a)" in some cases), be used to prepare a precursor to the membrane body 10, the membrane body 10 can be obtained by converting the precursor to the ion exchange group in an ion exchange group.

[001097] The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. The fluorine-containing polymer (a) can also be produced by homopolymerizing a monomer selected from any of the following first group, the following second group and the following third group.

[001098] Examples of the monomers of the first group include vinyl fluoride compounds. Examples of the vinyl fluoride compounds include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and perfluoralkyl vinyl ethers. Particularly when the ion exchange membrane is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoro monomer, and a perfluoro monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and perfluoralkylvinyl ethers is preferable.

[001099] Examples of the monomers of the second group include

287/803 vinyl compounds with a functional group convertible into an ion exchange group of the carboxylic acid type (carboxylic acid group). Examples of vinyl compounds with a functional group convertible to a carboxylic acid group include monomers represented by CF = CF (OCF; CYF); - O (CZF) .- COOR, where s represents an integer from 0 to 2, t represents an integer from 1 to 12, Y and Z each independently represent F or CF; 3, and R represents a lower alkyl group (a lower alkyl group is an alkyl group with 1 to 3 carbon atoms, for example).

[001100] Among them, compounds represented by CF; = CF (OCF; CYF), - O (CF2) n-COOR are preferable. Where n represents an integer from 0 to 2, m represents an integer from 1 to 4, Y represents F or CF; 3, and R represents CH3, CoHs, or C3H ;.

[001101] When the ion exchange membrane is used as a cation exchange membrane for alkaline electrolysis, a perfluoro compound is preferably at least used as the monomer, but the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis and, therefore, the alkyl group (R) need not be a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[001102] Of the monomers above, the monomers shown below are more preferable than the monomers of the second group: CF; = CFOCF; -CF (CF;) OCF; COOCH ;, CF; = CFOCF; CF (CF3) O (CF3) -COOCH ;, CF3 = CF [OCF, -CF (CF3)] 12O (CF.); - COOCH ;, CF; = CFOCF; CF (CF3) O (CF3); 5COOCH ;, CF3 = CFO (CF3); COOCH ;, and CF; = CFO (CF;); COOCH ;.

[001103] Examples of the monomers of the third group include vinyl compounds with a functional group convertible into an ion exchange group of the sulfone type (sulfonic acid group). As compounds

288/803 vinyls with a functional group convertible to a sulfonic acid group, for example, monomers represented by CF; = CFO-X-CF; -SO, F are preferable, where X represents a perfluoroalkylene group. Specific examples of these include the monomers represented below: CF; = CFOCFCFSOF, CF; = CFOCFCF (CF3) OCF3CF3SO »xF, CF; = CFOCF: CF (CF3) OCF; CFCF3SO) F, CF3 = CF (CF3); SOF, CF3 = CFO [CF; CF (CF3) O] 1CF.CFE3SOF, and CF. = CFOCF; CF (CF; OCF3) OCF; CFSO »xF.

[001104] Among them, CF = CFOCF; CF (CF3) OCF; CF; CFSO0.F = and CF; = CFOCF; CF (CF3) OCF; CF3SO, F are more preferable.

[001105] The copolymer obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, particularly a general polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, a polymerization reaction can be carried out in the presence of a radical polymerization initiator such as a perfluorocarbon peroxide or an azo compound under the conditions of a temperature of 0 to 200ºC and a pressure of 0, 1 to 20 MPa using an inert solvent such as a perfluorohydrocarbon or a chlorofluorocarbon.

[001106] In the above copolymerization, the type of combination of the above monomers and their proportion are not particularly limited and are selected and determined depending on the type and quantity of the desired functional group to be imparted to the fluorine-containing polymer to be obtained. For example, when a fluorine-containing polymer containing only one carboxylic acid group is formed, at least one monomer must be selected from each of the first group and the second group described above and copolymerized. In addition, when a fluorine-containing polymer containing

289/803 only one sulfonic acid group is formed, at least one monomer must be selected from each of the first group and the third group and copolymerized. In addition, when a fluorine-containing polymer with a carboxylic acid group and a sulfonic acid group is formed, at least one monomer must be selected from each of the first group, the second group and the third group described above and copolymerized. In that case, the target fluorine-containing polymer can also be obtained by separately preparing a copolymer comprising the monomers of the first group and the second group described above and a copolymer comprising the monomers of the first group and the third group described above, and then mixing the copolymers. The mixing ratio of the monomers is not particularly limited, and when the number of functional groups per unit of polymer is increased, the proportion of the selected monomers from the second and third groups described above should be increased.

[001107] The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, more preferably 0.6 to 1.5 mg equivalent / g. The total ion exchange capacity here refers to the exchange group equivalent per unit weight of the dry resin and can be measured by neutralization titration or the like.

[001108] In the membrane body 10 of the ion exchange membrane 1, a layer of sulfonic acid 3 containing a polymer containing fluorine with a group of sulfonic acid and a layer of carboxylic acid 2 containing a polymer containing fluorine with a group of carboxylic acid are laminated. By providing the membrane body 10 with this layer configuration, the selective permeability for cations, such as sodium fons, can be further improved.

[001109] The ion exchange membrane | is arranged in an electrolyser

290/803 such that, generally, the sulfonic acid layer 3 is located on the anode side of the electrolyzer and the carboxylic acid layer 2 is located on the cathode side of the electrolyzer.

[001110] The sulfonic acid layer 3 is preferably made of a material with low electrical resistance and has a membrane thickness greater than that of the carboxylic acid layer 2 from the point of view of the membrane resistance. The membrane thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, more preferably 3 to 15 times that of the carboxylic acid layer 2.

[001111] The carboxylic acid layer 2 preferably has high anion exclusion properties, even if it has a small membrane thickness. The anion exclusion properties here refer to the property of trying to prevent anion intrusion and permeation into and through the ion exchange membrane 1. In order to increase the anion exclusion properties, it is effective to lay out a layer of carboxylic acid with a small ion exchange capacity to the sulfonic acid layer.

[001112] As the fluorine-containing polymer for use in the sulfonic acid layer 3, a polymer obtained using CF; = CFOCF; CF (CF3) OCF; CF3SO, 3F as the third group monomer is preferable.

[001113] As the fluorine-containing polymer for use in the carboxylic acid-2 layer, a polymer obtained using CF; = CFOCF; CF (CF3) O (CF;); COOCH; as the monomer of the second group. (Coating layer)

[001114] The ion exchange membrane preferably has a coating layer on at least one surface of the membrane body. As shown in Figure 69, on the ion exchange membrane 1, coating layers 11a and 11b are formed on both surfaces of the membrane body 10.

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[001115] The coating layers contain particles of inorganic material and a binder.

[001116] The average particle size of the particles of inorganic material is preferably 0.90 µm or more. When the average particle size of the particles of inorganic material is 0.90 µm or more, the durability to impurities is greatly improved, in addition to the gas display. That is, increasing the average particle size of the particles of inorganic material, as well as satisfying the value of the specific surface area mentioned above, can achieve a particularly remarkable effect. Irregular inorganic material particles are preferable because the average particle size and specific surface area, as above, are satisfied. Particles of inorganic material obtained by melting and particles of inorganic material obtained by grinding ore can be used. Particles of inorganic material obtained by grinding raw ore can preferably be used.

[001117] The average particle size of inorganic material particles can be 2 µm or less. When the average particle size of the particles of inorganic material is 2 µm or less, it is possible to avoid damage to the membrane due to the particles of inorganic material. The average particle size of the inorganic material particle is more preferably 0.90 to 1.2 µm.

[001118] Here, the average particle size can be measured by a particle size analyzer (“SALD2200”, SHIMADZU CORPORATION).

[001119] Particles of inorganic material preferably have irregular shapes. Such shapes further improve resistance to impurities. Particles of inorganic material preferably have a wide particle size distribution.

[001120] Particles of inorganic material preferably contain

292/803 at least one inorganic material selected from the group consisting of oxides from Group IV elements in the Periodic Table, nitrides from Group IV elements in the Periodic Table and carbides from Group IV elements in the Periodic Table. From the point of view of durability, the zirconium oxide particle is more preferable.

[001121] The particles of inorganic material are preferably particles of inorganic material produced by grinding the raw ore of the particles of inorganic material or particles of inorganic material, as spherical particles with a uniform diameter, obtained by purification by melting the raw ore of the particles of inorganic material.

[001122] Examples of means for grinding raw ore include, but are not particularly limited to, ball mills, ball mills, colloid mills, conical mills, disc mills, roller mills, grain mills, hammer mills, granules, VSI mills, Wiley mills, laminators and jet mills. After grinding, the particles are preferably washed. As a washing method, the particles are preferably treated with acid. This treatment can reduce impurities, such as iron affixed to the surface of particles of inorganic material.

[001123] The coating layer preferably contains a binder. The binder is a component that forms the coating layers retaining particles of inorganic material on the surface of the ion exchange membrane. The binder preferably contains a polymer containing fluorine from the point of view of durability to the electrolytic solution and electrolysis products.

[001124] As the binder, a fluorine-containing polymer with a carboxylic acid group or a sulfonic acid group is preferred, from the point of view of durability to the electrolyte solution and products of electrolysis and adhesion to the surface of the ion exchange membrane. When a layer of

The coating is provided in a layer containing a fluorine-containing polymer with a sulfonic acid group (sulfonic acid layer), a fluorine-containing polymer with a sulfonic acid group is still preferably used as the binder of the coating layer. Alternatively, when a coating layer is provided on a layer containing a fluorine-containing polymer with a carboxylic acid group (carboxylic acid layer), a fluorine-containing polymer with a carboxylic acid group is still preferably used as the binder of the coating layer.

[001125] In the coating layer, the particle content of inorganic material is preferably 40 to 90% by weight, more preferably 50 to 90% by weight. The content of the binder is preferably 10 to 60% by weight, more preferably 10 to 50% by weight.

[001126] The density of distribution of the coating layer on the ion exchange membrane is preferably 0.05 to 2 mg per 1 µm. When the ion exchange membrane has roughness on its surface, the distribution density of the coating layer is preferably 0.5 to 2 mg per 1 in °.

[001127] As the method for forming the coating layer, which is not particularly limited, a known method can be used. An example is a method that includes spraying or the like of a coating liquid obtained by dispersing particles of inorganic material in a solution containing a binder. (Reinforcement core materials)

[001128] The ion exchange membrane preferably has reinforcement core materials arranged within the membrane body.

[001129] The reinforcement core materials are members that enhance the resistance and dimensional stability of the ion exchange membrane. When arranging the reinforcement core materials within the membrane body, particularly the expansion and contraction of the exchange membrane

294/803 ionic can be controlled in the desired range. Such an ion exchange membrane does not expand or contract more than necessary during electrolysis and the like and can maintain excellent dimensional stability in the long run.

[001130] The configuration of the reinforcement core materials is not particularly limited and, for example, the reinforcement core materials can be formed by spinning threads called reinforcement threads. The reinforcement threads here refer to threads that are members that make up the reinforcement core materials, can provide the desired dimensional stability and mechanical resistance to the ion exchange membrane and can be stably present in the ion exchange membrane. By using the reinforcement core materials obtained by spinning such reinforcement threads, better dimensional stability and mechanical resistance to the ion exchange membrane can be provided.

[001131] The material of the reinforcement core materials and the reinforcement yarns used for them is not particularly limited, but is preferably a material resistant to acids, alkalis, etc., and a fiber comprising a fluorine-containing polymer is preferable because the long-term thermal resistance and chemical resistance are required.

[001132] Examples of the fluoride-containing polymer to be used in the reinforcement core materials include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers, tetrafluoroethylene-ethylene (ETFE) copolymers, tetrafluoroethylene-copolymers, hexetrafluoroethylene-copolymers, tetrafluoroethylene-copolymers. trifluorochlorethylene-ethylene and polymers of vinylidene fluoride (PVDF). Among these, fibers comprising polytetrafluoroethylene are preferably used from the point of view of heat resistance and chemical resistance.

[001133] The wire diameter of the reinforcement wires used for the reinforcement core materials is not particularly limited, but is preferably 20

295/803 to 300 deniers, more preferably 50 to 250 deniers. The weave density (tissue count per unit length) is preferably 5 to 50 / inch. The shape of the reinforcement core materials is not particularly limited, for example, a woven fabric, a non-woven fabric and a knitted fabric are used, but it is preferably in the form of a woven fabric. The thickness of the woven fabric to be used is preferably 30 to 250 µm, more preferably 30 to 150 µm.

[001134] As woven fabric or knitted fabric, monofilaments, multifilaments, or yarns thereof, a slit yarn, or the like, and various types of weaving methods, such as single weft, leno weft, knitted weft, weft, can be used cord and sirsaca, can be used.

[001135] The weft and the arrangement of the reinforcement core materials in the membrane body are not particularly limited, and the preferred arrangement can be suitably provided considering the size and shape of the ion exchange membrane, desired physical properties for the membrane of ion exchange, the environment of use and the like.

[001136] For example, the reinforcement core materials can be arranged along a predetermined direction of the membrane body, but from the point of view of dimensional stability, it is preferable that the reinforcement core materials are arranged over a predetermined first direction, and other reinforcement core materials along a second direction substantially perpendicular to the first direction. By arranging the plurality of reinforcement core materials substantially orthogonally within the membrane body, it is possible to provide better dimensional stability and mechanical strength in several directions. For example, the arrangement in which reinforcement core materials arranged along the longitudinal direction (warp yarns) and reinforcement core materials arranged along the transverse direction (weft threads) are woven on the surface side of the body membrane is preferred. The arrangement is more

296/803 preferably in the form of driven flat weft and woven fabric allowing the warps and wefts to alternately move between themselves and underneath each other, smooth weft in which two warps are woven in wefts while twisted, weft in basket driven and woven by insertion in two or more warps arranged in parallel, wefts of the same or similar number, from the point of view of dimensional stability, mechanical resistance and ease of production.

[001137] It is preferred that, in particular, the reinforcement core materials are arranged along both directions, the MD (Machine Direction) and TD (Transversal Direction) of the ion exchange membrane. In other words, the reinforcement core materials are preferably single woven in MD and TD. Here, MD refers to the direction in which the membrane body and various core materials (for example, the reinforcement core materials, reinforcement wires and sacrificial wires described below) are transported in a production step of ion exchange membrane described later (flow direction) and TD refers to the direction substantially perpendicular to the MD. The threads woven along the MD are called MD threads, and the threads woven along the TD are called TD threads. Typically, the ion exchange membrane used for electrolysis is rectangular, and in many cases, the longitudinal direction is the MD, and the width direction is the TD. By weaving the reinforcement core materials that are MD yarns and the reinforcement core materials that are TD yarns, it is possible to provide better dimensional stability and mechanical strength in many directions.

[001138] The range of arrangement of the reinforcement core materials is not particularly limited, and the preferred arrangement can be suitably provided considering the desired physical properties for the ion exchange membrane, the environment of use and the like.

[001139] The orifice ratio for reinforcement core materials is not particularly limited, but is preferably 30% or more, more

297/803 preferably 50% or more and 90% or less. The orifice ratio is preferably 30% or more from the point of view of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the point of view of the mechanical strength of the ion exchange membrane.

[001140] The orifice ratio for reinforcement core materials refers to a ratio of a total area of a surface through which substances such as fons (an electrolyte solution and cations contained in it (for example, sodium fons)) they can pass (B) to the area of one of the surfaces of the membrane body (A) (B / A). The total surface area through which substances such as fons can pass (B) can refer to the total areas of regions in which the ion exchange membrane, cations, an electrolyte solution and the like are not blocked by the reinforcement core materials and similar substances contained in the ion exchange membrane.

[001141] Figure 70 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane. Figure 70, in which a portion of the ion exchange membrane is enlarged, shows only the arrangement of the reinforcement core materials 21 and 22 in the regions, omitting the illustration of the other members.

[001142] By subtracting the total area of the reinforcement core materials (C) from the area of the region surrounded by the reinforcement core materials 21 arranged along the longitudinal direction and the reinforcement core materials 22 arranged along the transverse direction, the region including the area of the reinforcement core materials (A), the total area of regions through which substances such as phons can pass (B) in the area of the region described above (A) can be obtained. That is, the orifice ratio can be determined by the following formula (1): Orifice ratio = (B) / (A) = ((A) - (O)) / (A) ... (D

[001143] Among the materials of the reinforcement core, a shape

Particularly preferred 298/803 are ribbon yarns or highly oriented monofilaments comprising PTFE from the point of view of chemical resistance and heat resistance. Specifically, reinforcement core materials forming a single web in which 50 to 300 denier ribbon yarns obtained by cutting a high strength porous sheet comprising PTFE into a ribbon form, or highly oriented 50 to 300 denier monofilaments are used comprising PTFE and having a weave density of 10 to 50 threads or monofilaments / inch and having a thickness in the range of 50 to 100 µm are more preferred. The orifice ratio of an ion exchange membrane comprising such reinforcement core materials is still preferably 60% or more.

[001144] Examples of the shape of the reinforcement threads include round threads and ribbon threads. (Continuous holes)

[001145] The ion exchange membrane preferably has continuous holes inside the membrane body. [001 146] Continuous holes refer to holes that can be flow paths for fons generated in electrolysis and an electrolyte solution. The continuous holes, which are tubular holes formed inside the membrane body, are formed by dissolving the sacrificial core materials (or sacrificial threads) described below. The shape, diameter or the like of the continuous holes can be controlled by selecting the shape or diameter of the sacrificial core materials (sacrificial threads).

[001147] Forming the continuous holes inside the ion exchange membrane can guarantee the mobility of an electrolyte solution in electrolysis. The shape of the continuous holes is not particularly limited, but it may be the shape of the sacrificial core materials to be used for forming the continuous holes according to the production method described below.

[001148] The continuous holes are preferably formed in order to

299/803 pass alternately on the anode side (sulfonic acid layer side) and on the cathode side (carboxylic acid layer side) of the reinforcement core materials. With this structure, in a portion in which continuous holes are formed on the cathode side of the reinforcement core materials, ions (eg sodium fons) carried by the electrolyte solution with which the continuous holes are filled can also flow on the side of the cathode of the reinforcement core materials. As a result, the flow of cations is not interrupted and, therefore, it is possible to further reduce the electrical resistance of the ion exchange membrane.

[001149] Continuous holes can be formed along only a predetermined direction of the membrane body that constitutes the ion exchange membrane, but are preferably formed both in the longitudinal and transverse direction of the membrane body from the point of view of presenting a more stable electrolytic performance. [Production method]

[001150] A suitable example of a method for producing an ion exchange membrane includes a method including the following steps (1) to (6): Step (1): the step of producing a fluorine-containing polymer with an exchange group ionic or an ion exchange group precursor capable of forming an ion exchange group by hydrolysis, Step (2): the step of weaving at least a plurality of reinforcement core materials, as required, and sacrificial yarns with a proprietary dissolving in an acid or an alkali, and forming continuous holes to obtain a reinforcement material in which the sacrifice wires are arranged between the reinforcement core materials adjacent to each other, Step (3): the formation step in a film of the above fluorine-containing polymer with an ion exchange group or a precursor to the ion exchange group capable of forming an ion exchange group by hydrolysis,

300/803 Step (4): the step of embedding the reinforcement materials above, as required, in the above film to obtain a membrane body within which the reinforcement materials are arranged, Step (5): the hydrolysis step of the membrane body obtained in step (4) (hydrolysis step), and Step (6): the step of providing a coating layer on the membrane body obtained in step (5) (application step).

[001151] Next, each of the steps will be described in detail. Step (1): Fluorine-containing polymer production step

[001152] In step (1), the raw material monomers described in the first group for the third group above are used to produce a fluorine-containing polymer. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the raw material monomers must be adjusted in the production of the fluorine-containing polymer that forms the layers. Step (2): Reinforcement materials production step

[001153] The reinforcement material is a woven fabric obtained by weaving reinforcement threads or the like. The reinforcement material is embedded in the membrane to form reinforcement core materials. When an ion exchange membrane with continuous holes is formed, the sacrificial threads are additionally woven into the reinforcement material. The amount of the sacrificial yarns contained in that case is preferably 10 to 80% by weight, more preferably 30 to 70% by weight based on the entire reinforcement material. Weaving the sacrificial yarns can also prevent the yarn from slipping the reinforcement core materials.

[001154] As sacrificial threads, which have solubility in the membrane production stage or under an electrolysis environment, rayon, polyethylene terephthalate (PET), cellulose, polyamide and the like are used. Also preferred are monofilaments or multifilaments with a thickness of 20 to 50

301/803 deniers and comprising polyvinyl alcohol and the like.

[001155] In step (2), the orifice ratio, the arrangement of the continuous holes and the like can be controlled by adjusting the arrangement of the reinforcement core materials and the sacrifice wires. Step (3): Film forming step

[001156] In step (3), the fluorine-containing polymer obtained in step (1) is formed into a film using an extruder. The film can be a single layer configuration, a two layer configuration of a sulfonic acid layer and a layer of carboxylic acid, as mentioned above, or a multilayer configuration of three layers or more.

[001157] Examples of the film-forming method include the following: a method in which a fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are formed separately in films; and a method in which the fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are coextruded into a composite film.

[001158] The number of each film can be more than one. Coextrusion of different films is preferred because of their contribution to an increase in adhesive strength at the interface. Stage (4): Stage of obtaining the membrane body

[001159] In step (4), the reinforcement material obtained in step (2) is embedded in the film obtained in step (3) to provide a membrane body including the reinforcement material therein.

[001160] Preferable examples of the method for forming a membrane body include (1) a method in which a fluorine-containing polymer with a precursor to the carboxylic acid group (e.g., functional group

302/803 carboxylate) (hereinafter, a layer comprising the same is called the first layer) located on the cathode side and a fluorine-containing polymer with a precursor to the sulfonic acid group (for example, sulfonyl fluoride functional group) ( hereinafter, a layer comprising the same is called a second layer) are formed into a film by a coextrusion method and, using a heat source and a vacuum source as needed, a reinforcement material and the second composite film layer / first layer are laminated in that order on heat-resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated by reduced pressure; and (11) a method in which, in addition to the composite film of the second layer / first layer, a fluorine-containing polymer with a precursor to the sulfonic acid group is formed separately in a film (the third layer) in advance and, using a heat source and a vacuum source as needed, the third layer film, the reinforcement core materials and the composite film comprising the second layer / first layer are laminated in that order on heat resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated under reduced pressure.

[001161] The coextrusion of the first layer and the second layer contributes to an increase in the adhesive strength at the interface.

[001162] The method including integration under reduced pressure is characterized by making the third layer in the reinforcement material thicker than that of the pressure method of applying pressure. In addition, since the reinforcement material is fixed on the inner surface of the membrane body, the method has a property capable of sufficiently retaining the

303/803 mechanical resistance of the ion exchange membrane.

[001163] The lamination variations described here are exemplary, and coextrusion can be performed after a preferred lamination pattern (for example, the combination of layers) has been appropriately selected considering the desired layer configuration of the membrane body and physical properties, and the like.

[001164] In order to further improve the electrical properties of the ion exchange membrane, it is also possible to additionally interpose a fourth layer comprising a fluorine-containing polymer with a precursor of the carboxylic acid group and a precursor of the sulfonic acid group between the first layer and the second layer or using a fourth layer comprising a fluorine-containing polymer with a carboxylic acid group precursor and a sulfonic acid group precursor instead of the second layer.

[001165] The method for forming the fourth layer can be a method in which a fluorine-containing polymer with a carboxylic acid group precursor and a fluorine-containing polymer with a sulfonic acid group precursor are separately produced and then mixed or can be a method wherein a monomer with a precursor to the carboxylic acid group and a monomer with a precursor to the sulfonic acid group are copolymerized.

[001166] When the fourth layer is used as a component of the ion exchange membrane, a coextruded film of the first layer and the fourth layer is formed, in addition, the third layer and the second layer are formed separately in films, and the lamination can be performed by the method mentioned above. Alternatively, the three layers of the first layer / fourth layer / second layer can be simultaneously formed into a film by coextrusion.

[001167] In this case, the direction in which the extruded film flows is the MD.

304/803 As mentioned above, it is possible to form a membrane body containing a fluorine-containing polymer with an ion exchange group in a reinforcement material.

[001168] Additionally, the ion exchange membrane preferably has protruding portions composed of the fluorine-containing polymer with a sulfonic acid group, that is, projections, on the surface side composed of the sulfonic acid layer. As a method for forming such projections, which is not particularly limited, one can also use a known method including forming projections on a resin surface. A specific example of the method is a method of embossing the surface of the membrane body. For example, the above projections can be formed using release paper embossed in advance when the composite film mentioned above, reinforcement material and the like are integrated. In the case where the projections are formed by embossing, the height and density of arrangement of the projections can be controlled by controlling the form of embossing to be transferred (shape of the release paper). (5) Hydrolysis step

[001169] In step (5), a hydrolysis step of the membrane body obtained in step (4) is carried out to convert the precursor of the ion exchange group into an ion exchange group (hydrolysis step).

[001170] In step (5), it is also possible to form dissolution holes in the membrane body by dissolving and removing the sacrifice wires included in the membrane body with acid or alkali. The sacrifice wires can remain in the continuous holes without being completely dissolved and removed. The sacrifice wires that remain in the continuous holes can be dissolved and removed by the electrolyte solution when the ion exchange membrane is subjected to electrolysis.

[001171] The sacrifice wire has solubility in acid or alkali in the step

305/803 production of an ion exchange membrane or under an electrolysis environment. The sacrifice wires are eluted to form continuous holes at the corresponding locations.

[001172] Step (5) can be carried out by immersing the membrane body obtained in step (4) in a hydrolysis solution containing acid or alkali. An example of the hydrolysis solution that can be used is a mixed solution containing KOH and dimethyl sulfoxide (DMSO).

[001173] The mixed solution preferably contains KOH of 2.5 to 4.0 Ne and DMSO of 25 to 35% by weight.

[001174] The temperature for hydrolysis is preferably 70 to 100 ° C. The higher the temperature, the greater the apparent thickness. The temperature is more preferably 75 to 100 ° C.

[001175] The time for hydrolysis is preferably 10 to 120 minutes. The longer the time, the greater the apparent thickness. The time is most preferably 20 to 120 minutes.

[001176] The step of forming continuous holes eluting the sacrificial wire will now be described in more detail. Figures 71 (a) and (b) are schematic views to explain a method for forming the continuous holes in the ion exchange membrane.

[001177] Figures 71 (a) and (b) show reinforcement wires 52, sacrifice wires 504a and continuous holes 504 formed only by sacrifice wires 504a, omitting the illustration of the other members, such as a body of membrane.

[001178] Firstly, the reinforcement wires 52 which constitute reinforcement core materials in the ion exchange membrane and the sacrifice wires 504a to form the continuous holes 504 in the ion exchange membrane are used as interlaced reinforcement materials. Then, in step (5), the sacrifice threads 504a are eluted to form continuous holes 504.

[001179] The above method is simple because the method for interlacing the

306/803 reinforcement wires 52 and sacrifice wires 504a can be adjusted depending on the arrangement of the reinforcement core materials and the continuous holes in the membrane body of the ion exchange membrane.

[001180] Figure 71 (a) exemplifies the single fabric reinforcement material in which reinforcement threads 52 and sacrifice threads 504a are interwoven along the longitudinal and lateral direction on the paper, and the arrangement of the reinforcement 52 and the sacrifice wires 504a in the reinforcement material may vary as required. (6) Application stage

[001181] In step (6), a coating layer can be formed by preparing a coating liquid containing particles of inorganic material obtained by grinding raw ore or melting raw ore and a binder, applying the coating liquid on the surface of the ion exchange membrane obtained in step (5), and drying of the coating liquid.

[001182] A preferred binder is a binder obtained by hydrolysis of a fluorine-containing polymer with an ion exchange group precursor with an aqueous solution containing dimethylsulfoxide (DMSO) and potassium hydroxide (KOH) and then immersion of the polymer in hydrochloric acid to replace the counter-ion of the ion exchange group with H + (for example, a fluorine-containing polymer with a carboxyl group or a sulfo group). Thus, the polymer is more likely to dissolve in water or ethanol mentioned below, which is preferable.

[001183] This binder is dissolved in a mixed solution of water and ethanol. The volume ratio between water and ethanol is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 2: 1 to 1: 2. The particles of inorganic material are dispersed with a ball mill in the dissolution liquid thus obtained to provide a coating liquid. In this case, it is also possible to adjust the average size of

307/803 particle and similar particles by adjusting the time and speed of rotation during dispersion. The preferable amount of the particles of inorganic material and the binder to be mixed is as mentioned above.

[001184] The concentration of the particles of inorganic material and the binder in the coating liquid is not particularly limited, but a thin-coated liquid is preferable. This allows uniform application to the surface of the ion exchange membrane.

[001185] Additionally, a surfactant can be added to the dispersion when the particles of inorganic material are dispersed. Like the surfactant, nonionic surfactants are preferable and examples of them include HS-210, NS-210, P-210 and E-212 manufactured by NOF CORPORATION.

[001186] The coating liquid obtained is applied on the surface of the ion exchange membrane by spray application or roller coating, thus providing an ion exchange membrane. [Microporous membrane]

[001187] The microporous membrane of the present modality is not particularly limited as long as the membrane can be formed in a laminate with the electrolysis electrode, as mentioned above. Several microporous membranes can be used.

[001188] The porosity of the microporous membrane of the present embodiment is not particularly limited, but it can be from 20 to 90, for example, and is preferably from 30 to 85. The porosity above can be calculated by the following formula: Porosity = (1 - (the weight of the membrane in a dry state) / (the weight calculated from the volume calculated from the thickness, width and length of the membrane and the density of the membrane material)) x 100

[001189] The average pore size of the microporous membrane of the present embodiment is not particularly limited, and can be from 0.01 µm to

308/803 µm, for example, preferably 0.05 µm to 5 µm. Regarding the average pore size, for example, the membrane is cut vertically in the direction of thickness, and the section is observed with an FE-SEM. The average pore size can be obtained by measuring the diameter of about 100 observed pores and averaging the measurements.

[001190] The thickness of the microporous membrane of the present embodiment is not particularly limited, and can be from 10 µm to 1000 µm, for example, preferably 50 µm to 600 µm. The above thickness can be measured using a micrometer (manufactured by Mitutoyo Corporation) or similar, for example.

[001191] Specific examples of the microporous membrane as mentioned above include Zirfon Perl UTP 500 manufactured by Agfa (also called Zirfon membrane in the present embodiment) and those described in International Publication No. WO 2013-183584 and International Publication No. WO 2016-203701.

[001192] In the present embodiment, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different EW (ion exchange capacity) than that of the first layer of ion exchange resin. In addition, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different functional group than that of the first layer of ion exchange resin. The ion exchange capacity can be adjusted by the functional group to be introduced, and functional groups that can be introduced are as mentioned above.

[001193] In the present embodiment, the portion of laminate 25 to be sandwiched between the anode gasket 12 and the cathode gasket 13 is preferably a non-conductive surface. The "conductive surface" corresponds to a portion designed to allow electrolytes

309/803 migrate between the anodic chamber and the cathodic chamber, and the “non-conductive surface” is a portion not corresponding to the conductive surface.

[001194] In the present embodiment, the outermost perimeter of the laminate may be located on an inner side or further away than the outermost perimeter of the anode-side gasket and the cathode-side gasket towards the conductive surface, but it is preferably located outside. In the case of such a configuration, the outermost perimeter located further away can be used as an adherence margin and, thus, the working capacity in the assembly of the electrolyzer tends to be improved. The outermost perimeter of the laminate here is the outermost perimeter of the membrane and electrode for electrolysis in combination. That is, when the outermost perimeter of the electrolysis electrode is located further away from the mutual contact surface than the outermost perimeter of the membrane, the outermost perimeter of the laminate means the outermost perimeter of the electrolysis electrode. In contrast, when the outermost perimeter of the electrolysis electrode is located on an inner side of the mutual contact surface than the outermost perimeter of the membrane, the outermost perimeter of the laminate means the outermost perimeter of the membrane.

[001195] The positional relationship will be described using Figures 72 and

73. Figures 72 and 73 show particularly the positional relationship of the gaskets and the laminate when the two electrolytic cells shown in Figure 64B, for example, are viewed from the direction a. In Figures 72 and 73, a rectangular gasket A with a hole portion in the center is located on the most frontal side. A rectangular membrane B is located at the back of A, and a rectangular electrode for electrolysis C is still located at the back of B. That is, the orifice portion of the gasket A is a portion corresponding to the conductive surface of the laminate.

[001196] In Figure 72, the outermost perimeter Al of the gasket A is

310/803 located on the inner side of the outermost perimeter B1 of membrane B and the outermost perimeter C1 of the electrode for electrolysis C towards the conductive surface.

[001197] In Figure 73, the outermost perimeter Al of the gasket A is located farther than the outermost perimeter C1 of the electrode for electrolysis C towards the conductive surface, but the outermost perimeter B1l of the membrane B is located further away than the outermost perimeter Al of the gasket A towards the conductive surface.

[001198] In the present embodiment, the laminate must be sandwiched between the anode-side gasket and the cathode-side gasket, and the electrolysis electrode itself cannot be sandwiched directly between the anode-gasket and the gasket on the anode. side of the cathode. That is, as long as the electrolysis electrode itself is attached to the membrane, only the membrane can be sandwiched directly between the anode-side gasket and the cathode-side gasket. In the present embodiment, from the point of view of more stable fixation of the electrolysis electrode in the electrolyser, both the electrolysis electrode and the membrane are preferably sandwiched between the anode-side gasket and the cathode-side gasket.

[001199] In the present modality, the membrane and electrode for electrolysis are fixed at least by the anode gasket and the cathode gasket to exist as a laminate, but can have another fixation configuration. For example, an attachment configuration exemplified below can be used. Only one fixture configuration can be used, or two or more fixture configurations can be used in combination.

[001200] In the present embodiment, at least a portion of the electrolysis electrode preferably penetrates the membrane and, therefore, is fixed. The appearance will be described using Figure 74A.

[001201] In Figure 74A, at least a portion of the electrolysis electrode 2 penetrates the membrane 3 and is thus fixed. Figure 74A shows an example in which the electrolysis electrode 2 is a porous metallic electrode. That is, in Figure 74A, a plurality of electrode electrode portions 2 are shown separately, but these portions are continuous. Thus, the cross section of an integral porous metal electrode is shown (the same applies to Figures 75 to 78 below).

[001202] In the electrode configuration, when the membrane 3 in the predetermined position (position to be the fixed portion), for example, is pressed on the electrode for electrolysis 2, a portion of the membrane 3 penetrates the roughness geometry or the opening geometry on the electrode surface for electrolysis 2. Then, recesses on the electrode surface and the projections around the openings penetrate the membrane 3 and preferably penetrate through the outer surface 3b of the membrane 3, as shown in Figure 74A.

[001203] As described above, the fixation configuration in Figure 74A can be produced by pressing membrane 3 on the electrolyte for electrolysis 2. In this case, membrane 3 is softened by heating and then subjected to thermal compression and thermal suction. Then, electrolyte electrode 2 penetrates membrane 3. Alternatively, membrane 3 can be used in a melting state. In this case, the membrane is preferably aspirated from the outer surface side 2b (rear surface side) of the electrolysis electrode 2 in the state shown in Figure 74B. The region in which membrane 3 is pressed on electrode for electrolysis 2 constitutes the “fixed portion”.

[001204] The fixation configuration shown in Figure 74A can be observed by an magnifier (magnifying glass), an optical microscope or an electron microscope. Once the electrolysis electrode 2 has penetrated the membrane 3, it is possible to estimate the fixation configuration in Figure 74A by a conduction test between the outer surface 3b of the membrane 3 and the outer surface 2b of the electrode for electrolysis 2 using a tester or similar.

[001205] In the present embodiment, at least a portion of the electrolysis electrode is located and fixed within the membrane in the fixed portion. The appearance will be described using Figure 75A.

[001206] As described above, the electrode surface for electrolysis 2 has a roughness geometry or opening geometry. In the embodiment shown in Figure 75A, a portion of the electrode surface enters the membrane 3 at the predetermined position (position to be the fixed portion) and is attached to it. The fixation configuration shown in Figure 75A can be produced by pressing the membrane 3 on the electrolysis electrode 2. In that case, the fixation configuration in Figure 75A is preferably formed by softening the membrane 3 by heating and then by thermal compression and thermal aspiration of the membrane 3. Alternatively, the fixation configuration in Figure 75A can be formed by melting the membrane 3. In this case, the membrane 3 is preferably aspirated from the side of the outer surface 2b (side of the back surface) of the electrode for electrolysis 2.

[001207] The fixation configuration shown in Figure 75A can be observed by an magnifier (magnifying glass), an optical microscope or an electron microscope. Particularly preferable is a method that includes subjecting the sample to an inlay treatment, then forming a cross section by a microtome and observing the cross section. In the fixation configuration shown in Figure 75A, the electrolysis electrode 2 does not penetrate the membrane 3. Thus, no conduction between the outer surface 3b of the membrane 3 and the outer surface 2b of the electrolysis electrode 2 is identified by the conduction test.

[001208] In the present embodiment, it is preferable that the laminate additionally has a fixing member to fix the membrane and electrode for electrolysis. The appearance will be described using Figures 76A to C.

[001209] The fixation configuration shown in Figure 76A is a

313/803 configuration in which a fixing member 7, which is separated from the electrolysis electrode 2 and the membrane 3, is used and the fixing member 7 penetrates and thereby fixes the electrolysis electrode 2 and the membrane 3. The electrode for electrolysis 2 it is not necessarily penetrated by the fixing member 7, and must be fixed by the fixing member 7 so as not to be separated from the membrane 2. The material for the fixing member 7 is not particularly limited, and materials consisting of metal , resin or the like, for example, can be used as the fixing member 7. Examples of the metal include nickel, nichrome, titanium and stainless steel (SUS). Oxides of the same can be used. Examples of the resin that can be used include fluorine resins (for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene and perfluoroalkoxyethylene (PFA) copolymers, tetrafluoroethylene and ethylene (ETFE) copolymers, membrane materials 3 described below), polyvinyl fluoride (PVDF), ethylene-propylene-diene rubber (EPDM), polyethylene (PP), polypropylene (PE), nylon and aramid.

[001210] In the present embodiment, for example, a wire-type metal or resin is used to sew the predetermined position (position to be the fixed portion) between the outer surface 2b of the electrolysis electrode 2 and the outer surface 3b of the membrane 3, as shown in Figures 76B and C. It is also possible to fix the electrolyte electrode 2 to the membrane 3, using a fixation mechanism, such as a fixation device.

[001211] The fixation configuration shown in Figure 77 is a configuration in which the fixation is made by an organic resin (adhesion layer) interposed between the electrolyte electrode 2 and the membrane 3. That is, in Figure 77, it is shown a configuration in which an organic resin as the fixing member 7 is arranged in the predetermined position (position to be the fixed portion) between the electrolysis electrode 2 and the membrane 3 to thereby fix by adhesion. For example, the organic resin applied to the inner surface 2a of the electrolysis electrode 2, the inner surface 3a of the

314/803 membrane 3, or one or both of the inner surface 2a of the electrode for electrolysis 2 and the inner surface 3a of the membrane 3. Then, the fixation configuration shown in Figure 77 can be formed by laminating the electrode for electrolysis 2 to the membrane 3. The materials for the organic resin are not particularly limited, but examples of the same that can be used include fluorine resins (e.g., PTFE, PFE and PFPE) and resins similar to the materials that make up membrane 3 as mentioned above. Commercially available fluoride-containing adhesives and PTFE dispersions can also be used as appropriate. In addition, multipurpose vinyl acetate adhesives, ethylene-vinyl acetate copolymer adhesives, acrylic resin adhesives, a-olefin adhesives, styrene-butadiene rubber latex adhesives, vinyl chloride resin adhesives, adhesives chloroprene, nitrile rubber adhesives, urethane rubber adhesives, epoxy adhesives, silicone resin adhesives, modified silicone adhesives, epoxy modified silicone resin adhesives, silylated urethane resin adhesives, cyanoacrylate adhesives and the like can be used.

[001212] In the present modality, organic resins that dissolve in an electrolyte solution or dissolve or decompose during electrolysis can be used. Examples of resins that dissolve in an electrolyte solution or dissolve or decompose during electrolysis include, but are not limited to, vinyl acetate adhesives, ethylene-vinyl acetate copolymer adhesives, acrylic resin adhesives, air adhesives -olefin, styrene-butadiene rubber latex adhesives, vinyl chloride resin adhesives, chloroprene adhesives, nitrile rubber adhesives, urethane rubber adhesives, epoxy adhesives, silicone resin adhesives, modified silicone adhesives, epoxy modified silicone resin adhesives, silylated urethane resin adhesives and cyanoacrylate adhesives.

315/803

[001213] The fixation configuration shown in Figure 77 can be observed by an optical microscope or electron microscope. Particularly preferable is a method that includes subjecting the sample to an inlay treatment, then forming a cross section by a microtome and observing the cross section.

[001214] In the present embodiment, at least a portion of the fixation member preferably externally grips the membrane and electrode for electrolysis. The appearance will be described using Figure 78A.

[001215] The fixation configuration shown in Figure 78A is a configuration in which electrode for electrolysis 2 and membrane 3 are attached and fixed externally. That is, the outer surface 2b of the electrolysis electrode 2 and the outer surface 3b of the membrane 3 are sandwiched and fixed by a gripping member such as the fixation member 7. In the fixation configuration shown in Figure 78A, a state in which the gripping member is engaging the electrolysis electrode 2 and the membrane 3 is also included. Examples of the gripping member include tape and clips.

[001216] In the present modality, a gripping member that dissolves in an electrolyte solution can be used. Examples of the gripping member that dissolves in an electrolyte solution include PET tape and clips and PVA tapes and clips.

[001217] In the fixation configuration shown in Figure 78A, unlike Figures 74 to 77, the electrolysis electrode 2 and the membrane 3 are not joined at the interface between them, but the inner surface 2a of the electrolysis electrode 2 and the inner surface 3a of the membrane 3 are just touching or opposite each other. Removing the gripping member can release the fixed state of the electrolysis electrode 2 and the membrane 3 and separate the electrolysis electrode 2 from the membrane 3.

[001218] Although not shown in Figure 78A, it is also possible

316/803 fix the electrode for electrolysis 2 and the membrane 3 using a gripping member in an electrolytic cell.

[001219] Also in the present embodiment, at least a portion of the fixation member preferably fixes the membrane and electrode for electrolysis by magnetic force. The appearance will be described using Figure 78B.

[001220] The fixation configuration shown in Figure 78B is a configuration in which electrode for electrolysis 2 and membrane 3 are attached and fixed externally. The difference from Figure 78A is that a pair of magnets is used as the gripping member, which is the fixing member. In the aspect of the fastening configuration shown in Figure 78B, a laminate | is attached to the electrolyser. Thereafter, during the operation of the electrolyser, the gripping member can be left as is or removed from the laminate |.

[001221] Although not shown in Figure 78B, it is also possible to fix electrode for electrolysis 2 and membrane 3 using a gripping member in an electrolytic cell. When a magnetic material that adheres to magnets is used as part of the material for the electrolytic cell, a gripping material is placed on the surface side of the membrane. Then, the gripping material and the electrolytic cell can sandwich and fix the electrolyte electrode 2 and the membrane 3 between them.

[001222] A plurality of fixed portion lines can be provided. That is, 1, 2, 3, .. n fixed portion lines can be arranged from the contour side towards the inner side of laminate 1. n is an integer of 1 or more. The m-th fixed portion line (m <n) and the L-th fixed portion line (m <L <n) can be formed to have a different fixation pattern.

[001223] A fixed portion line to be formed on the conductive surface preferably has a symmetrical line shape. This tends to

317/803 allow the voltage concentration to be controlled. For example, when two orthogonally intersecting directions are called the X direction and the Y direction, it is possible to configure the fixed portion by arranging a fixed portion line, each in the X direction and in the Y direction, or arranging a plurality of portion lines fixed at equal intervals, each in the X direction and in the Y direction. The number of fixed portion lines in the X direction and in the Y direction is not limited, but is preferably 100 or less each in the X direction and the Y direction. From the point of view of achieving the flatness of the conductive surface, the number of fixed portion lines is preferably 50 or less, each, in the X and Y directions.

[001224] When the fixed portion in the present embodiment has the fixation configuration shown in Figure 74A or Figure 76, a sealing material is preferably applied to the membrane surface of the fixed portion in order to prevent a short circuit caused by a contact between the anode and the cathode. As a sealing material, the materials described for the adhesives above can be used.

[001225] The laminate in the present embodiment can have several fixed portions in various positions as mentioned above, but from the point of view of achieving sufficient electrolytic performance, these fixed portions are preferably present on the non-conductive surface.

[001226] The laminate in the present embodiment may have several fixed portions in various positions as mentioned above, but the electrolysis electrode preferably satisfies the "applied force" mentioned above particularly in a portion in which no fixed portion is present (non-fixed portion) . That is, the force applied per unit of mass-unit area of the electrode for electrolysis in the non-fixed portion is preferably less than 1.5 N / mg: -em ?.

[001227] In the present embodiment, it is preferable that the membrane comprises an ion exchange membrane comprising a layer

318/803 surface containing an organic resin and the electrolysis electrode is fixed by the organic resin. The organic resin is as mentioned above and can be formed as the surface layer of the ion exchange membrane by several known methods. (Water electrolysis)

[001228] The electrolyser of the present modality, like an electrolyser in the case of water electrolysis, has a configuration in which the ion exchange membrane in an electrolyser for use in the case of common salt electrolysis mentioned above is replaced by a microporous membrane. The raw material to be supplied, which is water, is different from that for the electrolyser in the case of electrolysis of the common salt mentioned above. As for the other components, components similar to those of the electrolyser in the case of electrolysis of common salt can also be used in the electrolyser in the case of water electrolysis. Since chlorine gas is generated in the anodic chamber in the case of common salt electrolysis, titanium is used as the material in the anodic chamber, but in the case of water electrolysis, only oxygen gas is generated in the anodic chamber. Thus, a material identical to that of the cathodic chamber can be used. An example of this is nickel. For the anode coating, the catalyst coating for oxygen generation is suitable. Examples of the catalyst coating include metals, oxides and hydroxides of the metals of the platinum group and metals of the transition metal group. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used. (Method to produce the electrolyser and method to renew the laminate)

[001229] A method for renewing the laminate in the electrolyzer of the present mode has a step of separating the laminate in the present mode of the anode-side gasket and the cathode-side gasket to thereby remove the laminate from the electrolyzer, and a sandwiching step of a new laminate between the gasket on the anode side and the gasket on the

319/803 cathode. The new laminate means the laminate in the present modality, and at least one of the electrodes for electrolysis and the membrane must be new.

[001230] In the laminating sandwiching step described above, from the point of view of more stable fixation of the electrolyte electrode in the electrolyzer, both the electrolysis electrode and the membrane are preferably sandwiched between the anode-side gasket and the side-gasket. of the cathode.

[001231] Additionally, the method for producing the electrolyzer of the present modality has a laminating sandwich step in the present modality between the anode-side gasket and the cathode-side gasket.

[001232] The method for producing the electrolyzer and the method for renewing the laminate of the present modality, as configured as described above, can improve the work efficiency during the electrode renewal in the electrolyzer and, in addition, can provide an excellent electrolytic performance also after renovation.

[001233] Also in the laminating sandwiching step described above, from the point of view of more stable fixation of the electrolysis electrode in the electrolyzer, both the electrolysis electrode and the membrane are preferably sandwiched between the anode gasket and the gasket. side of the cathode. <Fifth modality>

[001234] Here, a fifth embodiment of the present invention will be described in detail with reference to Figures 91 to 102. [Method for producing the electrolyzer]

[001235] The method for producing an electrolyzer according to the fifth modality (hereinafter, in the section of <Fifth modality>, simply called “the present modality”) is a method for producing a new electrolyzer by arranging an electrolysis electrode or one

320/803 laminate of the electrolysis electrode and a new membrane in an existing electrolyzer comprising an anode, a cathode that is opposite the anode, and a membrane that is arranged between the anode and the cathode, in which the electrolysis electrode or the laminate , being in a rolled-up body shape, is used. As described above, according to the method for producing an electrolyser according to the present embodiment, an electrolysis electrode or a laminate of the electrolysis electrode and a new membrane, being in a coiled body shape, are used. Thus, the electrolyte electrode or the laminate, when used as a member of the electrolyzer, can be reduced for transport or the like, and the work efficiency during the electrode renewal in the electrolyzer can be improved.

[001236] In the present embodiment, the existing electrolyzer comprises an anode, a cathode that is opposite the anode and a membrane that is arranged between the anode and the cathode as constituent members, in other words, comprises an electrolytic cell. The existing electrolyzer is not particularly limited as long as it comprises the constituent members described above, and several known configurations can be used.

[001237] In the present modality, a new electrolyser additionally comprises an electrolysis electrode or a laminate, in addition to a member that has already served as an anode or cathode in the existing electrolyser. That is, the "electrolysis electrode" arranged in the production of a new electrolyzer serves as an anode or cathode, and is separated from the cathode and anode in the existing electrolyzer. In the present modality, even in the case where the electrolytic performance of the anode and / or cathode has deteriorated in association with the operation of the existing electrolyzer, the arrangement of a separate electrolysis electrode allows the anode and / or cathode characteristics to be renewed . In the case where a laminate is used in the present modality, a new ion exchange membrane is arranged in combination and thus the characteristics of the ion exchange membrane, which have deteriorated

321/803 in association with the operation, can be renewed simultaneously. “Renewing the characteristics” referred to here means having characteristics comparable to the initial characteristics possessed by the existing electrolyzer before being operated or having characteristics superior to the initial characteristics.

[001238] In the present modality, the existing electrolyzer is assumed to be an “electrolyzer that has already been operated” and it is assumed that the new electrolyzer is an “electrolyzer that has not yet been operated”. That is, once an electrolyser produced as a new electrolyser is operated, the electrolyser becomes “the existing electrolyser in the present modality”. The arrangement of an electrolysis electrode or a laminate in this existing electrolyser provides "a new electrolyser of the present modality".

[001239] Hereinafter, a case of conducting common salt electrolysis using an ion exchange membrane as the membrane is taken as an example, and an embodiment of the electrolyzer will be described in detail. In the <Fifth modality> section, unless otherwise specified, "the electrolyser in the present modality" incorporates both "the electrolyser existing in the present modality" and "the new electrolyser in the present modality". [Electrolytic cell]

[001240] First, the electrolytic cell will be described, which can be used as a constituent unit of the electrolyzer in the present modality. Figure 91 shows a cross-sectional view of an electrolytic cell 1.

[001241] The electrolytic cell 1 comprises an anodic chamber 10, a cathodic chamber 20, a partition wall 30 placed between the anodic chamber 10 and the cathodic chamber 20, an anode 11 placed in the anodic chamber and a cathode 21 placed in the cathodic chamber 20 As required, the electrolytic cell 1 has a substrate 18a and a reverse current absorbent layer 18b formed on the substrate 18a and can comprise a reverse current absorber 18 placed in the cathode chamber. Anode 11 and

322/803 cathode 21 belonging to electrolytic cell 1 are electrically connected to each other.

In other words, the electrolytic cell 1 comprises the following cathode structure.

The cathode structure 40 comprises the cathode chamber 20, the cathode 21 placed in the cathode chamber 20 and the reverse current absorber 18 placed in the cathode chamber 20, the reverse current absorber 18 has the substrate 18a and the reverse current absorbent layer 18b on substrate 18a, as shown in Figure 95, and cathode 21 and reverse current absorbing layer 18b are electrically connected.

The cathodic chamber 20 also has a collector 23, a support 24 supporting the collector and an elastic metal body 22. The elastic metal body 22 is placed between the collector 23 and the cathode 21. The support 24 is placed between the collector 23 and the partition wall 30. The collector 23 is electrically connected to the cathode 21 through the elastic metal body 22. The partition wall 30 is electrically connected to the collector 23 through the support 24. Therefore, the partition wall 30, the support 24, the collector 23, the elastic metal body 22 and the cathode 21 are electrically connected.

Cathode 21 and reverse current absorbing layer 18b are electrically connected.

Cathode 21 and the reverse current absorbing layer can be directly connected or they can be indirectly connected through the collector, the support, the elastic metal body, the partition wall or the like.

The entire surface of cathode 21 is preferably covered with a layer of catalyst for the reduction reaction.

The electrical connection form can be a form in which the partition wall 30 and the support 24, the support 24 and the collector 23, and the collector 23 and the elastic metal body 22 are each directly attached and the cathode 21 it is laminated to the elastic metal body 22. Examples of a method for directly affixing these constituent components to each other include welding and the like.

Alternatively, the reverse current absorber 18, cathode 21 and collector 23 can be collectively called a cathode structure 40.

323/803

[001242] Figure 92 illustrates a cross-sectional view of two electrolytic cells 1 that are adjacent in the electrolyzer 4. Figure 93 shows an electrolyzer 4. Figure 94 shows an assembly step of the electrolyzer 4.

[001243] As shown in Figure 92, an electrolytic cell 1, a cation exchange membrane 2 and an electrolytic cell 1 are arranged in series in the order mentioned. An ion exchange membrane 2 is arranged between the anode chamber of an electrolytic cell 1 between the two adjacent electrolytic cells in the electrolyzer and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent to it are separated by the cation exchange membrane 2. As shown in Figure 93, the electrolyzer 4 is composed of a plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer comprising the plurality of electrolytic cells 1 arranged in series and ion exchange membranes 2, each arranged between adjacent electrolytic cells 1. As shown in Figure 94, electrolyzer 4 is assembled arranging the plurality of cells electrolytics 1 in series through the ion exchange membrane 2 and coupling the cells by means of a pressure device 5.

[001244] Electrolyser 4 has an anodic terminal 7 and a cathodic terminal 6 to be connected to a power supply. Anode 11 of electrolytic cell 1 located at the far end between the plurality of electrolytic cells 1 coupled in series in electrolyzer 4 is electrically connected to anode terminal 7. Cathode 21 of the electrolytic cell located at the opposite end to anode terminal 7 between the plurality of electrolytic cells 1 coupled in series in the electrolyzer 4 is electrically connected to the cathode terminal 6. The electrical current during electrolysis flows from the side of the anode terminal 7, through the anode and cathode

324/803 each electrolytic cell 1, towards the cathodic terminal 6. At the two ends of the coupled electrolytic cells 1, an electrolytic cell with only one anodic chamber (cell of the anodic terminal) and an electrolytic cell with only one cathodic chamber (cell of the cathodic terminal) can be arranged. In that case, anode terminal 7 is connected to the cell of the anode terminal, arranged at one end, and cathode terminal 6 is connected to the cell of the cathode terminal, arranged at the other end.

[001245] In the case of electrolytic brine, brine is provided for each anodic chamber 10 and pure water or an aqueous solution of low concentration sodium hydroxide is provided for each cathodic chamber 20. Each liquid is supplied from a supply tube of electrolytic solution (not shown in the Figure), through an electrolytic solution supply hose (not shown in the Figure), for each electrolytic cell 1. The electrolyte solution and electrolysis products are recovered from an electrolyte recovery tube (not shown in the figure). During electrolysis, the sodium ions in the brine migrate from the anode chamber 10 of the electrolytic cell 1, through the ion exchange membrane 2, to the cathode chamber 20 of the adjacent electrolytic cell 1. Thus, the electric current during electrolysis flows in the direction wherein electrolytic cells 1 are coupled in series. That is, the electric current flows, through the cation exchange membrane 2, from the anodic chamber 10 towards the cathodic chamber 20. As the brine is electrolyzed, chlorine gas is generated on the anode side 11, and sodium hydroxide (solute ) and hydrogen gas are generated on the cathode side

21. (Anodic chamber)

[001246] The anodic chamber 10 has anode 11 or anode conductor 11. The supply conductor is referred to here to mean a degraded electrode (i.e., the existing electrode), an electrode without catalyst coating and the like. When the electrolysis electrode

325/803 in the present mode is inserted on the anode side, 11 serves as an anode supply conductor. When the electrode for electrolysis in the present embodiment is not inserted on the anode side, 11 serves as an anode. The anode chamber 10 preferably has an electrolyte solution supply unit on the anode side that provides an electrolyte solution for the anode chamber 10, a baffle plate which is arranged above the anode side electrolyte solution supply unit to be substantially parallel or oblique to a partition wall 30, and a liquid and gas separation unit on the anode side which is arranged above the baffle to separate the gas from the electrolytic solution including the mixed gas. (Anode)

[001247] When the electrode for electrolysis in the present modality is not inserted on the side of the anode, an anode 11 is provided in the frame of the anode chamber 10 (that is, the anode frame). Like anode 11, a metal electrode such as the so-called DSA (R) can be used. DSA is an electrode that includes a titanium substrate whose surface is covered with an oxide that contains ruthenium, iridium and titanium as components.

[001248] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Anode feed conductor)

[001249] When the electrode for electrolysis in the present modality is inserted on the anode side, the anode 11 feeder conductor is provided in the anode chamber 10 frame. As the anode 11 feeder conductor, a metal electrode can be used , such as the so-called DSA (R), and titanium without catalyst coating can also be used. Alternatively, DSA with a thinner catalyst coating can

326/803 can also be used. In addition, a used anode can also be used.

[001250] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Anode side electrolyte solution supply unit)

[001251] The electrode solution supply unit on the anode side, which supplies the electrolyte solution to the anode chamber 10, is connected to the electrolyte solution supply tube. The electrolytic solution supply unit on the anode side is preferably arranged below the anode chamber 10. As the electrolytic solution supply unit on the anode side, for example, a tube can be used on the surface from which orifice portions are formed. (dispersion tube) and the like. Such a tube is most preferably arranged along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell. This tube is connected to an electrolytic solution supply tube (liquid supply nozzle) that supplies the electrolytic solution to the electrolytic cell 1. The electrolyte solution supplied from the liquid supply nozzle is transported with a tube into the electrolytic cell 1 and supplied from the orifice portions provided on the surface of the tube into the anodic chamber 10. The arrangement of the tube along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell is preferable because the electrolyte solution can be uniformly supplied into the anodic chamber

10. (Liquid and gas separation unit on the anode side)

[001252] The liquid and gas separation unit on the anode side is preferably arranged above the baffle plate. The liquid and gas separation unit on the anode side has the function of separating the produced gas such as chlorine gas from the electrolytic solution during electrolysis. Unless

327/803 otherwise specified, above means the upper direction in the electrolytic cell 1 in Figure 91, and below means the lower direction in the electrolytic cell 1 in Figure 91.

[001253] During electrolysis, the produced gas generated in electrolytic cell 1 and the electrolytic solution form a mixed phase (mixed gas-liquid phase), which is then emitted out of the system. Subsequently, pressure fluctuations within the electrolytic cell 1 cause vibration, which can result in physical damage to the ion exchange membrane. In order to avoid this event, the electrolytic cell 1 in the present embodiment is preferably provided with a liquid and gas separation unit on the anode side to separate the gas from the liquid. The liquid and gas separation unit on the anode side is preferably provided with an anti-foam plate to eliminate bubbles. When the flow of the mixed gas-liquid phase passes through the antifoam plate, the bubbles burst, thus allowing the electrolyte solution and the gas to be separated. As a result, vibration during electrolysis can be avoided. (Baffle plate)

[001254] The baffle plate is preferably arranged above the electrolyte solution supply unit on the anode side and arranged substantially in parallel or obliquely to the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. When the deflector plate is provided, it is possible to make the electrolyte solution (brine or similar) circulate internally in the anodic chamber 10 to thus make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged in such a way as to separate the space in the vicinity of anode 11 from the space near the partition wall 30. From such a point of view, the baffle plate is preferably placed so as to be opposite the surface of anode 11 and the surface of the dividing wall 30. In the space next to the anode divided by

328/803 deflector plate, as the electrolysis progresses, the concentration of the electrolytic solution (brine concentration) is reduced and the gas produced, such as chlorine gas, is generated. This results in a difference in specific gas-liquid gravity between the space near anode 11 and the space near the dividing wall 30 divided by the deflector plate. By using the difference, it is possible to promote the internal circulation of the electrolytic solution in the anodic chamber 10 to thus make the distribution of concentration of the electrolytic solution in the anodic chamber 10 more uniform.

[001255] Although not shown in Figure 91, a collector can be additionally provided inside the anodic chamber 10. The material and configuration of such a collector can be the same as the collector of the cathodic chamber mentioned below. In anode chamber 10, anode 11 per se can also serve as a collector. (Partition wall)

[001256] The partition wall 30 is arranged between the anode chamber 10 and the cathode chamber 20. The partition wall 30 can be called a separator, and the anode chamber 10 and the cathode chamber 20 are divided by the partition wall 30. As the wall partition 30, one known as electrolysis separator can be used, and an example of this includes a partition wall formed by welding a plate comprising nickel next to the cathode and a plate comprising titanium beside the anode. (Cathodic chamber)

[001257] In the cathodic chamber 20, when the electrode for electrolysis in the present modality is inserted on the cathode side, 21 serves as a cathode supply conductor. When the electrolysis electrode in the present embodiment is not inserted on the cathode side, 21 it serves as a cathode. When a reverse current absorber is included, the cathode or cathode supply conductor 21 is electrically connected to the reverse current absorber. Cathodic chamber 20, similarly to the

329/803 anodic chamber 10, preferably has an electrolytic solution supply unit on the cathode side and a liquid and gas separation unit on the cathode side. Among the components that make up the cathodic chamber 20, components similar to those that make up the anode chamber 10 will not be described. (Cathode)

[001258] When the electrode for electrolysis in the present embodiment is not inserted on the side of the cathode, a cathode 21 is provided in the frame of the cathode chamber 20 (i.e., the cathode frame). Cathode 21 preferably has a nickel substrate and a catalyst layer that covers the nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include metals such as Ru, C, Si, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, y-alloying, composite dispersion / galvanization, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Cathode 21 can be subjected to a reduction treatment as needed. As the cathode 21 substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[001259] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Cathode supply conductor)

[001260] When the electrode for electrolysis in the present mode is inserted on the side of the cathode, a supply conductor for cathode 21 is

330/803 provided in the frame of the cathodic chamber 20. The cathode 21 feeding conductor can be covered with a catalytic component. The catalytic component can be a component that is originally used as the cathode and remains. Examples of the catalyst layer components include metals such as Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh , Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, I, Gd, Tb, Dy , Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, alloy galvanizing, composite dispersion / galvanizing, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Nickel, nickel alloys and nickel or stainless galvanized iron without catalyst coating can be used. As the cathode 21 feed conductor substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[001261] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Reverse current absorbing layer)

[001262] A material with a less noble redox potential than the element's redox potential for the catalyst layer of the cathode mentioned above can be selected as a material for the reverse current absorbing layer. Examples of it include nickel and iron. (Collector)

[001263] The cathodic chamber 20 preferably comprises the collector

23. Collector 23 improves the efficiency of the current collection. In the present embodiment, the collector 23 is a porous plate and is preferably arranged

331/803 substantially parallel to the surface of cathode 21.

[001264] The collector 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. Collector 23 can be a mixture, alloy or composite oxide of these metals. The collector 23 can have any shape, as long as the shape allows the function of the collector and can have a plate or network shape. (Elastic metal body)

[001265] Placing the elastic metal body 22 between the collector 23 and the cathode 21 presses each cathode 21 of the plurality of electrolytic cells 1 connected in series to the ion exchange membrane 2 to reduce the distance between each anode 11 and each cathode 21. Then, it is possible to reduce the voltage to be applied entirely through the plurality of electrolytic cells 1 connected in series. Reducing the voltage reduces energy consumption. With the elastic metal body 22 in place, the pressure caused by the elastic metal body 22 allows the electrolysis electrode to be held steadily in place when the laminate including the electrolysis electrode in the present embodiment is placed in the electrolytic cell.

[001266] As the elastic metal body 22, spring members such as spiral springs and coils and damping mats can be used. As the elastic metal body 22, a suitable one can be used appropriately, taking into account a tension to pressure the ion exchange membrane and the like. The elastic metal body 22 can be provided on the surface of the collector 23 on the side of the cathode chamber 20 or it can be provided on the surface of the partition wall on the side of the anode chamber 10. Both chambers are normally divided in such a way that the cathode chamber 20 it becomes smaller than the anodic chamber 10. Thus, from the point of view of the strength of the frame and the like, the elastic metal body 22 is preferably provided between the collector 23 and the cathode 21 in the anodic chamber

20. The elastic metal body 23 preferably comprises a metal

332/803 electrically conductive, such as nickel, iron, copper, silver and titanium. (Support)

[001267] The cathodic chamber 20 preferably comprises the support 24 that electrically connects the collector 23 to the partition wall 30. This can achieve an efficient current flow.

[001268] The support 24 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. The support 24 can have any shape as long as the support can support the collector 23 and can have a rod, plate or network shape. The support 24 has a plate shape, for example. A plurality of supports 24 is arranged between the partition wall 30 and the collector 23. The plurality of supports 24 are aligned in such a way that their surfaces are in parallel with each other. The supports 24 are arranged substantially perpendicular to the partition wall 30 and the collector 23. (Gasket on the anode side and gasket on the cathode side)

[001269] The anode-side gasket is preferably arranged on the surface of the structure that constitutes the anode chamber 10. The cathode-side gasket is preferably arranged on the surface of the structure that constitutes the cathodic chamber 20. The electrolytic cells are connected to each other others such that the anode-side gasket included in an electrolytic cell and the cathode-side gasket of an electrolytic cell adjacent to the cell sandwich the ion exchange membrane 2 (see Figure 92). These gaskets can make the connection points airtight when the plurality of electrolytic cells 1 is connected in series through the ion exchange membrane 2.

[001270] The gaskets form a seal between the ion exchange membrane and the electrolytic cells. Specific examples of gaskets include picture frame rubber sheets, in the center of which a hole portion is formed. Gaskets are required to have resistance against solutions

333/803 corrosive electrolytes or gas produced and be usable for a long period. Thus, with regard to chemical resistance and hardness, vulcanized products and products cross-linked with ethylene-propylene-diene rubber peroxide (EPDM rubber) and ethylene-propylene rubber (EPM rubber) are normally used as gaskets. Alternatively, gaskets from which the region to be in contact with liquid (liquid contact portion) with a fluorine-containing resin such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers can be used as needed. Such gaskets may have an orifice portion so as not to inhibit the flow of the electrolyte solution, and the shape of the orifice portion is not particularly limited. For example, a picture frame gasket is affixed with an adhesive or similar along the peripheral edge of each hole portion of the anodic chamber frame that constitutes the anodic chamber 10 or the cathodic chamber frame that constitutes the cathodic chamber 20. So, for example, in the case where the two electrolytic cells 1 are connected via the ion exchange membrane 2 (see Figure 92), each electrolytic cell 1 to which the gasket is attached must be tightened via the ion exchange membrane 2. This Tightening can prevent the electrolyte solution, alkali metal hydroxide, chlorine gas, hydrogen gas and the like, generated from electrolysis, from escaping from electrolytic cells 1.

[Step of using the curled body]

[001271] The coiled body in the present modality can be the electrolysis electrode being in a coiled body form, or it can be a laminate of the electrolysis electrode and a new membrane, being in a coiled body form. In the method for producing an electrolyzer according to the present modality, the rolled body is used. Specific examples of the step of using a rolled body include, but are not limited to, they include a method in which, first in the existing electrolyzer, it is

334/803 a fixed state is released from the adjacent electrolytic cell and ion exchange membrane by means of a pressure device to provide an interstice between the electrolytic cell and the ion exchange membrane, then an electrolyte electrode that is in a form of The rolled body, after its rolled state is released, is inserted into the interstice, and the limbs are re-coupled by means of the pressure device. In the case where the laminate is used in a rolled-up body shape, examples of the method include a method in which, after an interstice is formed between the electrolytic cell and the ion exchange membrane as described above, the existing ion exchange membrane at After being renewed, a laminate in the form of a rolled-up body is removed, after the rolled-up state is released, it is inserted into the interstice, and the members are again coupled by means of the pressure device. Through the method, an electrolysis or laminate electrode can be arranged on the surface of the existing electrolyzer anode or cathode, and the characteristics of the ion exchange membrane and the anode and / or cathode can be renewed.

[001272] As described above, in the present embodiment, the step of using a rolled-up body preferably has a step (B) of releasing the rolled-up state of a rolled-up body, and after step (B), more preferably it has a step ( C) to arrange an electrolysis electrode or laminate on the surface of at least one of the anode and cathode.

[001273] In the present embodiment, the step of using the coiled body preferably has a step (A) of retaining the electrode for electrolysis or the laminate in a coiled state to obtain a coiled body. In step (A), the electrolysis or laminate electrode per se can be wound to form a coiled body, or the electrolysis or laminate electrode can be wound around a core to form a coiled body. Like the core that can be used here, which is not particularly limited, a member with a substantially cylindrical shape and a size

335/803 corresponding to the electrolysis electrode or laminate can be used, for example. [Electrode for electrolysis]

[001274] In the present embodiment, the electrolyte for electrolysis is not particularly limited as long as the electrode is used as a coiled body as mentioned above, that is, that it is coiled. The electrolysis electrode can be an electrode that serves as a cathode in the electrolyzer or it can be an electrode that serves as an anode. Like the material, shape and the like of the electrolysis electrode, those suitable for forming a coiled body can be appropriately selected, in consideration of the step of using a coiled body, the configuration of the electrolyzer, and the like in the present embodiment. In the following, preferable aspects of the electrolysis electrode in the present embodiment will be described, but these are merely preferable exemplary aspects for forming a coiled body. Electrodes for electrolysis, in addition to the aspects mentioned below, can be properly used.

[001275] The electrolyte for electrolysis in the present embodiment has a force applied per unit mass-unit area of preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mg: in?), even more preferably less than 1.5 N / (mg: cm?), even more preferably 1.2 N / mg-cm? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a supply conductor (a degraded electrode and an uncoated electrode) catalyst) and the like. Is the applied force even more preferably 1.1 N / mg-cm? or less, even more preferably 1.10 N / mge? or less, particularly preferably 1.0 N / m? or less, especially preferably 1.00 N / mg-cm? or less.

336/803

[001276] From the point of view of further improving electrolytic performance, the strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: in?) Or more, even more preferably 0.1 N / mg: cm? or more, even more preferably 0.14 N / (mg: cm?) or more. By force it is even more preferably 0.2 N / (mg: cm?) Or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 m x 2.5 m).

[001277] The applied force described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness, arithmetic mean surface roughness and the like, for example. More specifically, for example, a higher opening ratio tends to lead to a lower applied force, and a lower opening ratio tends to lead to a higher applied force.

[001278] Is the mass per unit preferably 48 mg / cm? or less, more preferably 30 mg / cm? or less, even more preferably 20 mg / cm? or less from the point of view of allowing a good manipulation property, having a good adhesive force for a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a conductive conductor without catalyst coating, and economy , and in addition it is preferably 15 mg / hundred? or less from a comprehensive point of view including handling, grip and economy properties. The lower limit value is not particularly limited, but is in the order of 1 mg / hundred?, For example.

[001279] The mass per unit area described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness and the like, for example. More specifically, for example, when the thickness is constant, a larger opening ratio tends to lead to a smaller mass per unit area, and a smaller opening ratio tends to lead to a mass per unit area greater.

337/803

[001280] The applied force can be measured by the methods (1) or (ii) described below, which are as detailed in the Examples. As for the applied force, the value obtained by measuring the method (1) (also called “the applied force (1)”) and the value obtained by measuring the method (ii) (also called “the applied force (2) ”) Can be the same or different, and any of the values is preferably less than 1.5 N / (mg: -ecm?). [Method (i)]

[001281] A nickel plate obtained by stripping processing with grain size alumina 320 (thickness 1.2 mm, 200 mm square), an ion exchange membrane that is obtained by the application of particles of inorganic material and a binder on both surfaces of a perfluorocarbon polymer membrane into which an ion exchange group (170 square mm, the detail of the ion exchange membrane referred to here is as described in the Examples) and an electrode sample (130 mm square) ) are rolled in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. The arithmetic mean roughness of the surface (Ra) of the nickel plate after blasting treatment is 0.5 to 0.8 µm. The specific method for calculating the arithmetic mean surface roughness (Ra) is as described in the Examples.

[001282] Under temperature conditions of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the charge when the electrode sample is raised by 10 mm in a vertical direction is measured. This measurement is repeated three times and the average value is calculated.

[001283] This average value is divided by the area of the overlapping portion of the electrode sample and the ion exchange membrane and the mass of the portion that is

338/803 overlaps the ion exchange membrane in the electrode sample to calculate the applied force per unit mass-unit area (1) (N / mg-ecm?).

[001284] The force applied per unit mass-unit area (1) obtained by method (i) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg: -em? or less. The strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg: cm?) Or more than the point view of further improving electrolytic performance, and furthermore, it is even more preferably 0.14 N / (mgcm?), even more preferably 0.2 N / (mg: cm?) or more from the point of view of facilitating further manipulation in a large size (for example, a size of 1.5 mx2.5M). [Method (ii)]

[001285] A nickel plate obtained by stripping processing with alumina of grain size 320 (thickness 1.2 mm, 200 mm square, a nickel plate similar to the method (1) above) and an electrode sample ( 130 mm square) is laminated in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. Under temperature conditions of 23 + 2ºC and relative humidity of 30 + 5%, only

339/803 electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the load when the electrode sample is raised by 10 mm in a vertical direction is measured . This measurement is repeated three times and the average value is calculated.

[001286] This average value is divided by the area of the overlapping portion of the electrode sample and the nickel plate and the mass of the electrode sample in the portion overlapping the nickel plate to calculate the adhesive force per unit mass-unit of area (2) (N / mg: -cm?).

[001287] The force applied per unit mass-unit area (2) obtained by method (ii) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg: cm? or less. In addition, the strength is preferably greater than 0.005 N / (mg: cm?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg-in?) Or more from the point of view of further improving electrolytic performance, and it is even more preferably 0.14 N / (mg: cm?) or more from the point of view of further facilitating handling in a large size (for example, a 1.5 m x 2.5 m).

[001288] The electrolyte electrode in the present embodiment preferably includes a substrate for electrolysis electrode and a

340/803 catalyst layer. The substrate thickness for the electrolysis electrode (gauge thickness) is, but is not particularly limited to, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less , even more preferably 125 µm or less, even more preferably 120 µm or less, even more preferably 100 µm or less from the point of view of enabling a good handling property to be provided, having a good adhesive strength to a membrane, such as a ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, be able to be properly laminated on a roll and folded satisfactorily, facilitating handling in one size large (for example, a size of 1.5 mx 2.5 Mm), and is even more preferably 50 µm or less from the point of view of a handling and economy property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001289] The proportion measured by the following method (2) of the electrolysis electrode in the present embodiment is not particularly limited, but is preferably 90% or more, more preferably 92% or more from the point of view of allowing a good handling property is provided and has a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and more preferably 95% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (2)]

[001290] One ion exchange membrane (170 mm square) and one

341/803 electrode samples (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 280 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001291] The proportion measured by the following method (3) of the electrode for electrolysis in the present embodiment is not particularly limited, but is preferably 75% or more, more preferably 80% or more from the point of view of allowing a good handling property be provided, have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating and can be properly laminated in a roll is satisfactorily folded, and is more preferably 90% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (3)]

[001292] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 145 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited in a

342/803 surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of an area of a portion where the ion exchange membrane (170 mm square) is in close contact is then measured with the electrode sample.

[001293] The electrolysis electrode in the present embodiment preferably has, but is not particularly limited to, a porous structure and an opening ratio or void ratio of 5 to 90% or less from the point of view of enabling a good handling property, have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and prevent the accumulation of gas from being generated during electrolysis. The opening ratio is more preferably 10 to 80% or less, more preferably 20 to 75%.

[001294] The opening ratio is a proportion of the opening portions per unit volume. The calculation method may differ depending on whether the opening portions in submicron size are considered or that only visible openings are considered. In the present embodiment, a volume V is calculated from the values of the thickness of the gauge, width and length of the electrode and, in addition, a weight W is measured to thereby allow an aperture ratio A to be calculated by the following formula.

A = (1- (W / (YV xp)) x 100

[001295] p is the density of the electrode material (g / cm?). For example, nickel p is 8.908 g / em ”, and titanium p is 4.506 g / em ?. The opening ratio can be appropriately adjusted by changing the area of metal to be drilled per unit area in the case of perforated metal, changing the SW (short diameter), LW (long diameter) and feed values in the case of expanded metal, changing the diameter of metal fiber line and mesh number

343/803 in the case of mesh, changing the pattern of a photoresist to be used in the case of electroforming, changing the diameter of the metal fiber and fiber density in the case of non-woven fabric, changing the mold to form voids in the case of metal foamy or similar.

[001296] Hereinafter, a more specific modality of the electrode for electrolysis in the present modality will be described.

[001297] The electrolysis electrode according to the present embodiment preferably includes a substrate for electrolysis electrode and a catalyst layer. The catalyst layer can be composed of a plurality of layers, as shown below, or it can be a single layer configuration.

[001298] As shown in Figure 96, an electrolysis electrode 100 according to the present embodiment includes an electrode electrode substrate 10 and a pair of first layers 20 with which both surfaces of the electrolysis electrode substrate 10 are covered. . The entire electrolyte electrode substrate 10 is preferably covered with the first 20 layers. This coating is likely to improve the activity of the catalyst and the durability of the electrolysis electrode. A first layer 20 can be laminated only on one surface of the electrode substrate for electrolysis 10.

[001299] Also shown in Figure 96, the surfaces of the first layers 20 can be covered with the second layers 30. The first entire layers 20 are preferably covered by the second layers 30. Alternatively, a second layer 30 can be laminated only one surface of the first layer 20. (Electrode substrate for electrolysis)

[001300] As an electrode substrate for electrolysis 10, for example, nickel, nickel alloys, stainless steel or valve metals including titanium can be used, although not limited to them. Substrate 10 contains

344/803 preferably at least one element selected from nickel (Ni) and titanium (Ti).

[001301] When stainless steel is used in a high-concentration aqueous alkaline solution, iron and chromium are eluted and the electrical conductivity of stainless steel is about one tenth that of nickel. In view of the above, a substrate containing nickel (Ni) is preferable as a substrate for the electrolysis electrode.

[001302] Alternatively, when the electrode substrate for electrolysis 10 is used in a high concentration saline solution close to saturation under an atmosphere in which chlorine gas is generated, the substrate material for electrode 10 is also preferably high titanium corrosion resistance.

[001303] The shape of the electrode substrate for electrolysis 10 is not particularly limited, and a shape suitable for the purpose can be selected. As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. Among these, a perforated metal or expanded metal is preferable. Electroforming is a technique for producing a thin metal film with a precise pattern using photolithography and electroplating in combination. It is a method that includes the formation of a pattern on a substrate with a photoresist and electroplating of the portion not protected by the resistance to provide a thin metal film.

[001304] Regarding the shape of the substrate for the electrolysis electrode, an appropriate specification depends on the distance between the anode and the cathode in the electrolyzer. In the case where the distance between the anode and the cathode is finite, a form of expanded metal or perforated metal can be used, and in the case of a so-called zero-interstitial electrolyzer, in which the ion exchange membrane is in contact with the electrode, a mesh can be used

345/803 woven fabric produced by fine knitted threads, wire mesh, foamy metal, metallic non-woven fabric, expanded metal, perforated metal, porous metal foil and the like, although not limited to it.

[001305] Examples of the electrode substrate for electrolysis 10 include a porous metallic foil, a wire mesh, a non-woven metal fabric, a perforated metal, an expanded metal and a foamy metal.

[001306] As plate material before being processed into a perforated metal or expanded metal, laminated plate materials and electrolytic sheets are preferred. An electrolytic sheet is preferably still subjected to a galvanizing treatment using the same element as its base material, such as after-treatment, to thereby form roughness and one or both surfaces.

[001307] The thickness of the electrode substrate for electrolysis 10 is, as mentioned above, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less, even more preferably 125 one or less, even more preferably 120 µm or less, even more preferably 100 µm or less, and even more preferably 50 µm or less from the point of view of a handling and economical property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001308] In the electrode substrate for electrolysis, the residual stress during processing is preferably relaxed by annealing the electrode substrate for electrolysis in an oxidizing atmosphere. It is preferable to form roughness using a steel grid, alumina powder or similar on the surface of the electrode substrate for electrolysis followed by an acid treatment to increase the surface area of the electrode, in order to improve the adhesion to a catalyst layer with which the surface is covered. Alternatively, it is preferable to give a galvanizing treatment

346/803 using the same element as the substrate to increase the surface area.

[001309] In order to place the first layer 20 in close contact with the surface of the electrode electrode substrate 10, the electrode electrode substrate 10 is preferably subjected to a treatment to increase the surface area. Examples of the treatment of increasing the surface area include a pickling treatment using a cut wire, steel grid, alumina grid or similar, an acid treatment using sulfuric acid or hydrochloric acid, and a galvanizing treatment using the same element as the of the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 µm to 50 µm, more preferably 0.1 to 10 µm, even more preferably 0.1 to 8 µm.

[001310] Next, a case will be described in which the electrode for electrolysis in the present modality is used as an anode for electrolysis of common salt. (First layer)

[001311] In Figure 96, a first layer 20 as a catalyst layer contains at least one of the ruthenium oxides, iridium oxides and titanium oxides. Examples of ruthenium oxide include RuO; Examples of iridium oxide include IrO ,. Examples of titanium oxide include TiO,; The first layer 20 preferably contains two oxides: a ruthenium oxide and a titanium oxide or three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide. This makes the first layer 20 more stable and further improves adhesion with the second layer 30.

[001312] When the first layer 20 contains two oxides: a ruthenium oxide and a titanium oxide, the first layer 20 preferably contains 1 to 9 mol, more preferably 1 to 4 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition ratio of the two oxides in this range, the electrode for electrolysis

347/803 100 has excellent durability.

[001313] When the first layer 20 contains three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide, the first layer 20 preferably contains 0.2 to 3 mol, more preferably 0.3 to 2.5 mol of iridium oxide based on 1 mol of ruthenium oxide contained in the first layer 20. The first layer 20 preferably contains 0.3 to 8 mol, more preferably 1 to 7 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition of the three oxides in this range, the electrode for electrolysis 100 has excellent durability.

[001314] When the first layer 20 contains at least two of a ruthenium oxide, an iridium oxide and a titanium oxide, these oxides preferably form a solid solution. The formation of the solid oxide solution allows the electrolysis electrode 100 to have excellent durability.

[001315] In addition to the compositions described above, oxides of various compositions may be used provided that at least one oxide of a ruthenium oxide, an iridium oxide and titanium oxide is contained. For example, an oxide coating called DSA (R), which contains ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum and the like, can be used as a first layer 20.

[001316] The first layer 20 need not be a single layer and can include a plurality of layers. For example, the first layer 20 can include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 µm, more preferably 0.1 to 8 µm. (Second layer)

[001317] The second layer 30 preferably contains ruthenium and titanium. This allows chlorine overvoltage immediately after

348/803 electrolysis is reduced.

[001318] The second layer 30 preferably contains a palladium oxide, a solid solution of a palladium and platinum oxide, or an alloy of palladium and platinum. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001319] A second thicker layer 30 can maintain the electrolytic performance for a longer period, but from an economic point of view, the thickness is preferably 0.05 to 3 µm.

[001320] Next, a case will be described in which the electrode for electrolysis in the present modality is used as a cathode for electrolysis of common salt. (First layer)

[001321] Examples of components of the first layer 20 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[001322] The first layer 20 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal.

[001323] When the first layer 20 contains at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides, and alloys containing a platinum group metal, the metals of the platinum group platinum, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal preferably contain at least one platinum group metal of platinum, palladium, rhodium, ruthenium and iridium.

[001324] Like the platinum group metal, platinum is preferably contained.

349/803

[001325] Like the metal oxide of the platinum group, a ruthenium oxide is preferably contained.

[001326] Like the metal hydroxide of the platinum group, a ruthenium hydroxide is preferably contained.

[001327] Like the platinum group metal alloy, a platinum alloy with nickel, iron and cobalt is preferably contained.

[001328] In addition, as needed, an oxide or hydroxide of a lanthanide element is preferably contained as a second component. This allows the electrolysis electrode 100 to have excellent durability.

[001329] As the oxide or hydroxide of a lanthanide element, at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium and dysprosium is preferably contained.

[001330] Furthermore, as needed, an oxide or hydroxide of a transition metal is preferably contained as a third component.

[001331] The addition of the third component allows the electrolysis electrode 100 to have greater durability and the electrolysis voltage to be reduced.

[001332] Examples of a preferable combination include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + Platinum + Palladium, Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium +

350/803 iron, ruthenium + samarium + cobalt, ruthenium + samarium + zinc, ruthenium + samarium + gallium, ruthenium + samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium , platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + nickel + palladium, platinum + nickel + ruthenium, platinum and nickel alloys, platinum and cobalt alloys, and alloys platinum and iron.

[001333] When platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal are not contained, the main component of the catalyst is preferably the nickel element.

[001334] At least one of the nickel metals, oxides and hydroxides is preferably contained.

[001335] As the second component, a transition metal can be added. As the second component to be added, at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper and carbon is preferably contained.

[001336] Examples of a preferable combination include nickel + tin, nickel + titanium, nickel + molybdenum and nickel + cobalt.

[001337] As required, an intermediate layer can be placed between the first layer 20 and the electrode substrate for electrolysis

10. The durability of the electrolysis electrode 100 can be improved by placing the intermediate layer.

[001338] As the intermediate layer, those with affinity for both the first layer 20 and the electrode substrate for electrolysis 10 are preferred. As the intermediate layer, nickel oxides, platinum group metals, metal oxides are preferable of the platinum group and metal hydroxides of the platinum group. The intermediate layer can be formed by applying and cooking a solution containing a component that forms the intermediate layer. Alternatively, a

351/803 surface oxide layer can also be formed by subjecting a substrate to a heat treatment at a temperature of 300 to 600ºC in an air atmosphere. In addition, the layer can be formed by a known method, such as a thermal spray method and an ion galvanizing method. (Second layer)

[001339] Examples of components of the first layer 30 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[001340] The first layer 30 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal. Examples of a preferable combination of elements contained in the second layer include the combinations listed for the first layer. The combination of the first layer and the second layer can be a combination in which the compositions are the same and the composition reasons are different or can be a combination of different compositions.

[001341] Like the thickness of the catalyst layer, the total thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 µm to 20 µm. With a thickness of 0.01 µm or more, the catalyst layer can sufficiently serve as the catalyst. With a thickness of 20 µm or less, it is possible to form a robust catalyst layer that is unlikely to fall off the substrate. The thickness is more preferably 0.05 µm to 15 µm. The thickness is more preferably 0.1 µm to 10 µm. The thickness is even more preferably 0.2 µm to 8 µm.

[001342] The thickness of the electrode, that is, the total thickness of the substrate

352/803 for electrode for electrolysis and the catalyst layer is preferably 315 One or less, more preferably 220 one or less, more preferably 170 One or less, even more preferably 150 one or less, particularly - preferably 145 one or less, still more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less with respect to the handling property of the electrode. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably one or more. The thickness of the electrode can be determined by measurement with a digital thickness gauge (Mitutoyo Corporation, minimum scale 0.001 mm). The thickness of the electrode substrate for electrolysis is measured in the same way as the thickness of the electrode. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.

[001343] In the present embodiment, the electrolysis electrode preferably contains at least one catalytic component selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B / C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy from the point of view of achieving sufficient electrolytic performance.

[001344] In the present modality, from the point of view that the electrolysis electrode, if it is an electrode with a wide region of elastic deformation, can provide a better handling property and has a better adhesive force to a membrane as an exchange membrane ionic and a

353/803 microporous membrane, a degraded electrode, a feed conductor without any catalyst coating, and the like, the electrode thickness for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, still more preferably 150 µm or less, particularly preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably 20 µm or more. In the present modality, “having a wide region of elastic deformation” means that when an electrolysis electrode is wound to form a wound body, it is unlikely that distortion derived from the winding will occur after the wound state is released. The thickness of the electrolysis electrode refers, when a catalyst layer mentioned below is included, to the total thickness of both the electrolysis electrode substrate and the catalyst layer. (Method to produce electrode for electrolysis)

[001345] Next, an embodiment of the method for producing the electrolysis electrode 100 will be described in detail.

[001346] In the present embodiment, the electrolysis electrode 100 can be produced by forming the first layer 20, preferably the second layer 30, on the electrode electrode substrate by a method such as cooking a coating film under an oxygen atmosphere ( pyrolysis) or ion galvanizing, galvanizing or thermal spraying. THE

354/803 production method of the present embodiment as mentioned can achieve a high productivity of the electrode for electrolysis 100. Specifically, a catalyst layer is formed on the electrode substrate for electrolysis by an application step to apply a coating liquid containing a catalyst , a drying step to dry the coating liquid and a pyrolysis step to perform pyrolysis. Pyrolysis here means that a metal salt that is to be a precursor is decomposed by heating into a metal or metal oxide and a gaseous substance. The decomposition product depends on the metal species to be used, the type of salt and the atmosphere under which pyrolysis is carried out, and many metals tend to form oxides in an oxidizing atmosphere. In an industrial electrode production process, pyrolysis is usually carried out in air, and a metal oxide or metal hydroxide is formed in many cases. (Formation of the first anode layer) (Application stage)

[001347] The first layer 20 is obtained by applying a solution in which at least one metallic salt of ruthenium, iridium and titanium is dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the liquid coating in the presence of oxygen. The ruthenium, iridium and titanium content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001348] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the film.

355/803 coating to be formed by a single coating.

[001349] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a method of brushing the first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[001350] After being applied to the electrode substrate for electrolysis 100, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001351] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the second layer)

356/803

[001352] The second layer 30, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second liquid of first layer 20 and then pyrolyzing the coating liquid in the presence of oxygen. (Formation of the first cathode layer by the pyrolysis method) (Application stage)

[001353] The first layer 20 is obtained by applying a solution in which metal salts of various combinations are dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the coating liquid in the presence of oxygen. The metal content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001354] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[001355] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and a

357/803 electrostatic coating where the electrolyte electrode substrate 10 and the first coating liquid are charged in the opposite way and spraying is carried out. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[001356] After being applied to the electrode substrate for electrolysis 10, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001357] The application, drying and pyrolysis cycle described above is repeated to form a cover (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the intermediate layer)

[001358] The intermediate layer, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound or a platinum compound (second coating liquid) to the substrate and then pyrolyzing the coating liquid in the presence of oxygen. Alternatively, an intermediate layer of nickel oxide can be formed on the surface of the substrate just by heating the substrate, without applying a solution on it.

358/803 (Formation of the first cathode layer by ion galvanizing)

[001359] The first layer 20 can also be formed by ion plating.

[001360] An example includes a method in which the substrate is fixed in a chamber and the metal ruthenium target is irradiated with an electron beam. Evaporated metallic ruthenium particles are positively charged to the plasma in the chamber to deposit on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and deposits of ruthenium as ruthenium oxide in the substrate. (Formation of the first cathode layer by galvanizing)

[001361] The first layer 20 can also be formed by a method of galvanization.

[001362] For example, when the substrate is used as a cathode and subjected to electrolytic galvanization in an electrolytic solution containing nickel and tin, nickel and tin alloy galvanization can be formed. (Formation of the first cathode layer by thermal spray)

[001363] The first layer 20 can also be formed by thermal spraying.

[001364] As an example, the nickel oxide particles sprayed by plasma on the substrate can form a catalyst layer in which the nickel metal and nickel oxide are mixed. [Laminate]

[001365] The electrolyte electrode in the present embodiment can be combined with a membrane, such as an ion exchange membrane or a microporous membrane, and used as a laminate. That is, the laminate in the present modality comprises the electrode for electrolysis and a new membrane. The new membrane is not particularly limited as long as it is separated from the membrane in the existing electrolyzer, and several known "membranes" can be used. The material, shape, physical properties and

359/803 similar to the new membrane may be similar to those of the membrane in the existing electrolyzer.

[001366] Hereinafter, an ion exchange membrane according to an aspect of the membrane will be described in detail. [Ion exchange membrane]

[001367] The ion exchange membrane is not particularly limited as long as the membrane can be laminated with the electrolysis electrode, and several ion exchange membranes can be used. In the present embodiment, an ion exchange membrane is preferably used which has a membrane body containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and a coating layer provided on at least one surface of the membrane body. It is preferable that the coating layer contains particles of inorganic material and a binder, and the specific surface area of the coating layer is 0.1 to 10 µm / g. The ion exchange membrane that has such a structure has a small influence of the gas generated during electrolysis on electrolytic performance and tends to exert stable electrolytic performance.

[001368] The membrane of a perfluorocarbon polymer into which an ion exchange group is introduced described above includes a layer of sulfonic acid with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called a "sulfonic acid group") or a layer of carboxylic acid with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a "carboxylic acid group"). From the point of view of strength and dimensional stability, reinforcement core materials are preferably included.

[001369] The particles of inorganic material and binder will be described in detail in the coating layer description section below.

[001370] Figure 97 illustrates a schematic section view

360/803 transverse showing an ion exchange membrane modality. An ion exchange membrane | it has a membrane body 10 containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and coating layers 11a and 11b formed on both surfaces of the membrane body 10.

[001371] In the ion exchange membrane 1, the membrane body 10 comprises a layer of sulfonic acid 3 with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called an “acid group sulfonic ”) and a layer of carboxylic acid 2 with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a“ carboxylic acid group ”), and the core materials of reinforcement 4 intensifies strength and dimensional stability. The ion exchange membrane 1, comprising the sulfonic acid layer 3 and the carboxylic acid layer 2, is suitably used as an anion exchange membrane.

[001372] The ion exchange membrane can include the sulfonic acid layer or the carboxylic acid layer. The ion exchange membrane may not necessarily be reinforced by reinforcement core materials, and the arrangement of the reinforcement core materials is not limited to the example in Figure 97. (Membrane body)

[001373] First, the membrane body 10 which constitutes the ion exchange membrane 1 will be described.

[001374] The membrane body 10 must be one that has the function of selectively allowing cations to permeate and comprises a hydrocarbon polymer or a fluorine-containing polymer with an ion exchange group. Its configuration and material are not particularly limited, and the preferred ones can be selected appropriately.

[001375] The hydrocarbon polymer or fluorine-containing polymer with

361/803 an ion exchange group in the membrane body 10 can be obtained from a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group precursor capable of forming an ion exchange group by hydrolysis or the like. Specifically, for example, after a polymer comprising a fluorinated hydrocarbon backbone that has, as a pendant side chain, a group convertible into an ion exchange group by hydrolysis or similar (precursor to the ion exchange group), and is processable by melting (hereinafter called "fluorine-containing polymer (a)" in some cases), be used to prepare a precursor to the membrane body 10, the membrane body 10 can be obtained by converting the precursor to the ion exchange group in an ion exchange group.

[001376] The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. The fluorine-containing polymer (a) can also be produced by homopolymerizing a monomer selected from any of the following first group, the following second group and the following third group.

[001377] Examples of the monomers of the first group include vinyl fluoride compounds. Examples of the vinyl fluoride compounds include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and perfluoralkyl vinyl ethers. Particularly when the ion exchange membrane is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoro monomer, and a perfluoro monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and perfluoralkylvinyl ethers is preferable.

[001378] Examples of the monomers of the second group include vinyl compounds with a functional group convertible into a group of

362/803 ion exchange of the carboxylic acid type (carboxylic acid group). Examples of vinyl compounds with a functional group convertible to a carboxylic acid group include monomers represented by CF = CF (OCF; CYF); - O (CZF) .- COOR, where s represents an integer from 0 to 2, t represents an integer from 1 to 12, Y and Z each independently represent F or CF; 3, and R represents a lower alkyl group (a lower alkyl group is an alkyl group with 1 to 3 carbon atoms, for example).

[001379] Among them, compounds represented by CF; = CF (OCF; CYF), - O (CF2) n-COOR are preferable. Where n represents an integer from 0 to 2, m represents an integer from 1 to 4, Y represents F or CF; 3, and R represents CH3, CoHs, or C3H ;.

[001380] When the ion exchange membrane is used as a cation exchange membrane for alkaline electrolysis, a perfluoro compound is preferably at least used as the monomer, but the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis and, therefore, the alkyl group (R) need not be a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[001381] Of the monomers above, the monomers shown below are more preferable than the monomers of the second group: CF; = CFOCF; -CF (CF;) OCF; COOCH ;, CF; = CFOCF; CF (CF3) O (CF3) -COOCH ;, CF; = CF [OCF3-CF (CF3) 12O (CF>) - COOCH ;, CF; = CFOCF; CF (CF3) O (CF3); 5COOCH ;, CF3 = CFO (CF3); COOCH; , and CF; = CFO (CF;); COOCH ;.

[001382] Examples of the monomers of the third group include vinyl compounds with a functional group convertible into an ion exchange group of the sulfone type (sulfonic acid group). Like vinyl compounds with a functional group convertible to a sulfonic acid group,

363/803 for example, monomers represented by CF; = CFO-X-CF; -SO, F are preferred, where X represents a perfluoroalkylene group. Specific examples of these include the monomers represented below: CF; = CFOCFCFSOF, CF; = CFOCFCF (CF3) OCF3CF3SO »xF, CF; = CFOCF: CF (CF3) OCF; CFCF3SO) F, CF3 = CF (CF3); SOF, CF3 = CFO [CF; CF (CF3) O] 1CF.CFE3SOF, and CF. = CFOCF; CF (CF; OCF3) OCF; CFSO »xF.

[001383] Among them, CF = CFOCF; CF (CF3) OCF; CF; CFSO0.F = and CF; = CFOCF; CF (CF3) OCF; CF3SO, F are more preferable.

[001384] The copolymer obtained from these monomers can be produced by a polymerization method developed for homopolymerization and copolymerization of ethylene fluoride, particularly a general polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, a polymerization reaction can be carried out in the presence of a radical polymerization initiator such as a perfluorocarbon peroxide or an azo compound under the conditions of a temperature of 0 to 200ºC and a pressure of 0, 1 to 20 MPa using an inert solvent such as a perfluorohydrocarbon or a chlorofluorocarbon.

[001385] In the above copolymerization, the type of combination of the above monomers and their proportion are not particularly limited and are selected and determined depending on the type and quantity of the desired functional group to be imparted to the fluorine-containing polymer to be obtained. For example, when a fluorine-containing polymer containing only one carboxylic acid group is formed, at least one monomer must be selected from each of the first group and the second group described above and copolymerized. In addition, when a fluorine-containing polymer containing only one sulfonic acid group is formed, at least one monomer must be formed.

364/803 be selected from each of the first group and the third group and copolymerized. In addition, when a fluorine-containing polymer with a carboxylic acid group and a sulfonic acid group is formed, at least one monomer must be selected from each of the first group, the second group and the third group described above and copolymerized. In that case, the target fluorine-containing polymer can also be obtained by separately preparing a copolymer comprising the monomers of the first group and the second group described above and a copolymer comprising the monomers of the first group and the third group described above, and then mixing the copolymers. The mixing ratio of the monomers is not particularly limited, and when the number of functional groups per unit of polymer is increased, the proportion of the selected monomers from the second and third groups described above should be increased.

[001386] The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, more preferably 0.6 to 1.5 mg equivalent / g. The total ion exchange capacity here refers to the exchange group equivalent per unit weight of the dry resin and can be measured by neutralization titration or the like.

[001387] In the membrane body 10 of the ion exchange membrane 1, a layer of sulfonic acid 3 containing a polymer containing fluorine with a group of sulfonic acid and a layer of carboxylic acid 2 containing a polymer containing fluorine with a group of carboxylic acid are laminated. By providing the membrane body 10 with this layer configuration, the selective permeability for cations, such as sodium fons, can be further improved.

[001388] The ion exchange membrane | is arranged in an electrolyser in such a way that, generally, the layer of sulfonic acid 3 is located in the

365/803 side of the electrolyzer anode and the carboxylic acid layer 2 is located on the cathode side of the electrolyzer.

[001389] The sulfonic acid layer 3 is preferably made of a material with low electrical resistance and has a membrane thickness greater than that of the carboxylic acid layer 2 from the point of view of the membrane resistance. The membrane thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, more preferably 3 to 15 times that of the carboxylic acid layer 2.

[001390] The carboxylic acid layer 2 preferably has high anion exclusion properties, even if it has a small membrane thickness. The anion exclusion properties here refer to the property of trying to prevent anion intrusion and permeation into and through the ion exchange membrane 1. In order to increase the anion exclusion properties, it is effective to lay out a layer of carboxylic acid with a small ion exchange capacity to the sulfonic acid layer.

[001391] As the fluorine-containing polymer for use in the sulfonic acid layer 3, a polymer obtained using CF; = CFOCF; CF (CF3) OCF; CF3SO, 3F as the monomer of the third group is preferred.

[001392] As the fluorine-containing polymer for use in the carboxylic acid-2 layer, a polymer obtained using CF; = CFOCF; CF (CF3) O (CF;); COOCH; as the monomer of the second group. (Coating layer)

[001393] The ion exchange membrane preferably has a coating layer on at least one surface of the membrane body. As shown in Figure 97, on the ion exchange membrane 1, coating layers 11a and 11b are formed on both surfaces of the membrane body 10.

[001394] The coating layers contain particles of material

366/803 inorganic and a binder.

[001395] The average particle size of the particles of inorganic material is preferably 0.90 µm or more. When the average particle size of the particles of inorganic material is 0.90 µm or more, the durability to impurities is greatly improved, in addition to the gas display. That is, increasing the average particle size of the particles of inorganic material, as well as satisfying the value of the specific surface area mentioned above, can achieve a particularly remarkable effect. Irregular inorganic material particles are preferable because the average particle size and specific surface area, as above, are satisfied. Particles of inorganic material obtained by melting and particles of inorganic material obtained by grinding ore can be used. Particles of inorganic material obtained by grinding raw ore can preferably be used.

[001396] The average particle size of the particles of inorganic material can be 2 µm or less. When the average particle size of the particles of inorganic material is 2 µm or less, it is possible to avoid damage to the membrane due to the particles of inorganic material. The average particle size of the inorganic material particle is more preferably 0.90 to 1.2 µm.

[001397] Here, the average particle size can be measured by a particle size analyzer (“SALD2200”, SHIMADZU CORPORATION).

[001398] Particles of inorganic material preferably have irregular shapes. Such shapes further improve resistance to impurities. Particles of inorganic material preferably have a wide particle size distribution.

[001399] The particles of inorganic material preferably contain at least one inorganic material selected from the group consisting of

367/803 in oxides of Group IV elements in the Periodic Table, nitrides of Group IV elements in the Periodic Table and carbides of Group IV elements in the Periodic Table. From the point of view of durability, the zirconium oxide particle is more preferable.

[001400] The particles of inorganic material are preferably particles of inorganic material produced by grinding the raw ore of the particles of inorganic material or particles of inorganic material, as spherical particles with a uniform diameter, obtained by purification by melting the raw ore of the particles of inorganic material.

[001401] Examples of means for grinding raw ore include, but are not particularly limited to, ball mills, ball mills, colloid mills, conical mills, disc mills, roller mills, grain mills, hammer mills, granules, VSI mills, Wiley mills, laminators and jet mills. After grinding, the particles are preferably washed. As a washing method, the particles are preferably treated with acid. This treatment can reduce impurities, such as iron affixed to the surface of particles of inorganic material.

[001402] The coating layer preferably contains a binder. The binder is a component that forms the coating layers retaining particles of inorganic material on the surface of the ion exchange membrane. The binder preferably contains a polymer containing fluorine from the point of view of durability to the electrolytic solution and electrolysis products.

[001403] As the binder, a fluorine-containing polymer with a carboxylic acid group or a sulfonic acid group is preferred, from the point of view of durability to the electrolytic solution and products of electrolysis and adhesion to the surface of the ion exchange membrane. When a coating layer is provided in a layer containing a fluorine-containing polymer

368/803 with a sulfonic acid group (sulfonic acid layer), a fluorine-containing polymer with a sulfonic acid group is still preferably used as the binder of the coating layer. Alternatively, when a coating layer is provided on a layer containing a fluorine-containing polymer with a carboxylic acid group (carboxylic acid layer), a fluorine-containing polymer with a carboxylic acid group is still preferably used as the binder of the coating layer.

[001404] In the coating layer, the content of the particles of inorganic material is preferably 40 to 90% by weight, more preferably 50 to 90% by weight. The content of the binder is preferably 10 to 60% by weight, more preferably 10 to 50% by weight.

[001405] The density of distribution of the coating layer on the ion exchange membrane is preferably 0.05 to 2 mg per 1 µm. When the ion exchange membrane has roughness on its surface, the distribution density of the coating layer is preferably 0.5 to 2 mg per 1 in °.

[001406] As the method for forming the coating layer, which is not particularly limited, a known method can be used. An example is a method that includes spraying or the like of a coating liquid obtained by dispersing particles of inorganic material in a solution containing a binder. (Reinforcement core materials)

[001407] The ion exchange membrane preferably has reinforcement core materials arranged within the membrane body.

[001408] The reinforcement core materials are members that enhance the resistance and dimensional stability of the ion exchange membrane. By arranging the reinforcement core materials within the membrane body, particularly the expansion and contraction of the ion exchange membrane can be controlled in the desired range. Such an ion exchange membrane

369/803 does not expand or contract more than necessary during electrolysis and the like and can maintain excellent dimensional stability in the long run.

[001409] The configuration of the reinforcement core materials is not particularly limited and, for example, the reinforcement core materials can be formed by spinning threads called reinforcement threads. The reinforcement threads here refer to threads that are members that make up the reinforcement core materials, can provide the desired dimensional stability and mechanical resistance to the ion exchange membrane and can be stably present in the ion exchange membrane. By using the reinforcement core materials obtained by spinning such reinforcement threads, better dimensional stability and mechanical resistance to the ion exchange membrane can be provided.

[001410] The material of the reinforcement core materials and the reinforcement yarns used for them is not particularly limited, but is preferably a material resistant to acids, alkalis, etc., and a fiber comprising a fluorine-containing polymer is preferable because the long-term thermal resistance and chemical resistance are required.

[001411] Examples of the fluorine-containing polymer to be used in the reinforcement core materials include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers, tetrafluoroethylene-ethylene (ETFE) copolymers, tetrafluoroethylene-copolymers, hexetrafluoroethylene and copolymers. trifluorochlorethylene-ethylene and polymers of vinylidene fluoride (PVDF). Among these, fibers comprising polytetrafluoroethylene are preferably used from the point of view of heat resistance and chemical resistance.

[001412] The wire diameter of the reinforcement threads used for the reinforcement core materials is not particularly limited, but is preferably 20 to 300 deniers, more preferably 50 to 250 deniers. The density of

370/803 weaving (fabric count per unit length) is preferably 5 to 50 / inch. The shape of the reinforcement core materials is not particularly limited, for example, a woven fabric, a non-woven fabric and a knitted fabric are used, but it is preferably in the form of a woven fabric. The thickness of the woven fabric to be used is preferably 30 to 250 µm, more preferably 30 to 150 µm.

[001413] As woven fabric or knitted fabric, monofilaments, multifilaments, or yarns thereof, a slit yarn, or the like, and various types of weaving methods, such as single weft, leno weft, knitted weft, weft can be used cord and sirsaca, can be used.

[001414] The weft and the arrangement of the reinforcement core materials in the membrane body are not particularly limited, and the preferred arrangement can be suitably provided considering the size and shape of the ion exchange membrane, desired physical properties for the membrane of ion exchange, the environment of use and the like.

[001415] For example, the reinforcement core materials can be arranged along a predetermined direction of the membrane body, but from the point of view of dimensional stability, it is preferable that the reinforcement core materials are arranged over a predetermined first direction, and other reinforcement core materials along a second direction substantially perpendicular to the first direction. By arranging the plurality of reinforcement core materials substantially orthogonally within the membrane body, it is possible to provide better dimensional stability and mechanical strength in several directions. For example, the arrangement in which reinforcement core materials arranged along the longitudinal direction (warp yarns) and reinforcement core materials arranged along the transverse direction (weft threads) are woven on the surface side of the body membrane is preferred. The arrangement is most preferably in the form of a driven flat weave and fabric allowing the

371/803 warps and wefts move alternately between themselves and underneath each other, plain weave in which two warps are woven into wefts while twisted, woven into a driven basket and woven by insertion into two or more warps arranged in parallel, wefts of the same number or similar, from the point of view of dimensional stability, mechanical strength and ease of production.

[001416] It is preferred that, in particular, the reinforcement core materials are arranged along both directions, the MD (Machine Direction) and TD (Transversal Direction) of the ion exchange membrane. In other words, the reinforcement core materials are preferably single woven in MD and TD. Here, MD refers to the direction in which the membrane body and various core materials (for example, the reinforcement core materials, reinforcement wires and sacrificial wires described below) are transported in a production step of ion exchange membrane described later (flow direction) and TD refers to the direction substantially perpendicular to the MD. The threads woven along the MD are called MD threads, and the threads woven along the TD are called TD threads. Typically, the ion exchange membrane used for electrolysis is rectangular, and in many cases, the longitudinal direction is the MD, and the width direction is the TD. By weaving the reinforcement core materials that are MD yarns and the reinforcement core materials that are TD yarns, it is possible to provide better dimensional stability and mechanical strength in many directions.

[001417] The range of arrangement of the reinforcement core materials is not particularly limited, and the preferred arrangement can be adequately provided considering the desired physical properties for the ion exchange membrane, the environment of use and the like.

[001418] The orifice ratio for the reinforcement core materials is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The orifice ratio is

372/803 preferably 30% or more from the point of view of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the point of view of the mechanical resistance of the ion exchange membrane.

[001419] The orifice ratio for reinforcement core materials refers to a ratio of a total area of a surface through which substances such as fons (an electrolyte solution and cations contained in it (for example, sodium fons)) they can pass (B) to the area of one of the surfaces of the membrane body (A) (B / A). The total surface area through which substances such as fons can pass (B) can refer to the total areas of regions in which the ion exchange membrane, cations, an electrolyte solution and the like are not blocked by the reinforcement core materials and similar substances contained in the ion exchange membrane.

[001420] Figure 98 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane. Figure 98, in which a portion of the ion exchange membrane is enlarged, shows only the arrangement of the reinforcement core materials 21 and 22 in the regions, omitting the illustration of the other members.

[001421] By subtracting the total area of the reinforcement core materials (C) from the area of the region surrounded by the reinforcement core materials 21 arranged along the longitudinal direction and the reinforcement core materials 22 arranged along the transverse direction, the region including the area of the reinforcement core materials (A), the total area of regions through which substances such as phons can pass (B) in the area of the region described above (A) can be obtained. That is, the orifice ratio can be determined by the following formula (1): Orifice ratio = (B) / (A) = ((A) - (C)) / (A) ... (D

[001422] Among the materials of the reinforcement core, a particularly preferred form are ribbon yarn or highly monofilament

373/803 oriented comprising PTFE from the point of view of chemical resistance and heat resistance. Specifically, reinforcement core materials forming a single web in which 50 to 300 denier ribbon yarns obtained by cutting a high strength porous sheet comprising PTFE into a ribbon form, or highly oriented 50 to 300 denier monofilaments are used comprising PTFE and having a weave density of 10 to 50 threads or monofilaments / inch and having a thickness in the range of 50 to 100 µm are more preferred. The orifice ratio of an ion exchange membrane comprising such reinforcement core materials is still preferably 60% or more.

[001423] Examples of the shape of the reinforcement threads include round threads and ribbon threads. (Continuous holes)

[001424] The ion exchange membrane preferably has continuous holes inside the body of the membrane.

[001425] Continuous holes refer to holes that can be flow paths for fons generated in electrolysis and an electrolyte solution. The continuous holes, which are tubular holes formed inside the membrane body, are formed by dissolving the sacrificial core materials (or sacrificial threads) described below. The shape, diameter or the like of the continuous holes can be controlled by selecting the shape or diameter of the sacrificial core materials (sacrificial threads).

[001426] Forming the continuous holes inside the ion exchange membrane can guarantee the mobility of an electrolyte solution in electrolysis. The shape of the continuous holes is not particularly limited, but it may be the shape of the sacrificial core materials to be used for forming the continuous holes according to the production method described below.

[001427] The continuous holes are preferably formed so that they pass alternately on the anode side (sulfonic acid layer side)

374/803 and on the cathode side (carboxylic acid layer side) of the reinforcement core materials. With this structure, in a portion in which continuous holes are formed on the cathode side of the reinforcement core materials, ions (eg sodium fons) carried by the electrolyte solution with which the continuous holes are filled can also flow on the side of the cathode of the reinforcement core materials. As a result, the flow of cations is not interrupted and, therefore, it is possible to further reduce the electrical resistance of the ion exchange membrane.

[001428] Continuous holes can be formed along only a predetermined direction of the membrane body that constitutes the ion exchange membrane, but are preferably formed both in the longitudinal and transverse direction of the membrane body from the point of view of presenting a more stable electrolytic performance. [Production method]

[001429] A suitable example of a method for producing an ion exchange membrane includes a method including the following steps (1) to (6): Step (1): the step of producing a fluorine-containing polymer with an exchange group ionic or an ion exchange group precursor capable of forming an ion exchange group by hydrolysis, Step (2): the step of weaving at least a plurality of reinforcement core materials, as required, and sacrificial yarns with a proprietary dissolving in an acid or an alkali, and forming continuous holes to obtain a reinforcement material in which the sacrifice wires are arranged between the reinforcement core materials adjacent to each other, Step (3): the formation step in a fluorine-containing polymer film above with an ion exchange group or a precursor to the ion exchange group capable of forming an ion exchange group by hydrolysis, Step (4): the step of embedding the reinforcement materials

375/803 above, as required, in the above film to obtain a membrane body within which the reinforcement materials are arranged, Step (5): the hydrolysis step of the membrane body obtained in step (4) (step of hydrolysis), and Step (6): the step of providing a coating layer on the membrane body obtained in step (5) (application step).

[001430] Next, each of the steps will be described in detail. Step (1): Fluorine-containing polymer production step

[001431] In step (1), the raw material monomers described in the first group for the third group above are used to produce a fluorine-containing polymer. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the raw material monomers must be adjusted in the production of the fluorine-containing polymer that forms the layers. Step (2): Reinforcement materials production step

[001432] The reinforcement material is a woven fabric obtained by weaving reinforcement threads or the like. The reinforcement material is embedded in the membrane to form reinforcement core materials. When an ion exchange membrane with continuous holes is formed, the sacrificial threads are additionally woven into the reinforcement material. The amount of the sacrificial yarns contained in that case is preferably 10 to 80% by weight, more preferably 30 to 70% by weight based on the entire reinforcement material. Weaving the sacrificial yarns can also prevent the yarn from slipping the reinforcement core materials.

[001433] As sacrificial threads, which have solubility in the membrane production stage or under an electrolysis environment, rayon, polyethylene terephthalate (PET), cellulose, polyamide and the like are used. Also preferred are monofilaments or multifilaments having a thickness of 20 to 50 deniers and comprising polyvinyl alcohol and the like.

376/803

[001434] In step (2), the orifice ratio, the arrangement of the continuous holes and the like can be controlled by adjusting the arrangement of the reinforcement core materials and the sacrifice wires. Step (3): Film forming step

[001435] In step (3), the fluorine-containing polymer obtained in step (1) is formed into a film using an extruder. The film can be a single layer configuration, a two layer configuration of a sulfonic acid layer and a layer of carboxylic acid, as mentioned above, or a multilayer configuration of three layers or more.

[001436] Examples of the film-forming method include the following: a method in which a fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are formed separately in films; and a method in which the fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are coextruded into a composite film.

[001437] The number of each film can be more than one. Coextrusion of different films is preferred because of their contribution to an increase in adhesive strength at the interface. Stage (4): Stage of obtaining the membrane body

[001438] In step (4), the reinforcement material obtained in step (2) is embedded in the film obtained in step (3) to provide a membrane body including the reinforcement material therein.

[001439] Preferable examples of the method for forming a membrane body include (1) a method in which a fluorine-containing polymer with a precursor to the carboxylic acid group (e.g., carboxylate functional group) (hereinafter, a layer comprising the same is called the first layer) located on the cathode side and a fluorine-containing polymer with a precursor to the sulfonic acid group (eg, sulfonyl fluoride functional group) (hereinafter, a layer comprising the same is called the second layer) are formed into a film by a coextrusion method and, using a heat source and a vacuum source as needed, a reinforcement material and the second layer / first layer composite film are laminated in that order on breathable release paper resistant to heat in a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated by reduced pressure; and (11) a method in which, in addition to the composite film of the second layer / first layer, a fluorine-containing polymer with a precursor to the sulfonic acid group is formed separately in a film (the third layer) in advance and, using a heat source and a vacuum source as needed, the third layer film, the reinforcement core materials and the composite film comprising the second layer / first layer are laminated in that order on heat resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated under reduced pressure.

[001440] The coextrusion of the first layer and the second layer contributes to an increase in the adhesive strength at the interface.

[001441] The method including integration under reduced pressure is characterized by making the third layer in the reinforcement material thicker than that of the pressure method of applying pressure. In addition, since the reinforcement material is fixed on the inner surface of the membrane body, the method has a property of sufficiently retaining the mechanical resistance of the ion exchange membrane.

378/803

[001442] The lamination variations described here are exemplary, and coextrusion can be performed after a preferred lamination pattern (for example, the combination of layers) is appropriately selected considering the desired layer configuration of the membrane body and physical properties, and the like.

[001443] In order to further improve the electrical properties of the ion exchange membrane, it is also possible to additionally interpose a fourth layer comprising a fluorine-containing polymer with a precursor of the carboxylic acid group and a precursor of the sulfonic acid group between the first layer and the second layer or using a fourth layer comprising a fluorine-containing polymer with a carboxylic acid group precursor and a sulfonic acid group precursor instead of the second layer.

[001444] The method for forming the fourth layer can be a method in which a fluorine-containing polymer with a carboxylic acid group precursor and a fluorine-containing polymer with a sulfonic acid group precursor are separately produced and then mixed or can be a method wherein a monomer with a precursor to the carboxylic acid group and a monomer with a precursor to the sulfonic acid group are copolymerized.

[001445] When the fourth layer is used as a component of the ion exchange membrane, a coextruded film of the first layer and the fourth layer is formed, in addition, the third layer and the second layer are formed separately in films, and the lamination can be performed by the method mentioned above. Alternatively, the three layers of the first layer / fourth layer / second layer can be simultaneously formed into a film by coextrusion.

[001446] In this case, the direction in which the extruded film flows is the MD. As mentioned above, it is possible to form a membrane body containing

379/803 a fluorine-containing polymer with an ion exchange group in a reinforcement material.

[001447] Additionally, the ion exchange membrane preferably has protruding portions composed of the fluorine-containing polymer with a sulfonic acid group, that is, projections, on the surface side composed of the sulfonic acid layer. As a method for forming such projections, which is not particularly limited, one can also use a known method including forming projections on a resin surface. A specific example of the method is a method of embossing the surface of the membrane body. For example, the above projections can be formed using release paper embossed in advance when the composite film mentioned above, reinforcement material and the like are integrated. In the case where the projections are formed by embossing, the height and density of arrangement of the projections can be controlled by controlling the form of embossing to be transferred (shape of the release paper). (5) Hydrolysis step

[001448] In step (5), a step of hydrolysis of the membrane body obtained in step (4) is carried out to convert the precursor of the ion exchange group into an ion exchange group (hydrolysis step).

[001449] In step (5), it is also possible to form dissolution holes in the membrane body by dissolving and removing the sacrifice wires included in the membrane body with acid or alkali. The sacrifice wires can remain in the continuous holes without being completely dissolved and removed. The sacrifice wires that remain in the continuous holes can be dissolved and removed by the electrolyte solution when the ion exchange membrane is subjected to electrolysis.

[001450] The sacrifice wire has solubility in acid or alkali in the production stage of an ion exchange membrane or under an environment of

380/803 electrolysis. The sacrifice wires are eluted to form continuous holes at the corresponding locations.

[001451] Step (5) can be carried out by immersing the membrane body obtained in step (4) in a hydrolysis solution containing acid or alkali. An example of the hydrolysis solution that can be used is a mixed solution containing KOH and dimethyl sulfoxide (DMSO).

[001452] The mixed solution preferably contains KOH of 2.5 to 4.0 Ne and DMSO of 25 to 35% by weight.

[001453] The temperature for hydrolysis is preferably 70 to 100 ° C. The higher the temperature, the greater the apparent thickness. The temperature is more preferably 75 to 100 ° C.

[001454] The time for hydrolysis is preferably 10 to 120 minutes. The longer the time, the greater the apparent thickness. The time is most preferably 20 to 120 minutes.

[001455] The step of forming continuous holes eluting the sacrificial wire will now be described in more detail. Figures 99 (a) and (b) are schematic views to explain a method for forming the continuous holes in the ion exchange membrane.

[001456] Figures 99 (a) and (b) show the reinforcement threads 52, the sacrifice threads 504a and the continuous holes 504 formed only by the sacrifice threads 504a, omitting the illustration of the other members, such as a body of membrane.

[001457] Firstly, the reinforcement wires 52 that constitute reinforcement core materials in the ion exchange membrane and the sacrifice wires 504a to form the continuous holes 504 in the ion exchange membrane are used as interlaced reinforcement materials. Then, in step (5), the sacrifice threads 504a are eluted to form continuous holes 504.

[001458] The above method is simple because the method for interlacing reinforcement wires 52 and sacrifice wires 504a can be adjusted

381/803 depending on the arrangement of the reinforcement core materials and the continuous holes in the membrane body of the ion exchange membrane.

[001459] Figure 99 (a) exemplifies the single fabric reinforcement material in which reinforcement threads 52 and sacrifice threads 504a are interwoven along the longitudinal and lateral direction on the paper, and the arrangement of the reinforcement 52 and the sacrifice wires 504a in the reinforcement material may vary as required. (6) Application stage

[001460] In step (6), a coating layer can be formed by preparing a coating liquid containing particles of inorganic material obtained by grinding raw ore or melting raw ore and a binder, applying the coating liquid on the surface of the ion exchange membrane obtained in step (5), and drying of the coating liquid.

[001461] A preferred binder is a binder obtained by hydrolysis of a fluorine-containing polymer with an ion exchange group precursor with an aqueous solution containing dimethylsulfoxide (DMSO) and potassium hydroxide (KOH) and then immersion of the polymer in hydrochloric acid to replace the counter-ion of the ion exchange group with H + (for example, a fluorine-containing polymer with a carboxyl group or a sulfo group). Thus, the polymer is more likely to dissolve in water or ethanol mentioned below, which is preferable.

[001462] This binder is dissolved in a mixed solution of water and ethanol. The volume ratio between water and ethanol is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 2: 1 to 1: 2. The particles of inorganic material are dispersed with a ball mill in the dissolution liquid thus obtained to provide a coating liquid. In this case, it is also possible to adjust the average particle size and similar particles by adjusting the time and speed of

382/803 rotation during dispersion. The preferable amount of the particles of inorganic material and the binder to be mixed is as mentioned above.

[001463] The concentration of the particles of inorganic material and the binder in the coating liquid is not particularly limited, but a thin-coated liquid is preferable. This allows uniform application to the surface of the ion exchange membrane.

[001464] Additionally, a surfactant can be added to the dispersion when the particles of inorganic material are dispersed. Like the surfactant, nonionic surfactants are preferable and examples of them include HS-210, NS-210, P-210 and E-212 manufactured by NOF CORPORATION.

[001465] The coating liquid obtained is applied on the surface of the ion exchange membrane by spray application or roller coating, thus providing an ion exchange membrane. [Microporous membrane]

[001466] The microporous membrane of the present modality is not particularly limited as long as the membrane can be formed in a laminate with the electrolysis electrode, as mentioned above. Several microporous membranes can be used.

[001467] The porosity of the microporous membrane of the present embodiment is not particularly limited, but it can be from 20 to 90, for example, and is preferably from 30 to 85. The porosity above can be calculated by the following formula: Porosity = (1 - (the weight of the membrane in a dry state) / (the weight calculated from the volume calculated from the thickness, width and length of the membrane and the density of the membrane material)) x 100

[001468] The average pore size of the microporous membrane of the present embodiment is not particularly limited, and can be 0.01 µm to 1 µm, for example, preferably 0.05 µm to 5 µm. In relation to

383/803 average pore size, for example, the membrane is cut vertically in the direction of thickness, and the section is observed with an FE-SEM. The average pore size can be obtained by measuring the diameter of about 100 observed pores and averaging the measurements.

[001469] The thickness of the microporous membrane of the present embodiment is not particularly limited, and can be from 10 µm to 1000 µm, for example, preferably 50 µm to 600 µm. The above thickness can be measured using a micrometer (manufactured by Mitutoyo Corporation) or similar, for example.

[001470] Specific examples of the microporous membrane as mentioned above include Zirfon Perl UTP 500 manufactured by Agfa (also called Zirfon membrane in the present embodiment) and those described in International Publication No. WO 2013-183584 and International Publication No. WO 2016-203701.

[001471] In the present embodiment, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different EW (ion exchange capacity) than that of the first layer of ion exchange resin. In addition, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different functional group than that of the first layer of ion exchange resin. The ion exchange capacity can be adjusted by the functional group to be introduced, and functional groups that can be introduced are as mentioned above. (Water electrolysis)

[001472] The electrolyser in the present modality, like an electrolyser in the case of water electrolysis, has a configuration in which the ion exchange membrane in an electrolyser for use in the case of common salt electrolysis mentioned above is replaced by a microporous membrane. School subjects-

384/803 raw material to be supplied, which is water, is different from that for the electrolyser in the case of electrolysis of the common salt mentioned above. As for the other components, components similar to those of the electrolyser in the case of electrolysis of common salt can also be used in the electrolyser in the case of water electrolysis. Since chlorine gas is generated in the anodic chamber in the case of common salt electrolysis, titanium is used as the material in the anodic chamber, but in the case of water electrolysis, only oxygen gas is generated in the anodic chamber. Thus, a material identical to that of the cathodic chamber can be used. An example of this is nickel. For the anode coating, the catalyst coating for oxygen generation is suitable. Examples of the catalyst coating include metals, oxides and hydroxides of the metals of the platinum group and metals of the transition metal group. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used. [Method to renew the electrode]

[001473] The method for producing an electrolyzer according to the present modality can also be carried out as a method for renewing an electrode (anode and / or cathode). That is, the method for renewing an electrode according to the present modality is a method for renewing an existing electrode using an electrolysis electrode, in which the electrolysis electrode that is in a coiled body shape is used.

[001474] Specific examples of a step of using a rolled-up body include, but are not particularly limited to, a method in which the electrolysis electrode being in a rolled-up body shape, after its rolled state is released, is arranged on the surface of the existing electrode. Through the method, the electrolysis electrode can be arranged on the surface of the existing anode or cathode, and the characteristics of the anode and / or cathode can be renewed.

[001475] As described above, in the present modality, the use stage

385/803 of a coiled body preferably has a step (B) of releasing the coiled state from the coiled body, and after step (B), more preferably it has a step (C) of arranging an electrolysis electrode on the existing electrode surface .

[001476] Also in the method to renew an electrode according to the present modality, the step of using the wound body preferably has a step (A) of retaining the electrode for electrolysis in a wound state to obtain a wound body. In step (A), the electrolysis electrode per se can be coiled to form a coiled body, or the electrolysis electrode is coiled around a core to form a coiled body. As the core that can be used here, which is not particularly limited, a member with a substantially cylindrical shape and a size corresponding to the electrolyte electrode can be used, for example. [Method to produce the rolled-up body]

[001477] In the method to produce an electrolyzer according to the present modality and the method to renew an electrode according to the present modality, step (A) or (A), which can be carried out, can also be carried out as a method for producing a rolled-up body. That is, the method for producing a coiled body according to the present embodiment is a method for producing a coiled body to be used to renew an existing electrolyzer comprising an anode, a cathode that is opposite the anode, and a membrane that is arranged between the anode and the cathode, the method comprising a step of winding an electrolyte electrode or a laminate of the electrode for electrolysis and a new membrane to obtain the wound body. In the step of obtaining a coiled body, the electrolysis electrode per se can be coiled to form a coiled body, or the electrolysis electrode can be coiled around a core to form a coiled body. As the core that can be

386/803 used here, which is not particularly limited, a member with a substantially cylindrical shape and a size corresponding to the electrolyte electrode can be used, for example. <Sixth modality>

[001478] Here, a sixth embodiment of the present invention will be described in detail with reference to Figures 103 to 111. [Method for producing the electrolyzer]

[001479] The method for producing an electrolyzer according to the sixth modality (hereinafter, in the section of <Sixth modality>, simply called “the present modality”) is a method for producing a new electrolyzer by arranging a laminate in a existing electrolyzer comprising an anode, a cathode that is opposite the anode, and a membrane that is arranged between the anode and the cathode, the method comprising a step (A) of integrating an electrode for electrolysis with a new membrane at a temperature in that the membrane does not fuse to obtain the laminate, and a step (B) of replacing the membrane in the existing electrolyzer with the laminate after step (A).

[001480] As described above, according to the method for producing an electrolyzer according to the present modality, it is possible to integrate and use the electrolyte electrode and the membrane, not according to an impractical method, such as thermal compression. Thus, it is possible to improve work efficiency during the electrode renewal in an electrolyser.

[001481] In the present embodiment, the existing electrolyzer comprises an anode, a cathode that is opposite the anode and a membrane that is arranged between the anode and the cathode as constituent members, in other words, comprises an electrolytic cell. The existing electrolyzer is not particularly limited as long as it comprises the constituent members described above, and several known configurations can be used.

[001482] In the present modality, a new electrolyzer comprises

387/803 additionally an electrode for electrolysis or a laminate, in addition to a member that already served as an anode or cathode in the existing electrolyzer. That is, the "electrolysis electrode" arranged in the production of a new electrolyzer serves as an anode or cathode, and is separated from the cathode and anode in the existing electrolyzer. In the present modality, even in the case where the electrolytic performance of the anode and / or cathode has deteriorated in association with the operation of the existing electrolyzer, the arrangement of a separate electrolysis electrode allows the anode and / or cathode characteristics to be renewed . In addition, a new ion exchange membrane that constitutes the laminate is arranged in combination and, thus, the characteristics of the ion exchange membrane with characteristics that have deteriorated in association with the operation can be renewed simultaneously. “Renewing the characteristics” referred to here means having characteristics comparable to the initial characteristics possessed by the existing electrolyzer before being operated or having characteristics superior to the initial characteristics.

[001483] In the present modality, it is assumed that the existing electrolyzer is an “electrolyzer that has already been operated” and it is assumed that the new electrolyzer is an “electrolyzer that has not yet been operated”. That is, once an electrolyser produced as a new electrolyser is operated, the electrolyser becomes “the existing electrolyser in the present modality”. The arrangement of an electrolysis electrode or a laminate in this existing electrolyser provides "a new electrolyser of the present modality".

[001484] Hereinafter, a case of conducting common salt electrolysis using an ion exchange membrane as the membrane is taken as an example, and an embodiment of the electrolyzer will be described in detail. In the <Sixth modality> section, unless otherwise specified, "the electrolyser in the present modality" incorporates both "the electrolyser existing in the present modality" and "the new electrolyser in the present modality".

388/803 [Electrolytic cell]

[001485] First, the electrolytic cell will be described, which can be used as a constituent unit of the electrolyzer in the present modality. Figure 103 illustrates a cross-sectional view of an electrolytic cell 1.

[001486] The electrolytic cell 1 comprises an anodic chamber 10, a cathodic chamber 20, a partition wall 30 placed between the anodic chamber 10 and the cathodic chamber 20, an anode 11 placed in the anodic chamber and a cathode 21 placed in the cathodic chamber 20 As required, the electrolytic cell 1 has a substrate 18a and a reverse current absorbent layer 18b formed on the substrate 18a and can comprise a reverse current absorber 18 placed in the cathode chamber. Anode 11 and cathode 21 belonging to electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 comprises the following cathode structure. The cathode structure 40 comprises the cathode chamber 20, the cathode 21 placed in the cathode chamber 20 and the reverse current absorber 18 placed in the cathode chamber 20, the reverse current absorber 18 has the substrate 18a and the reverse current absorbent layer 18b on substrate 18a, as shown in Figure 107, and cathode 21 and reverse current absorbing layer 18b are electrically connected. The cathodic chamber 20 also has a collector 23, a support 24 supporting the collector and an elastic metal body 22. The elastic metal body 22 is placed between the collector 23 and the cathode 21. The support 24 is placed between the collector 23 and the partition wall 30. The collector 23 is electrically connected to the cathode 21 through the elastic metal body 22. The partition wall 30 is electrically connected to the collector 23 through the support 24. Therefore, the partition wall 30, the support 24, the collector 23, the elastic metal body 22 and the cathode 21 are electrically connected. Cathode 21 and reverse current absorbing layer 18b are electrically connected. Cathode 21 and the reverse current absorbing layer can be directly connected

389/803 or can be indirectly connected through the collector, the support, the elastic metal body, the partition wall or the like. The entire surface of cathode 21 is preferably covered with a layer of catalyst for the reduction reaction. The electrical connection form can be a form in which the partition wall 30 and the support 24, the support 24 and the collector 23, and the collector 23 and the elastic metal body 22 are each directly attached and the cathode 21 it is laminated to the elastic metal body 22. Examples of a method for directly affixing these constituent components to each other include welding and the like. Alternatively, the reverse current absorber 18, cathode 21 and collector 23 can be collectively called a cathode structure 40.

[001487] Figure 104 illustrates a cross-sectional view of two electrolytic cells 1 that are adjacent to the electrolyzer 4. Figure 105 shows an electrolyzer 4. Figure 106 shows an assembly step for the electrolyzer 4.

[001488] As shown in Figure 104, an electrolytic cell 1, a cation exchange membrane 2 and an electrolytic cell 1 are arranged in series in the order mentioned. An ion exchange membrane 2 is arranged between the anode chamber of an electrolytic cell 1 between the two adjacent electrolytic cells in the electrolyzer and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent to it are separated by the cation exchange membrane 2. As shown in Figure 105, the electrolyzer 4 is composed of a plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2. That is, the electrolyzer 4 is a bipolar electrolyzer comprising the plurality of electrolytic cells 1 arranged in series and ion exchange membranes 2, each arranged between adjacent electrolytic cells 1. As shown in Figure 106, electrolyzer 4 is assembled arranging the plurality of cells electrolytic 1

390/803 in series through the ion exchange membrane 2 and coupling the cells using a pressure device 5.

[001489] Electrolyser 4 has an anodic terminal 7 and a cathodic terminal 6 to be connected to a power supply. Anode 11 of electrolytic cell 1 located at the far end between the plurality of electrolytic cells 1 coupled in series in electrolyzer 4 is electrically connected to anode terminal 7. Cathode 21 of the electrolytic cell located at the opposite end to anode terminal 7 between the plurality of electrolytic cells 1 coupled in series in the electrolyzer 4 is electrically connected to the cathodic terminal 6. The electrical current during electrolysis flows from the side of the anodic terminal 7, through the anode and cathode of each electrolytic cell 1, towards the cathodic terminal 6. At the two ends of the coupled electrolytic cells 1, an electrolytic cell with only one anodic chamber (anode terminal cell) and an electrolytic cell with only one cathodic chamber (cathode terminal cell) can be arranged. In that case, anode terminal 7 is connected to the cell of the anode terminal, arranged at one end, and cathode terminal 6 is connected to the cell of the cathode terminal, arranged at the other end.

[001490] In the case of electrolytic brine, brine is provided for each anodic chamber 10 and pure water or an aqueous solution of low concentration sodium hydroxide is provided for each cathodic chamber 20. Each liquid is supplied from a supply tube of electrolytic solution (not shown in the Figure), through an electrolytic solution supply hose (not shown in the Figure), for each electrolytic cell 1. The electrolyte solution and electrolysis products are recovered from an electrolyte recovery tube (not shown in the figure). During electrolysis, the sodium ions in the brine migrate from the anode chamber 10 of the electrolytic cell 1, through the ion exchange membrane 2, to the cathode chamber 20 of the adjacent electrolytic cell 1. Thus, the electrical current

391/803 during electrolysis flows in the direction in which electrolytic cells 1 are coupled in series. That is, the electric current flows, through the cation exchange membrane 2, from the anodic chamber 10 towards the cathodic chamber 20. As the brine is electrolyzed, chlorine gas is generated on the anode side 11, and sodium hydroxide (solute ) and hydrogen gas are generated on the cathode side

21. (Anodic chamber)

[001491] The anodic chamber 10 has anode 11 or anode conductor 11. The supply conductor is referred to here to mean a degraded electrode (i.e., the existing electrode), an electrode without a catalyst coating and the like. When the electrode for electrolysis in the present embodiment is inserted on the anode side, 11 serves as a feed conductor for the anode. When the electrode for electrolysis in the present embodiment is not inserted on the anode side, 11 serves as an anode. The anode chamber 10 preferably has an electrolyte solution supply unit on the anode side that provides an electrolyte solution for the anode chamber 10, a baffle plate which is arranged above the anode side electrolyte solution supply unit to be substantially parallel or oblique to a partition wall 30, and a liquid and gas separation unit on the anode side which is arranged above the baffle to separate the gas from the electrolytic solution including the mixed gas. (Anode)

[001492] When the electrode for electrolysis in the present modality is not inserted on the side of the anode, an anode 11 is provided in the frame of the anode chamber 10 (that is, the anode frame). Like anode 11, a metal electrode such as the so-called DSA (R) can be used. DSA is an electrode that includes a titanium substrate whose surface is covered with an oxide that contains ruthenium, iridium and titanium as components.

392/803

[001493] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Anode feed conductor)

[001494] When the electrode for electrolysis in the present modality is inserted on the anode side, the anode 11 feeder conductor is provided in the anode chamber 10 frame. As the anode 11 feeder conductor, a metal electrode can be used , such as the so-called DSA (R), and titanium without catalyst coating can also be used. Alternatively, DSA with a thinner catalyst coating can also be used. In addition, a used anode can also be used.

[001495] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Anode side electrolyte solution supply unit)

[001496] The electrolytic solution supply unit on the anode side, which supplies the electrolytic solution to the anodic chamber 10, is connected to the electrolyte solution supply tube. The electrolytic solution supply unit on the anode side is preferably arranged below the anode chamber 10. As the electrolytic solution supply unit on the anode side, for example, a tube can be used on the surface from which orifice portions are formed. (dispersion tube) and the like. Such a tube is most preferably arranged along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell. This tube is connected to an electrolytic solution supply tube (liquid supply nozzle) that supplies the electrolytic solution to the electrolytic cell 1. The electrolyte solution supplied from the liquid supply nozzle is

393/803 transported with a tube into the electrolytic cell 1 and forced from the orifice portions provided on the surface of the tube into the anode chamber 10. The arrangement of the tube along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell is preferable because the electrolyte solution can be uniformly supplied into the anodic chamber

10. (Liquid and gas separation unit on the anode side)

[001497] The liquid and gas separation unit on the anode side is preferably arranged above the baffle plate. The liquid and gas separation unit on the anode side has the function of separating the produced gas such as chlorine gas from the electrolytic solution during electrolysis. Unless otherwise specified, above means the upper direction in electrolytic cell 1 in Figure 103, and below means the lower direction in electrolytic cell 1 in Figure 103.

[001498] During electrolysis, the produced gas generated in the electrolytic cell 1 and the electrolytic solution form a mixed phase (mixed gas-liquid phase), which is then emitted out of the system. Subsequently, pressure fluctuations within the electrolytic cell 1 cause vibration, which can result in physical damage to the ion exchange membrane. In order to avoid this event, the electrolytic cell 1 in the present embodiment is preferably provided with a liquid and gas separation unit on the anode side to separate the gas from the liquid. The liquid and gas separation unit on the anode side is preferably provided with an anti-foam plate to eliminate bubbles. When the flow of the mixed gas-liquid phase passes through the antifoam plate, the bubbles burst, thus allowing the electrolyte solution and the gas to be separated. As a result, vibration during electrolysis can be avoided. (Baffle plate)

[001499] The baffle plate is preferably arranged above the

394/803 electrolyte solution supply unit on the anode side and arranged substantially parallel or obliquely to the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anode chamber 10. When the baffle plate is provided , it is possible to make the electrolyte solution (brine or similar) circulate internally in the anodic chamber 10 to thus make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged in such a way as to separate the space in the vicinity of anode 11 from the space near the partition wall 30. From such a point of view, the baffle plate is preferably placed so as to be opposite the surface of anode 11 and the surface of the dividing wall 30. In the space next to the anode divided by the deflector plate, as the electrolysis progresses, the concentration of the electrolytic solution (brine concentration) is reduced and the gas produced, such as chlorine gas is generated. This results in a difference in specific gas-liquid gravity between the space near anode 11 and the space near the dividing wall 30 divided by the deflector plate. By using the difference, it is possible to promote the internal circulation of the electrolytic solution in the anodic chamber 10 to thus make the distribution of concentration of the electrolytic solution in the anodic chamber 10 more uniform.

[001500] Although not shown in Figure 103, a collector can be additionally provided inside the anodic chamber 10. The material and configuration of such a collector can be the same as the collector of the cathodic chamber mentioned below. In anode chamber 10, anode 11 per se can also serve as a collector. (Partition wall)

[001501] The dividing wall 30 is arranged between the anodic chamber 10 and the cathodic chamber 20. The dividing wall 30 can be called a separator, and the anodic chamber 10 and the cathodic chamber 20 are divided by the dividing wall 30. Like the wall divider 30, one known as a separator

395/803 for electrolysis can be used, and an example of this includes a partition wall formed by welding a plate comprising nickel beside the cathode and a plate comprising titanium beside the anode. (Cathodic chamber)

[001502] In the cathodic chamber 20, when the electrode for electrolysis in the present modality is inserted on the cathode side, 21 serves as a cathode supply conductor. When the electrolysis electrode in the present embodiment is not inserted on the cathode side, 21 it serves as a cathode. When a reverse current absorber is included, the cathode or cathode supply conductor 21 is electrically connected to the reverse current absorber. The cathode chamber 20, similarly to the anode chamber 10, preferably has an electrolytic solution supply unit on the cathode side and a liquid and gas separation unit on the cathode side. Among the components that make up the cathodic chamber 20, components similar to those that make up the anode chamber 10 will not be described. (Cathode)

[001503] When the electrode for electrolysis in the present embodiment is not inserted on the side of the cathode, a cathode 21 is provided in the frame of the cathode chamber 20 (i.e., the cathode frame). Cathode 21 preferably has a nickel substrate and a catalyst layer that covers the nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include metals such as Ru, C, Si, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, y-alloying, composite dispersion / galvanization, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer may have

396/803 a plurality of layers and a plurality of elements, as needed. Cathode 21 can be subjected to a reduction treatment as needed. As the cathode 21 substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[001504] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. (Cathode supply conductor)

[001505] When the electrode for electrolysis in the present embodiment is inserted on the cathode side, a cathode 21 conductor is provided in the cathode chamber 20 frame. The cathode 21 catheter can be covered with a catalytic component. The catalytic component can be a component that is originally used as the cathode and remains. Examples of the catalyst layer components include metals such as Ru, C, S1, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh , Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, I, Gd, Tb, Dy , Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, alloy galvanizing, composite dispersion / galvanizing, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Nickel, nickel alloys and nickel or stainless galvanized iron without catalyst coating can be used. As the cathode 21 feed conductor substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[001506] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal foil can be used

397/803 formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like. (Reverse current absorbing layer)

[001507] A material with a less noble redox potential than the element's redox potential for the catalyst layer of the cathode mentioned above can be selected as a material for the reverse current absorbing layer. Examples of it include nickel and iron. (Collector)

[001508] The cathodic chamber 20 preferably comprises the collector

23. Collector 23 improves the efficiency of the current collection. In the present embodiment, the collector 23 is a porous plate and is preferably arranged substantially parallel to the surface of the cathode 21.

[001509] The collector 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. Collector 23 can be a mixture, alloy or composite oxide of these metals. The collector 23 can have any shape, as long as the shape allows the function of the collector and can have a plate or network shape. (Elastic metal body)

[001510] Placing the elastic metal body 22 between the collector 23 and the cathode 21 presses each cathode 21 of the plurality of electrolytic cells 1 connected in series to the ion exchange membrane 2 to reduce the distance between each anode 11 and each cathode 21. Then, it is possible to reduce the voltage to be applied entirely through the plurality of electrolytic cells 1 connected in series. Reducing the voltage reduces energy consumption. With the elastic metal body 22 in place, the pressure caused by the elastic metal body 22 allows the electrolysis electrode to be held steadily in place when the laminate including the electrolysis electrode in the present embodiment is placed in the electrolytic cell.

[001511] Like the elastic metal body 22, can be used

398/803 spring members such as spiral springs and damping coils and mats. As the elastic metal body 22, a suitable one can be used appropriately, taking into account a tension to pressure the ion exchange membrane and the like. The elastic metal body 22 can be provided on the surface of the collector 23 on the side of the cathode chamber 20 or it can be provided on the surface of the partition wall on the side of the anode chamber 10. Both chambers are normally divided in such a way that the cathode chamber 20 it becomes smaller than the anodic chamber 10. Thus, from the point of view of the strength of the frame and the like, the elastic metal body 22 is preferably provided between the collector 23 and the cathode 21 in the anodic chamber

20. The elastic metal body 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. (Support)

[001512] The cathodic chamber 20 preferably comprises the support 24 that electrically connects the collector 23 to the partition wall 30. This can achieve an efficient current flow.

[001513] The support 24 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. The support 24 can have any shape as long as the support can support the collector 23 and can have a rod, plate or network shape. The support 24 has a plate shape, for example. A plurality of supports 24 is arranged between the partition wall 30 and the collector 23. The plurality of supports 24 are aligned in such a way that their surfaces are in parallel with each other. The supports 24 are arranged substantially perpendicular to the partition wall 30 and the collector 23. (Gasket on the anode side and gasket on the cathode side)

[001514] The anode-side gasket is preferably arranged on the surface of the structure that constitutes the anodic chamber 10. The cathode-side gasket is preferably arranged on the surface of the structure that constitutes the

399/803 cathodic chamber 20. The electrolytic cells are connected to each other in such a way that the anode-side gasket included in an electrolytic cell and the cathode-side gasket of an electrolytic cell adjacent to the cell sandwich the ion exchange membrane 2 (see Figure 104). These gaskets can make the connection points airtight when the plurality of electrolytic cells 1 is connected in series through the ion exchange membrane 2.

[001515] The gaskets form a seal between the ion exchange membrane and the electrolytic cells. Specific examples of gaskets include picture frame rubber sheets, in the center of which a hole portion is formed. Gaskets are required to be resistant to corrosive electrolyte solutions or gas produced and to be usable for a long period. Thus, with regard to chemical resistance and hardness, vulcanized products and products cross-linked with ethylene-propylene-diene rubber peroxide (EPDM rubber) and ethylene-propylene rubber (EPM rubber) are normally used as gaskets. Alternatively, gaskets from which the region to be in contact with liquid (liquid contact portion) with a fluorine-containing resin such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers can be used as needed. Such gaskets may have an orifice portion so as not to inhibit the flow of the electrolyte solution, and the shape of the orifice portion is not particularly limited. For example, a picture frame gasket is affixed with an adhesive or similar along the peripheral edge of each hole portion of the anodic chamber frame that constitutes the anodic chamber 10 or the cathodic chamber frame that constitutes the cathodic chamber 20. So, for example, in the case where the two electrolytic cells 1 are connected through the ion exchange membrane 2 (see Figure 104), each electrolytic cell 1 to which the gasket is attached must be tightened via the ion exchange membrane 2. This tightening can prevent the

400/803 electrolytic solution, alkali metal hydroxide, chlorine gas, hydrogen gas and the like, generated from electrolysis, escape from electrolytic cells 1. [Laminate]

[001516] The electrode for electrolysis in the present modality is used as a laminate of a membrane, such as an ion exchange membrane or a microporous membrane. That is, the laminate in the present modality comprises the electrode for electrolysis and a new membrane. The new membrane is not particularly limited as long as it is separated from the membrane in the existing electrolyzer, and several known "membranes" can be used. The material, shape, physical and similar properties of the new membrane may be similar to those of the membrane in the existing electrolyzer. Specific examples of the electrolysis electrode and the membrane will be detailed below. (Step (A)

[001517] In step (A) of the present modality, the electrolyte electrode and a new membrane are integrated at a temperature at which the membrane does not melt to obtain a laminate.

[001518] The "temperature at which the membrane does not melt" can be identified as the softening point of the new membrane. The temperature may vary depending on the material constituting the membrane, but it is preferably 0 to 100 ° C, more preferably 5 to 80 ° C, even more preferably 10 to 50 ° C.

[001519] The integration described above is preferably performed under normal pressure.

[001520] As a specific method for the above integration, which is not particularly limited, all types of methods, with the exception of typical methods for membrane fusion, such as thermal compression, can be used. A preferable example is a method in which a liquid is

401/803 interposed between an electrolysis electrode mentioned below and the membrane and the surface tension of the liquid is used to integrate the electrode and the “membrane”. [Step (B)]

[001521] In step (B) in the present modality, the membrane in the existing electrolyser is replaced by a laminate after step (A). The substitution method is not particularly limited, and examples of it include a method in which, first in the existing electrolyzer, a fixed state of the adjacent electrolytic cell and ion exchange membrane is released by means of a pressure device to provide an interstice between the electrolytic cell and the ion exchange membrane, then the existing ion exchange membrane to be renewed is removed, then a laminate is inserted into the interstice, and the members are re-coupled by means of the pressure device. Through the method, a laminate can be arranged on the surface of the anode or cathode of the existing electrolyzer, and the characteristics of the ion exchange membrane and the anode and / or cathode can be renewed. [Electrode for electrolysis]

[001522] In the present embodiment, the electrode for electrolysis is not particularly limited as long as the electrode can be integrated with a new membrane as mentioned above, that is, that it is integrable. The electrolysis electrode can be an electrode that serves as a cathode in the electrolyzer or it can be an electrode that serves as an anode. As the material, shape and similar of the electrolyte for electrolysis, the appropriate ones can be appropriately selected, considering the steps (A) and (B) in the present modality, the configuration of the electrolyzer, and the like. In the following, preferable aspects of the electrolysis electrode in the present modality will be described, but these are merely preferable exemplary aspects for integration with a new membrane. Electrodes for

402/803 electrolysis, in addition to the aspects mentioned below, can be properly used.

[001523] The electrolyte for electrolysis in the present embodiment has a force applied per unit mass-unit area of preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mg: in?), even more preferably less than 1.5 N / (mg: cm?), even more preferably 1.2 N / mg-cm? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a supply conductor (a degraded electrode and an uncoated electrode) catalyst) and the like. Is the applied force even more preferably 1.1 N / mg-cm? or less, even more preferably 1.10 N / mge? or less, particularly preferably 1.0 N / m? or less, especially preferably 1.00 N / mg-cm? or less.

[001524] From the point of view of further improving electrolytic performance, the strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: in?) Or more, even more preferably 0.1 N / mg: cm? or more, even more preferably 0.14 N / (mg: cm?) or more. By force it is even more preferably 0.2 N / (mg: cm?) Or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 m x 2.5 m).

[001525] The applied force described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness, arithmetic mean surface roughness and the like, for example. More specifically, for example, a higher opening ratio tends to lead to a lower applied force, and a lower opening ratio tends to lead to a higher applied force.

[001526] Is the mass per unit preferably 48 mg / cm? or less,

403/803 more preferably 30 mg / cm? or less, even more preferably 20 mg / cm? or less from the point of view of allowing a good manipulation property, having a good adhesive force for a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a conductive conductor without catalyst coating, and economy , and in addition it is preferably 15 mg / hundred? or less from a comprehensive point of view including handling, grip and economy properties. The lower limit value is not particularly limited, but is in the order of 1 mg / hundred?, For example.

[001527] The mass per unit area described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness and the like, for example. More specifically, for example, when the thickness is constant, a larger opening ratio tends to lead to a smaller mass per unit area, and a smaller opening ratio tends to lead to a mass per unit area greater.

[001528] The applied force can be measured by the methods (1) or (11) described below, which are as detailed in the Examples. As for the applied force, the value obtained by measuring the method (1) (also called “the applied force (1)”) and the value obtained by measuring the method (ii) (also called “the applied force (2) ”) Can be the same or different, and any of the values is preferably less than 1.5 N / (mg: -ecm?). [Method (i)]

[001529] A nickel plate obtained by stripping processing with 320 grain size alumina (1.2 mm thickness, 200 square mm), an ion exchange membrane that is obtained by applying particles of inorganic material and a binder on both surfaces of a perfluorocarbon polymer membrane into which an ion exchange group is introduced (170 square mm, the detail of the ion exchange membrane referred to here is as described in the Examples) and a sample of

404/803 electrodes (130 square mm) are rolled in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. The arithmetic mean roughness of the surface (Ra) of the nickel plate after blasting treatment is 0.5 to 0.8 µm. The specific method for calculating the arithmetic mean surface roughness (Ra) is as described in the Examples.

[001530] Under temperature conditions of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the charge when the electrode sample is raised by 10 mm in a vertical direction is measured. This measurement is repeated three times and the average value is calculated.

[001531] This average value is divided by the area of the overlapping portion of the electrode sample and the ion exchange membrane and the mass of the portion that overlaps the ion exchange membrane in the electrode sample to calculate the force applied per unit of mass- area unit (1) (N / mg-ecm?).

[001532] The force applied per unit mass-unit area (1) obtained by method (i) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: in? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg-in? or less. The force is

405/803 preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg: cm?) Or more of the point view of further improving electrolytic performance, and furthermore, it is even more preferably 0.14 N / (mgcm?), even more preferably 0.2 N / (mg: cm?) or more from the point of view of facilitating further manipulation in a large size (for example, a size of 1.5 mx2.5 Mm). [Method (ii)]

[001533] A nickel plate obtained by stripping processing with grain size 320 alumina (1.2 mm thickness, 200 mm square, a nickel plate similar to the method (1) above) and an electrode sample ( 130 mm square) is laminated in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the load when the electrode sample is raised by 10 mm in a vertical direction it is measured. This measurement is repeated three times and the average value is calculated.

[001534] This average value is divided by the area of the overlapping portion of the electrode sample and the nickel plate and the mass of the electrode sample in the portion that overlaps the nickel plate to calculate the adhesive force per unit mass-unit of area (2) (N / mg: -cm?).

[001535] The force applied per unit mass-unit area (2) obtained by method (ii) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of

406/803 seen to allow a good handling property to be provided and to have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg: cm? or less. In addition, the strength is preferably greater than 0.005 N / (mg: cm?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg-in?) Or more from the point of view of further improving electrolytic performance, and it is even more preferably 0.14 N / (mg: cm?) or more from the point of view of further facilitating handling in a large size (for example, a 1.5 m x 2.5 m).

[001536] The electrolyte electrode in the present embodiment preferably includes an electrode electrode substrate and a catalyst layer. The substrate thickness for the electrolysis electrode (gauge thickness) is, but is not particularly limited to, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less , even more preferably 125 µm or less, even more preferably 120 µm or less, even more preferably 100 µm or less from the point of view of enabling a good handling property to be provided, having a good adhesive strength to a membrane, such as a ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, be able to be properly laminated on a roll and folded satisfactorily, facilitating handling in one size large (for example, a size of 1.5 mx 2.5 Mm), and is even more preferably 50 µm or less from the point of view of

407/803 a property of manipulation and economy. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001537] In the present modality, in order to integrate a new membrane and electrode for electrolysis, a liquid is preferably interposed between them. Like the liquid, any liquid, such as water and organic solvents, can be used as long as the liquid generates a surface tension. The higher the surface tension of the liquid, the greater the force applied between the new membrane and the electrolysis electrode. Thus, a liquid with a higher surface tension is preferred. Examples of the liquid include the following (the numerical value in parentheses is the surface tension of the liquid at 20ºC): hexane (20.44 mN / m), acetone (23.30 mN / m), methanol (24.00 mN / m ), ethanol (24.05 mN / m), ethylene glycol (50.21 mN / m) and water (72.76 mN / m).

[001538] A liquid with a high surface tension allows the new membrane and electrode for electrolysis to be integrated (to be a laminate), and the renewal of the electrode tends to be easier. The liquid between the new membrane and the electrolysis electrode may be present in an amount such that both adhere to each other by surface tension. As a result, after the laminate is placed in an electrolytic cell, the liquid, if mixed in the electrolytic solution, does not affect the electrolysis itself due to the small amount of the liquid.

[001539] From a practical point of view, a liquid with a surface tension of 24 mN / m to 80 mN / m, such as ethanol, ethylene glycol and water, is preferably used as the liquid. Particularly preferred is water or an aqueous alkaline solution prepared by dissolving caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate or

407/803 a property of manipulation and economy. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001537] In the present modality, in order to integrate a new membrane and electrode for electrolysis, a liquid is preferably interposed between them. Like the liquid, any liquid, such as water and organic solvents, can be used as long as the liquid generates a surface tension. The higher the surface tension of the liquid, the greater the force applied between the new membrane and the electrolysis electrode. Thus, a liquid with a higher surface tension is preferred. Examples of the liquid include the following (the numerical value in parentheses is the surface tension of the liquid at 20ºC): hexane (20.44 mN / m), acetone (23.30 mN / m), methanol (24.00 mN / m ), ethanol (24.05 mN / m), ethylene glycol (50.21 mN / m) and water (72.76 mN / m).

[001538] A liquid with a high surface tension allows the new membrane and electrode for electrolysis to be integrated (to be a laminate), and the renewal of the electrode tends to be easier. The liquid between the new membrane and the electrolysis electrode may be present in an amount such that both adhere to each other by surface tension. As a result, after the laminate is placed in an electrolytic cell, the liquid, if mixed in the electrolytic solution, does not affect the electrolysis itself due to the small amount of the liquid.

[001539] From a practical point of view, a liquid with a surface tension of 24 mN / m to 80 mN / m, such as ethanol, ethylene glycol and water, is preferably used as the liquid. Particularly preferred is water or an aqueous alkaline solution prepared by dissolving caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate or

408/803 similar in water. Alternatively, the surface tension can be adjusted by allowing these liquids to contain a surfactant. When a surfactant is contained, the adhesion between the new membrane and the electrolysis electrode varies to allow the handling property to be adjusted. The surfactant is not particularly limited and ionic and non-ionic surfactants can be used.

[001540] The proportion measured by the following method (2) of the electrode for electrolysis in the present embodiment is not particularly limited, but is preferably 90% or more, more preferably 92% or more from the point of view of allowing a good handling property is provided and has a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and more preferably 95% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (2)]

[001541] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 280 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001542] The proportion measured by the following method (3) of the electrode for

408/803 similar in water. Alternatively, the surface tension can be adjusted by allowing these liquids to contain a surfactant. When a surfactant is contained, the adhesion between the new membrane and the electrolysis electrode varies to allow the handling property to be adjusted. The surfactant is not particularly limited and ionic and non-ionic surfactants can be used.

[001540] The proportion measured by the following method (2) of the electrode for electrolysis in the present embodiment is not particularly limited, but is preferably 90% or more, more preferably 92% or more from the point of view of allowing a good handling property is provided and has a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and more preferably 95% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (2)]

[001541] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 280 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001542] The proportion measured by the following method (3) of the electrode for

409/803 electrolysis in the present embodiment is not particularly limited, but is preferably 75% or more, more preferably 80% or more from the point of view of allowing a good handling property to be provided, having a good adhesive strength to such a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating and can be properly rolled onto a roll and satisfactorily folded, and is most preferably 90% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (3)]

[001543] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 145 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001544] The electrolysis electrode in the present embodiment preferably has, but is not particularly limited to, a porous structure and an aperture ratio or void ratio of 5 to 90% or less from the point of view of enabling a good handling property, have good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and

409/803 electrolysis in the present embodiment is not particularly limited, but is preferably 75% or more, more preferably 80% or more from the point of view of allowing a good handling property to be provided, having a good adhesive strength to such a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating and can be properly rolled onto a roll and satisfactorily folded, and is most preferably 90% or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx 2.5 m). The upper limit value is 100%. [Method (3)]

[001543] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 145 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001544] The electrolysis electrode in the present embodiment preferably has, but is not particularly limited to, a porous structure and an aperture ratio or void ratio of 5 to 90% or less from the point of view of enabling a good handling property, have good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and

410/803 prevent the accumulation of gas from being generated during electrolysis. The opening ratio is more preferably 10 to 80% or less, more preferably 20 to 75%.

[001545] The opening ratio is a proportion of the opening portions per unit volume. The calculation method may differ depending on whether the opening portions in submicron size are considered or that only visible openings are considered. In the present embodiment, a volume V is calculated from the values of the thickness of the gauge, width and length of the electrode and, in addition, a weight W is measured to thereby allow an aperture ratio A to be calculated by the following formula.

A = (1- (W / (YV xp)) x 100

[001546] p is the density of the electrode material (g / cm?). For example, nickel p is 8.908 g / em ”, and titanium p is 4.506 g / em ?. The opening ratio can be appropriately adjusted by changing the area of metal to be drilled per unit area in the case of perforated metal, changing the SW (short diameter), LW (long diameter) and feed values in the case of expanded metal, changing the metal fiber line diameter and mesh number in the case of mesh, changing the pattern of a photoresist to be used in the case of electroforming, changing the diameter of the metal fiber and fiber density in the case of non-woven fabric, changing the mold to form voids in the case of foamed metal or similar.

[001547] From now on, a more specific modality of the electrode for electrolysis will be described in the present modality.

[001548] The electrolysis electrode according to the present embodiment preferably includes a substrate for electrolysis electrode and a layer of catalyst. The catalyst layer can be composed of a plurality of layers, as shown below, or it can be a single layer configuration.

410/803 prevent the accumulation of gas from being generated during electrolysis. The opening ratio is more preferably 10 to 80% or less, more preferably 20 to 75%.

[001545] The opening ratio is a proportion of the opening portions per unit volume. The calculation method may differ depending on whether the opening portions in submicron size are considered or that only visible openings are considered. In the present embodiment, a volume V is calculated from the values of the thickness of the gauge, width and length of the electrode and, in addition, a weight W is measured to thereby allow an aperture ratio A to be calculated by the following formula.

A = (1- (W / (YV xp)) x 100

[001546] p is the density of the electrode material (g / cm?). For example, nickel p is 8.908 g / em ”, and titanium p is 4.506 g / em ?. The opening ratio can be appropriately adjusted by changing the area of metal to be drilled per unit area in the case of perforated metal, changing the SW (short diameter), LW (long diameter) and feed values in the case of expanded metal, changing the metal fiber line diameter and mesh number in the case of mesh, changing the pattern of a photoresist to be used in the case of electroforming, changing the diameter of the metal fiber and fiber density in the case of non-woven fabric, changing the mold to form voids in the case of foamed metal or similar.

[001547] From now on, a more specific modality of the electrode for electrolysis will be described in the present modality.

[001548] The electrolysis electrode according to the present embodiment preferably includes a substrate for electrolysis electrode and a layer of catalyst. The catalyst layer can be composed of a plurality of layers, as shown below, or it can be a single layer configuration.

411/803

[001549] As shown in Figure 108, an electrolysis electrode 100 according to the present embodiment includes an electrode substrate for electrolysis 10 and a pair of first layers 20 with which both surfaces of the electrode substrate for electrolysis 10 are covered. . The entire electrolyte electrode substrate 10 is preferably covered with the first 20 layers. This coating is likely to improve the activity of the catalyst and the durability of the electrolysis electrode. A first layer 20 can be laminated only on one surface of the electrode substrate for electrolysis 10.

[001550] Also as shown in Figure 108, the surfaces of the first layers 20 can be covered with the second layers 30. The first entire layers 20 are preferably covered by the second layers 30. Alternatively, a second layer 30 can be laminated to only one surface of the first layer 20. (Electrode substrate for electrolysis)

[001551] As an electrode substrate for electrolysis 10, for example, nickel, nickel alloys, stainless steel or valve metals including titanium can be used, although not limited to them. The substrate 10 preferably contains at least one element selected from nickel (Ni) and titanium (Ti).

[001552] When stainless steel is used in an aqueous alkaline solution of high concentration, iron and chromium are eluted and the electrical conductivity of stainless steel is about one tenth that of nickel. In view of the above, a substrate containing nickel (Ni) is preferable as a substrate for the electrolysis electrode.

[001553] Alternatively, when the electrode substrate for electrolysis 10 is used in a high concentration saline solution close to saturation under an atmosphere in which chlorine gas is generated, the substrate material for electrode 10 is also preferably titanium with high

411/803

[001549] As shown in Figure 108, an electrolysis electrode 100 according to the present embodiment includes an electrode substrate for electrolysis 10 and a pair of first layers 20 with which both surfaces of the electrode substrate for electrolysis 10 are covered. . The entire electrolyte electrode substrate 10 is preferably covered with the first 20 layers. This coating is likely to improve the activity of the catalyst and the durability of the electrolysis electrode. A first layer 20 can be laminated only on one surface of the electrode substrate for electrolysis 10.

[001550] Also as shown in Figure 108, the surfaces of the first layers 20 can be covered with the second layers 30. The first entire layers 20 are preferably covered by the second layers 30. Alternatively, a second layer 30 can be laminated to only one surface of the first layer 20. (Electrode substrate for electrolysis)

[001551] As an electrode substrate for electrolysis 10, for example, nickel, nickel alloys, stainless steel or valve metals including titanium can be used, although not limited to them. The substrate 10 preferably contains at least one element selected from nickel (Ni) and titanium (Ti).

[001552] When stainless steel is used in an aqueous alkaline solution of high concentration, iron and chromium are eluted and the electrical conductivity of stainless steel is about one tenth that of nickel. In view of the above, a substrate containing nickel (Ni) is preferable as a substrate for the electrolysis electrode.

[001553] Alternatively, when the electrode substrate for electrolysis 10 is used in a high concentration saline solution close to saturation under an atmosphere in which chlorine gas is generated, the substrate material for electrode 10 is also preferably titanium with high

412/803 corrosion resistance.

[001554] The shape of the electrode substrate for electrolysis 10 is not particularly limited, and a shape suitable for the purpose can be selected. As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. Among these, a perforated metal or expanded metal is preferable. Electroforming is a technique for producing a thin metal film with a precise pattern using photolithography and electroplating in combination. It is a method that includes the formation of a pattern on a substrate with a photoresist and electroplating of the portion not protected by the resistance to provide a thin metal film.

[001555] Regarding the shape of the substrate for the electrolysis electrode, an appropriate specification depends on the distance between the anode and the cathode in the electrolyzer. In the case where the distance between the anode and the cathode is finite, a form of expanded metal or perforated metal can be used, and in the case of a so-called zero-interstitial electrolyzer, in which the ion exchange membrane is in contact with the electrode, a woven mesh produced by fine knitted threads, wire mesh, foamy metal, non-woven metallic fabric, expanded metal, perforated metal, porous metal foil and the like can be used, although not limited to it.

[001556] Examples of the electrode substrate for electrolysis 10 include a porous metal foil, a wire mesh, a nonwoven metal fabric, a perforated metal, an expanded metal and a foamy metal.

[001557] As plate material before being processed into a perforated metal or expanded metal, laminated plate materials and electrolytic sheets are preferred. An electrolytic sheet is preferably still subjected to a galvanizing treatment using the same element as its base material, such as after-treatment, to thereby form

412/803 corrosion resistance.

[001554] The shape of the electrode substrate for electrolysis 10 is not particularly limited, and a shape suitable for the purpose can be selected. As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. Among these, a perforated metal or expanded metal is preferable. Electroforming is a technique for producing a thin metal film with a precise pattern using photolithography and electroplating in combination. It is a method that includes the formation of a pattern on a substrate with a photoresist and electroplating of the portion not protected by the resistance to provide a thin metal film.

[001555] Regarding the shape of the substrate for the electrolysis electrode, an appropriate specification depends on the distance between the anode and the cathode in the electrolyzer. In the case where the distance between the anode and the cathode is finite, a form of expanded metal or perforated metal can be used, and in the case of a so-called zero-interstitial electrolyzer, in which the ion exchange membrane is in contact with the electrode, a woven mesh produced by fine knitted threads, wire mesh, foamy metal, non-woven metallic fabric, expanded metal, perforated metal, porous metal foil and the like can be used, although not limited to it.

[001556] Examples of the electrode substrate for electrolysis 10 include a porous metal foil, a wire mesh, a nonwoven metal fabric, a perforated metal, an expanded metal and a foamy metal.

[001557] As plate material before being processed into a perforated metal or expanded metal, laminated plate materials and electrolytic sheets are preferred. An electrolytic sheet is preferably still subjected to a galvanizing treatment using the same element as its base material, such as after-treatment, to thereby form

413/803 roughness and one or both surfaces.

[001558] The thickness of the electrode substrate for electrolysis 10 is, as mentioned above, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less, even more preferably 125 one or less, even more preferably 120 µm or less, even more preferably 100 µm or less, and even more preferably 50 µm or less from the point of view of a handling and economical property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001559] In the electrode substrate for electrolysis, the residual stress during processing is preferably relaxed by annealing the electrode substrate for electrolysis in an oxidizing atmosphere. It is preferable to form roughness using a steel grid, alumina powder or similar on the surface of the electrode substrate for electrolysis followed by an acid treatment to increase the surface area of the electrode, in order to improve the adhesion to a catalyst layer with which the surface is covered. Alternatively, it is preferable to give a galvanizing treatment using the same element as the substrate to increase the surface area.

[001560] In order to place the first layer 20 in close contact with the electrode electrode substrate surface 10, the electrode electrode substrate 10 is preferably subjected to a treatment to increase the surface area. Examples of the treatment of increasing the surface area include a pickling treatment using a cut wire, steel grid, alumina grid or similar, an acid treatment using sulfuric acid or hydrochloric acid, and a galvanizing treatment using the same element as the of the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 µm to 50 µm, more preferably 0.1 to 10 µm, still

413/803 roughness and one or both surfaces.

[001558] The thickness of the electrode substrate for electrolysis 10 is, as mentioned above, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less, even more preferably 125 one or less, even more preferably 120 µm or less, even more preferably 100 µm or less, and even more preferably 50 µm or less from the point of view of a handling and economical property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001559] In the electrode substrate for electrolysis, the residual stress during processing is preferably relaxed by annealing the electrode substrate for electrolysis in an oxidizing atmosphere. It is preferable to form roughness using a steel grid, alumina powder or similar on the surface of the electrode substrate for electrolysis followed by an acid treatment to increase the surface area of the electrode, in order to improve the adhesion to a catalyst layer with which the surface is covered. Alternatively, it is preferable to give a galvanizing treatment using the same element as the substrate to increase the surface area.

[001560] In order to place the first layer 20 in close contact with the electrode electrode substrate surface 10, the electrode electrode substrate 10 is preferably subjected to a treatment to increase the surface area. Examples of the treatment of increasing the surface area include a pickling treatment using a cut wire, steel grid, alumina grid or similar, an acid treatment using sulfuric acid or hydrochloric acid, and a galvanizing treatment using the same element as the of the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 µm to 50 µm, more preferably 0.1 to 10 µm, still

414/803 more preferably 0.1 to 8 µm.

[001561] Next, a case will be described in which the electrode for electrolysis in the present modality is used as an anode for electrolysis of common salt. (First layer)

[001562] In Figure 108, a first layer 20 as a catalyst layer contains at least one of the ruthenium oxides, iridium oxides and titanium oxides. Examples of ruthenium oxide include RuO; Examples of iridium oxide include IrO ,. Examples of titanium oxide include TiO,; The first layer 20 preferably contains two oxides: a ruthenium oxide and a titanium oxide or three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide. This makes the first layer 20 more stable and further improves adhesion with the second layer 30.

[001563] When the first layer 20 contains two oxides: a ruthenium oxide and a titanium oxide, the first layer 20 preferably contains 1 to 9 mol, more preferably 1 to 4 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition ratio of the two oxides in this range, the electrode for electrolysis 100 has excellent durability.

[001564] When the first layer 20 contains three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide, the first layer 20 preferably contains 0.2 to 3 mol, more preferably 0.3 to 2.5 mol of iridium oxide based on 1 mol of ruthenium oxide contained in the first layer 20. The first layer 20 preferably contains 0.3 to 8 mol, more preferably 1 to 7 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition of the three oxides in this range, the electrode for electrolysis 100 has excellent durability.

[001565] When the first layer 20 contains at least two of a

414/803 more preferably 0.1 to 8 µm.

[001561] Next, a case will be described in which the electrode for electrolysis in the present modality is used as an anode for electrolysis of common salt. (First layer)

[001562] In Figure 108, a first layer 20 as a catalyst layer contains at least one of the ruthenium oxides, iridium oxides and titanium oxides. Examples of ruthenium oxide include RuO; Examples of iridium oxide include IrO ,. Examples of titanium oxide include TiO,; The first layer 20 preferably contains two oxides: a ruthenium oxide and a titanium oxide or three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide. This makes the first layer 20 more stable and further improves adhesion with the second layer 30.

[001563] When the first layer 20 contains two oxides: a ruthenium oxide and a titanium oxide, the first layer 20 preferably contains 1 to 9 mol, more preferably 1 to 4 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition ratio of the two oxides in this range, the electrode for electrolysis 100 has excellent durability.

[001564] When the first layer 20 contains three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide, the first layer 20 preferably contains 0.2 to 3 mol, more preferably 0.3 to 2.5 mol of iridium oxide based on 1 mol of ruthenium oxide contained in the first layer 20. The first layer 20 preferably contains 0.3 to 8 mol, more preferably 1 to 7 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition of the three oxides in this range, the electrode for electrolysis 100 has excellent durability.

[001565] When the first layer 20 contains at least two of a

415/803 ruthenium oxide, an iridium oxide and a titanium oxide, these oxides preferably form a solid solution. The formation of the solid oxide solution allows the electrolysis electrode 100 to have excellent durability.

[001566] In addition to the compositions described above, oxides of various compositions can be used provided that at least one oxide of a ruthenium oxide, an iridium oxide and titanium oxide is contained. For example, an oxide coating called DSA (R), which contains ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum and the like, can be used as a first layer 20.

[001567] The first layer 20 does not have to be a single layer and can include a plurality of layers. For example, the first layer 20 can include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 µm, more preferably 0.1 to 8 µm. (Second layer)

[001568] The second layer 30 preferably contains ruthenium and titanium. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001569] The second layer 30 preferably contains a palladium oxide, a solid solution of a palladium and platinum oxide, or an alloy of palladium and platinum. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001570] A second thicker layer 30 can maintain electrolytic performance for a longer period, but from an economic point of view, the thickness is preferably 0.05 to 3 µm.

[001571] Next, a case will be described in which the electrode for electrolysis in the present modality is used as a cathode for electrolysis of common salt.

415/803 ruthenium oxide, an iridium oxide and a titanium oxide, these oxides preferably form a solid solution. The formation of the solid oxide solution allows the electrolysis electrode 100 to have excellent durability.

[001566] In addition to the compositions described above, oxides of various compositions can be used provided that at least one oxide of a ruthenium oxide, an iridium oxide and titanium oxide is contained. For example, an oxide coating called DSA (R), which contains ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum and the like, can be used as a first layer 20.

[001567] The first layer 20 does not have to be a single layer and can include a plurality of layers. For example, the first layer 20 can include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 µm, more preferably 0.1 to 8 µm. (Second layer)

[001568] The second layer 30 preferably contains ruthenium and titanium. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001569] The second layer 30 preferably contains a palladium oxide, a solid solution of a palladium and platinum oxide, or an alloy of palladium and platinum. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001570] A second thicker layer 30 can maintain electrolytic performance for a longer period, but from an economic point of view, the thickness is preferably 0.05 to 3 µm.

[001571] Next, a case will be described in which the electrode for electrolysis in the present modality is used as a cathode for electrolysis of common salt.

416/803 (First layer)

[001572] Examples of components of the first layer 20 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[001573] The first layer 20 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal.

[001574] When the first layer 20 contains at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides, and alloys containing a platinum group metal, the metals of the platinum group platinum, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal preferably contain at least one platinum group metal of platinum, palladium, rhodium, ruthenium and iridium.

[001575] Like the platinum group metal, platinum is preferably contained.

[001576] Like the metal oxide of the platinum group, a ruthenium oxide is preferably contained.

[001577] Like the metal hydroxide of the platinum group, a ruthenium hydroxide is preferably contained.

[001578] Like the platinum group metal alloy, a platinum alloy with nickel, iron and cobalt is preferably contained.

[001579] In addition, as needed, an oxide or hydroxide of a lanthanide element is preferably contained as a second component. This allows the electrolysis electrode 100 to have excellent durability.

[001580] Like the oxide or hydroxide of a lanthanide element, at least

416/803 (First layer)

[001572] Examples of components of the first layer 20 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[001573] The first layer 20 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal.

[001574] When the first layer 20 contains at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides, and alloys containing a platinum group metal, the metals of the platinum group platinum, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal preferably contain at least one platinum group metal of platinum, palladium, rhodium, ruthenium and iridium.

[001575] Like the platinum group metal, platinum is preferably contained.

[001576] Like the metal oxide of the platinum group, a ruthenium oxide is preferably contained.

[001577] Like the metal hydroxide of the platinum group, a ruthenium hydroxide is preferably contained.

[001578] Like the platinum group metal alloy, a platinum alloy with nickel, iron and cobalt is preferably contained.

[001579] In addition, as needed, an oxide or hydroxide of a lanthanide element is preferably contained as a second component. This allows the electrolysis electrode 100 to have excellent durability.

[001580] Like the oxide or hydroxide of a lanthanide element, at least

417/803 minus one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium and dysprosium is preferably contained.

[001581] Furthermore, as needed, an oxide or hydroxide of a transition metal is preferably contained as a third component.

[001582] The addition of the third component allows the electrolysis electrode 100 to have greater durability and the electrolysis voltage to be reduced.

[001583] Examples of a preferable combination include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + Platinum + Palladium, Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + cobalt, ruthenium + samarium + zinc, ruthenium + samarium + gallium, ruthenium + samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + nickel uel + palladium, platinum + nickel + ruthenium, platinum and nickel alloys, platinum and cobalt alloys, and platinum and iron alloys.

[001584] When platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal are not contained, the main component of the catalyst is preferably the nickel element.

[001585] At least one of the nickel metals, oxides and hydroxides is

417/803 minus one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium and dysprosium is preferably contained.

[001581] Furthermore, as needed, an oxide or hydroxide of a transition metal is preferably contained as a third component.

[001582] The addition of the third component allows the electrolysis electrode 100 to have greater durability and the electrolysis voltage to be reduced.

[001583] Examples of a preferable combination include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + Platinum + Palladium, Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + cobalt, ruthenium + samarium + zinc, ruthenium + samarium + gallium, ruthenium + samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + nickel uel + palladium, platinum + nickel + ruthenium, platinum and nickel alloys, platinum and cobalt alloys, and platinum and iron alloys.

[001584] When platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal are not contained, the main component of the catalyst is preferably the nickel element.

[001585] At least one of the nickel metals, oxides and hydroxides is

418/803 preferably contained.

[001586] As the second component, a transition metal can be added. As the second component to be added, at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper and carbon is preferably contained.

[001587] Examples of a preferable combination include nickel + tin, nickel + titanium, nickel + molybdenum and nickel + cobalt.

[001588] As required, an intermediate layer can be placed between the first layer 20 and the electrode substrate for electrolysis

10. The durability of the electrolysis electrode 100 can be improved by placing the intermediate layer.

[001589] As the intermediate layer, those with affinity for both the first layer 20 and the electrode substrate for electrolysis 10 are preferred. As the intermediate layer, nickel oxides, platinum group metals, metal oxides are preferable of the platinum group and metal hydroxides of the platinum group. The intermediate layer can be formed by applying and cooking a solution containing a component that forms the intermediate layer. Alternatively, a surface oxide layer can also be formed by subjecting a substrate to a heat treatment at a temperature of 300 to 600ºC in an air atmosphere. In addition, the layer can be formed by a known method, such as a thermal spray method and an ion galvanizing method. (Second layer)

[001590] Examples of components of the first layer 30 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Tn, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

418/803 preferably contained.

[001586] As the second component, a transition metal can be added. As the second component to be added, at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper and carbon is preferably contained.

[001587] Examples of a preferable combination include nickel + tin, nickel + titanium, nickel + molybdenum and nickel + cobalt.

[001588] As required, an intermediate layer can be placed between the first layer 20 and the electrode substrate for electrolysis

10. The durability of the electrolysis electrode 100 can be improved by placing the intermediate layer.

[001589] As the intermediate layer, those with affinity for both the first layer 20 and the electrode substrate for electrolysis 10 are preferred. As the intermediate layer, nickel oxides, platinum group metals, metal oxides are preferable of the platinum group and metal hydroxides of the platinum group. The intermediate layer can be formed by applying and cooking a solution containing a component that forms the intermediate layer. Alternatively, a surface oxide layer can also be formed by subjecting a substrate to a heat treatment at a temperature of 300 to 600ºC in an air atmosphere. In addition, the layer can be formed by a known method, such as a thermal spray method and an ion galvanizing method. (Second layer)

[001590] Examples of components of the first layer 30 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Tn, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

419/803

[001591] The first layer 30 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal. Examples of a preferable combination of elements contained in the second layer include the combinations listed for the first layer. The combination of the first layer and the second layer can be a combination in which the compositions are the same and the composition reasons are different or can be a combination of different compositions.

[001592] Like the thickness of the catalyst layer, the total thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 µm to 20 µm. With a thickness of 0.01 µm or more, the catalyst layer can sufficiently serve as the catalyst. With a thickness of 20 µm or less, it is possible to form a robust catalyst layer that is unlikely to fall off the substrate. The thickness is more preferably 0.05 µm to 15 µm. The thickness is more preferably 0.1 µm to 10 µm. The thickness is even more preferably 0.2 µm to 8 µm.

[001593] The thickness of the electrode, i.e. the total thickness of the electrode substrate for electrolysis and the catalyst layer is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, even more preferably 150 one or less, particularly - preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less with respect to the electrode handling property. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The limit value

419/803

[001591] The first layer 30 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal. Examples of a preferable combination of elements contained in the second layer include the combinations listed for the first layer. The combination of the first layer and the second layer can be a combination in which the compositions are the same and the composition reasons are different or can be a combination of different compositions.

[001592] Like the thickness of the catalyst layer, the total thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 µm to 20 µm. With a thickness of 0.01 µm or more, the catalyst layer can sufficiently serve as the catalyst. With a thickness of 20 µm or less, it is possible to form a robust catalyst layer that is unlikely to fall off the substrate. The thickness is more preferably 0.05 µm to 15 µm. The thickness is more preferably 0.1 µm to 10 µm. The thickness is even more preferably 0.2 µm to 8 µm.

[001593] The thickness of the electrode, i.e. the total thickness of the electrode substrate for electrolysis and the catalyst layer is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, even more preferably 150 one or less, particularly - preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less with respect to the electrode handling property. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The limit value

420/803 lower is not particularly limited, but it is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably one or more. The thickness of the electrode can be determined by measurement with a digital thickness gauge (Mitutoyo Corporation, minimum scale 0.001 mm). The thickness of the electrode substrate for electrolysis is measured in the same way as the thickness of the electrode. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.

[001594] In the present embodiment, the electrolysis electrode preferably contains at least one catalytic component selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B / C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy from the point of view of achieving sufficient electrolytic performance.

[001595] In the present modality, from the point of view that the electrolysis electrode, if it is an electrode with a wide region of elastic deformation, can provide a better handling property and has a better adhesive force to a membrane as an exchange membrane ionic and a microporous membrane, a degraded electrode, a feed conductor without any catalyst coating, and the like, the electrode thickness for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, still more preferably 150 µm or less, particularly preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more

420/803 lower is not particularly limited, but it is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably one or more. The thickness of the electrode can be determined by measurement with a digital thickness gauge (Mitutoyo Corporation, minimum scale 0.001 mm). The thickness of the electrode substrate for electrolysis is measured in the same way as the thickness of the electrode. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.

[001594] In the present embodiment, the electrolysis electrode preferably contains at least one catalytic component selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B / C, N, O, Si, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy from the point of view of achieving sufficient electrolytic performance.

[001595] In the present modality, from the point of view that the electrolysis electrode, if it is an electrode with a wide region of elastic deformation, can provide a better handling property and has a better adhesive force to a membrane as an exchange membrane ionic and a microporous membrane, a degraded electrode, a feed conductor without any catalyst coating, and the like, the electrode thickness for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, still more preferably 150 µm or less, particularly preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more

421/803 preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably 20 µm or more. In the present modality, “having a wide region of elastic deformation” means that when an electrolysis electrode is wound to form a wound body, it is unlikely that distortion derived from the winding will occur after the wound state is released. The thickness of the electrolysis electrode refers, when a catalyst layer mentioned below is included, to the total thickness of both the electrolysis electrode substrate and the catalyst layer. (Method to produce electrode for electrolysis)

[001596] Next, an embodiment of the method for producing the electrolysis electrode 100 will be described in detail.

[001597] In the present embodiment, the electrolysis electrode 100 can be produced by forming the first layer 20, preferably the second layer 30, on the electrode electrode substrate by a method such as cooking a coating film under an oxygen atmosphere ( pyrolysis) or ion galvanizing, galvanizing or thermal spraying. The production method of the present embodiment as mentioned can achieve a high productivity of the electrode for electrolysis 100. Specifically, a catalyst layer is formed on the electrode substrate for electrolysis by an application step to apply a coating liquid containing a catalyst, a drying step to dry the coating liquid and a pyrolysis step to perform pyrolysis. Pyrolysis here means that a metal salt that is to be a precursor is decomposed by heating into a metal or metal oxide and a gaseous substance. The decomposition product depends on the metal species to be used, the type of salt and the atmosphere under which pyrolysis is carried out, and many metals tend to form oxides in an oxidizing atmosphere. In an industrial process of production of a

421/803 preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably 20 µm or more. In the present modality, “having a wide region of elastic deformation” means that when an electrolysis electrode is wound to form a wound body, it is unlikely that distortion derived from the winding will occur after the wound state is released. The thickness of the electrolysis electrode refers, when a catalyst layer mentioned below is included, to the total thickness of both the electrolysis electrode substrate and the catalyst layer. (Method to produce electrode for electrolysis)

[001596] Next, an embodiment of the method for producing the electrolysis electrode 100 will be described in detail.

[001597] In the present embodiment, the electrolysis electrode 100 can be produced by forming the first layer 20, preferably the second layer 30, on the electrode electrode substrate by a method such as cooking a coating film under an oxygen atmosphere ( pyrolysis) or ion galvanizing, galvanizing or thermal spraying. The production method of the present embodiment as mentioned can achieve a high productivity of the electrode for electrolysis 100. Specifically, a catalyst layer is formed on the electrode substrate for electrolysis by an application step to apply a coating liquid containing a catalyst, a drying step to dry the coating liquid and a pyrolysis step to perform pyrolysis. Pyrolysis here means that a metal salt that is to be a precursor is decomposed by heating into a metal or metal oxide and a gaseous substance. The decomposition product depends on the metal species to be used, the type of salt and the atmosphere under which pyrolysis is carried out, and many metals tend to form oxides in an oxidizing atmosphere. In an industrial process of production of a

422/803 electrode, pyrolysis is generally carried out in air, and a metal oxide or metal hydroxide is formed in many cases. (Formation of the first anode layer) (Application stage)

[001598] The first layer 20 is obtained by applying a solution in which at least one metallic salt of ruthenium, iridium and titanium is dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the coating in the presence of oxygen. The ruthenium, iridium and titanium content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001599] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[001600] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a bathing method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method is preferred, which has excellent productivity

422/803 electrode, pyrolysis is generally carried out in air, and a metal oxide or metal hydroxide is formed in many cases. (Formation of the first anode layer) (Application stage)

[001598] The first layer 20 is obtained by applying a solution in which at least one metallic salt of ruthenium, iridium and titanium is dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the coating in the presence of oxygen. The ruthenium, iridium and titanium content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001599] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[001600] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a bathing method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method is preferred, which has excellent productivity

423/803 industrial. (Drying step and pyrolysis step)

[001601] After being applied to the electrode substrate for electrolysis 100, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolysed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001602] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the second layer)

[001603] The second layer 30, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second liquid of first layer 20 and then pyrolyzing the coating liquid in the presence of oxygen. (Formation of the first cathode layer by the pyrolysis method) (Application stage)

[001604] The first layer 20 is obtained by applying a solution in which metal salts of various combinations are dissolved (first coating liquid) in the electrode substrate for electrolysis and then

423/803 industrial. (Drying step and pyrolysis step)

[001601] After being applied to the electrode substrate for electrolysis 100, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolysed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001602] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the second layer)

[001603] The second layer 30, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second liquid of first layer 20 and then pyrolyzing the coating liquid in the presence of oxygen. (Formation of the first cathode layer by the pyrolysis method) (Application stage)

[001604] The first layer 20 is obtained by applying a solution in which metal salts of various combinations are dissolved (first coating liquid) in the electrode substrate for electrolysis and then

424/803 pyrolysis (cooking) of the coating liquid in the presence of oxygen. The metal content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001605] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[001606] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersion bathing of the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[001607] After being applied to the electrode substrate for electrolysis 10, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature

424/803 pyrolysis (cooking) of the coating liquid in the presence of oxygen. The metal content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001605] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[001606] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersion bathing of the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[001607] After being applied to the electrode substrate for electrolysis 10, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature

425/803 can be suitably selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001608] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the intermediate layer)

[001609] The intermediate layer, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound or a platinum compound (second coating liquid) to the substrate and then pyrolyzing the coating liquid in the presence of oxygen. Alternatively, an intermediate layer of nickel oxide can be formed on the surface of the substrate just by heating the substrate, without applying a solution on it. (Formation of the first cathode layer by ion galvanizing)

[001610] The first layer 20 can also be formed by ion plating.

[001611] An example includes a method in which the substrate is fixed in a chamber and the metal ruthenium target is irradiated with an electron beam. Evaporated metallic ruthenium particles are positively charged to the plasma in the chamber to deposit on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and deposits of ruthenium as ruthenium oxide in the substrate. (Formation of the first cathode layer by galvanizing)

[001612] The first layer 20 can also be formed by a

425/803 can be suitably selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001608] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the intermediate layer)

[001609] The intermediate layer, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound or a platinum compound (second coating liquid) to the substrate and then pyrolyzing the coating liquid in the presence of oxygen. Alternatively, an intermediate layer of nickel oxide can be formed on the surface of the substrate just by heating the substrate, without applying a solution on it. (Formation of the first cathode layer by ion galvanizing)

[001610] The first layer 20 can also be formed by ion plating.

[001611] An example includes a method in which the substrate is fixed in a chamber and the metal ruthenium target is irradiated with an electron beam. Evaporated metallic ruthenium particles are positively charged to the plasma in the chamber to deposit on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and deposits of ruthenium as ruthenium oxide in the substrate. (Formation of the first cathode layer by galvanizing)

[001612] The first layer 20 can also be formed by a

426/803 galvanizing method.

[001613] For example, when the substrate is used as a cathode and subjected to electrolytic galvanization in an electrolytic solution containing nickel and tin, nickel and tin alloy galvanization can be formed. (Formation of the first cathode layer by thermal spray)

[001614] The first layer 20 can also be formed by thermal spraying.

[001615] As an example, the nickel oxide particles sprayed by plasma on the substrate can form a catalyst layer in which the metal nickel and nickel oxide are mixed.

[001616] Hereinafter, an ion exchange membrane will be described in detail according to an aspect of the membrane. [Ion exchange membrane]

[001617] The ion exchange membrane is not particularly limited as long as the membrane can be laminated with the electrolysis electrode, and several ion exchange membranes can be used. In the present embodiment, an ion exchange membrane is preferably used which has a membrane body containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and a coating layer provided on at least one surface of the membrane body. It is preferable that the coating layer contains particles of inorganic material and a binder, and the specific surface area of the coating layer is 0.1 to 10 µm / g. The ion exchange membrane that has such a structure has a small influence of the gas generated during electrolysis on electrolytic performance and tends to exert stable electrolytic performance.

[001618] The membrane of a perfluorocarbon polymer into which an ion exchange group is introduced described above includes a layer of sulfonic acid with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called an “acid group

426/803 galvanizing method.

[001613] For example, when the substrate is used as a cathode and subjected to electrolytic galvanization in an electrolytic solution containing nickel and tin, nickel and tin alloy galvanization can be formed. (Formation of the first cathode layer by thermal spray)

[001614] The first layer 20 can also be formed by thermal spraying.

[001615] As an example, the nickel oxide particles sprayed by plasma on the substrate can form a catalyst layer in which the metal nickel and nickel oxide are mixed.

[001616] Hereinafter, an ion exchange membrane will be described in detail according to an aspect of the membrane. [Ion exchange membrane]

[001617] The ion exchange membrane is not particularly limited as long as the membrane can be laminated with the electrolysis electrode, and several ion exchange membranes can be used. In the present embodiment, an ion exchange membrane is preferably used which has a membrane body containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and a coating layer provided on at least one surface of the membrane body. It is preferable that the coating layer contains particles of inorganic material and a binder, and the specific surface area of the coating layer is 0.1 to 10 µm / g. The ion exchange membrane that has such a structure has a small influence of the gas generated during electrolysis on electrolytic performance and tends to exert stable electrolytic performance.

[001618] The membrane of a perfluorocarbon polymer into which an ion exchange group is introduced described above includes a layer of sulfonic acid with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called an “acid group

427/803 sulfonic ”) or a layer of carboxylic acid with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a“ carboxylic acid group ”). From the point of view of strength and dimensional stability, reinforcement core materials are preferably included.

[001619] The particles of inorganic material and binder will be described in detail in the coating layer description section below.

[001620] Figure 109 illustrates a schematic cross-sectional view showing an ion exchange membrane modality. An ion exchange membrane | it has a membrane body 10 containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and coating layers 11a and 11b formed on both surfaces of the membrane body 10.

[001621] In the ion exchange membrane 1, the membrane body 10 comprises a layer of sulfonic acid 3 with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called an “acid group sulfonic ”) and a layer of carboxylic acid 2 with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a“ carboxylic acid group ”), and the core materials of reinforcement 4 intensifies strength and dimensional stability. The ion exchange membrane 1, comprising the sulfonic acid layer 3 and the carboxylic acid layer 2, is suitably used as an anion exchange membrane.

[001622] The ion exchange membrane can include the sulfonic acid layer or the carboxylic acid layer. The ion exchange membrane may not necessarily be reinforced by reinforcement core materials, and the arrangement of the reinforcement core materials is not limited to the example in Figure 109. (Membrane body)

427/803 sulfonic ”) or a layer of carboxylic acid with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a“ carboxylic acid group ”). From the point of view of strength and dimensional stability, reinforcement core materials are preferably included.

[001619] The particles of inorganic material and binder will be described in detail in the coating layer description section below.

[001620] Figure 109 illustrates a schematic cross-sectional view showing an ion exchange membrane modality. An ion exchange membrane | it has a membrane body 10 containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and coating layers 11a and 11b formed on both surfaces of the membrane body 10.

[001621] In the ion exchange membrane 1, the membrane body 10 comprises a layer of sulfonic acid 3 with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called an “acid group sulfonic ”) and a layer of carboxylic acid 2 with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a“ carboxylic acid group ”), and the core materials of reinforcement 4 intensifies strength and dimensional stability. The ion exchange membrane 1, comprising the sulfonic acid layer 3 and the carboxylic acid layer 2, is suitably used as an anion exchange membrane.

[001622] The ion exchange membrane can include the sulfonic acid layer or the carboxylic acid layer. The ion exchange membrane may not necessarily be reinforced by reinforcement core materials, and the arrangement of the reinforcement core materials is not limited to the example in Figure 109. (Membrane body)

428/803

[001623] First, the membrane body 10 which constitutes the ion exchange membrane 1 will be described.

[001624] The membrane body 10 must be one that has the function of selectively allowing cations to permeate and comprises a hydrocarbon polymer or a fluorine-containing polymer with an ion exchange group. Its configuration and material are not particularly limited, and the preferred ones can be selected appropriately.

[001625] The hydrocarbon polymer or fluorine-containing polymer with an ion exchange group in the membrane body 10 can be obtained from a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group precursor capable of forming a group of ion exchange by hydrolysis or similar. Specifically, for example, after a polymer comprising a fluorinated hydrocarbon backbone that has, as a pendant side chain, a group convertible into an ion exchange group by hydrolysis or similar (precursor to the ion exchange group), and is processable by melting (hereinafter called "fluorine-containing polymer (a)" in some cases), be used to prepare a precursor to the membrane body 10, the membrane body 10 can be obtained by converting the precursor to the ion exchange group in an ion exchange group.

[001626] The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. The fluorine-containing polymer (a) can also be produced by homopolymerizing a monomer selected from any of the following first group, the following second group and the following third group.

[001627] Examples of the monomers of the first group include vinyl fluoride compounds. Examples of the vinyl fluoride compounds include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene,

428/803

[001623] First, the membrane body 10 which constitutes the ion exchange membrane 1 will be described.

[001624] The membrane body 10 must be one that has the function of selectively allowing cations to permeate and comprises a hydrocarbon polymer or a fluorine-containing polymer with an ion exchange group. Its configuration and material are not particularly limited, and the preferred ones can be selected appropriately.

[001625] The hydrocarbon polymer or fluorine-containing polymer with an ion exchange group in the membrane body 10 can be obtained from a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group precursor capable of forming a group of ion exchange by hydrolysis or similar. Specifically, for example, after a polymer comprising a fluorinated hydrocarbon backbone that has, as a pendant side chain, a group convertible into an ion exchange group by hydrolysis or similar (precursor to the ion exchange group), and is processable by melting (hereinafter called "fluorine-containing polymer (a)" in some cases), be used to prepare a precursor to the membrane body 10, the membrane body 10 can be obtained by converting the precursor to the ion exchange group in an ion exchange group.

[001626] The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. The fluorine-containing polymer (a) can also be produced by homopolymerizing a monomer selected from any of the following first group, the following second group and the following third group.

[001627] Examples of the monomers of the first group include vinyl fluoride compounds. Examples of the vinyl fluoride compounds include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene,

429/803 vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and perfluoralkyl vinyl ethers. Particularly when the ion exchange membrane is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoro monomer, and a perfluoro monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and perfluoralkylvinyl ethers is preferable.

[001628] Examples of the monomers of the second group include vinyl compounds with a functional group convertible into an ion exchange group of the carboxylic acid type (carboxylic acid group). Examples of vinyl compounds with a functional group convertible to a carboxylic acid group include monomers represented by CF = CF (OCF; CYF); - O (CZF) .- COOR, where s represents an integer from 0 to 2, t represents an integer from 1 to 12, Y and Z each independently represent F or CF; 3, and R represents a lower alkyl group (a lower alkyl group is an alkyl group with 1 to 3 carbon atoms, for example).

[001629] Among them, compounds represented by CF; = CF (OCF; CYF), - O (CF2) n-COOR are preferable. Where n represents an integer from 0 to 2, m represents an integer from 1 to 4, Y represents F or CF; 3, and R represents CH3, CoHs, or C3H ;.

[001630] When the ion exchange membrane is used as a cation exchange membrane for alkaline electrolysis, a perfluoro compound is preferably at least used as the monomer, but the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis and, therefore, the alkyl group (R) need not be a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[001631] Of the monomers above, the monomers shown below are more preferable than the monomers of the second group: CF; = CFOCF3; -CF (CF;) OCF; COOCH ;, CF; = CFOCF; CF (CF3) O (CF; ) -COOCH ;,

429/803 vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and perfluoralkyl vinyl ethers. Particularly when the ion exchange membrane is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoro monomer, and a perfluoro monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and perfluoralkylvinyl ethers is preferable.

[001628] Examples of the monomers of the second group include vinyl compounds with a functional group convertible into an ion exchange group of the carboxylic acid type (carboxylic acid group). Examples of vinyl compounds with a functional group convertible to a carboxylic acid group include monomers represented by CF = CF (OCF; CYF); - O (CZF) .- COOR, where s represents an integer from 0 to 2, t represents an integer from 1 to 12, Y and Z each independently represent F or CF; 3, and R represents a lower alkyl group (a lower alkyl group is an alkyl group with 1 to 3 carbon atoms, for example).

[001629] Among them, compounds represented by CF; = CF (OCF; CYF), - O (CF2) n-COOR are preferable. Where n represents an integer from 0 to 2, m represents an integer from 1 to 4, Y represents F or CF; 3, and R represents CH3, CoHs, or C3H ;.

[001630] When the ion exchange membrane is used as a cation exchange membrane for alkaline electrolysis, a perfluoro compound is preferably at least used as the monomer, but the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis and, therefore, the alkyl group (R) need not be a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[001631] Of the monomers above, the monomers shown below are more preferable than the monomers of the second group: CF; = CFOCF3; -CF (CF;) OCF; COOCH ;, CF; = CFOCF; CF (CF3) O (CF; ) -COOCH ;,

430/803 CF; = CF [OCF3-CF (CF3) 12O (CF>) - COOCH ;, CF; = CFOCF; CF (CF3) O (CF3); 5COOCH ;, CF3 = CFO (CF3); COOCH ;, and CF; = CFO (CF;); COOCH ;.

[001632] Examples of the monomers of the third group include vinyl compounds with a functional group convertible into an ion exchange group of the sulfone type (sulfonic acid group). As vinyl compounds with a functional group convertible to a sulfonic acid group, for example, monomers represented by CF; = CFO-X-CF; -SO, F are preferred, where X represents a perfluoroalkylene group. Specific examples of these include the monomers represented below: CF; = CFOCFCFSOF, CF; = CFOCFCF (CF3) OCF3CF3SO »xF, CF; = CFOCF: CF (CF3) OCF; CFCF3SO) F, CF3 = CF (CF3); SOF, CF3 = CFO [CF; CF (CF3) O] 1CF.CFE3SOF, and CF. = CFOCF; CF (CF; OCF3) OCF; CFSO »xF.

[001633] Among them, CF = CFOCF; CF (CF3) OCF; CF; CFSO0.F = and CF; = CFOCF; CF (CF3) OCF; CF3SO, F are more preferable.

[001634] The copolymer obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, particularly a general polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, a polymerization reaction can be carried out in the presence of a radical polymerization initiator such as a perfluorocarbon peroxide or an azo compound under the conditions of a temperature of 0 to 200ºC and a pressure of 0, 1 to 20 MPa using an inert solvent such as a perfluorohydrocarbon or a chlorofluorocarbon.

[001635] In the copolymerization above, the type of combination of

430/803 CF; = CF [OCF3-CF (CF3) 12O (CF>) - COOCH ;, CF; = CFOCF; CF (CF3) O (CF3); 5COOCH ;, CF3 = CFO (CF3); COOCH ;, and CF; = CFO (CF;); COOCH ;.

[001632] Examples of the monomers of the third group include vinyl compounds with a functional group convertible into an ion exchange group of the sulfone type (sulfonic acid group). As vinyl compounds with a functional group convertible to a sulfonic acid group, for example, monomers represented by CF; = CFO-X-CF; -SO, F are preferred, where X represents a perfluoroalkylene group. Specific examples of these include the monomers represented below: CF; = CFOCFCFSOF, CF; = CFOCFCF (CF3) OCF3CF3SO »xF, CF; = CFOCF: CF (CF3) OCF; CFCF3SO) F, CF3 = CF (CF3); SOF, CF3 = CFO [CF; CF (CF3) O] 1CF.CFE3SOF, and CF. = CFOCF; CF (CF; OCF3) OCF; CFSO »xF.

[001633] Among them, CF = CFOCF; CF (CF3) OCF; CF; CFSO0.F = and CF; = CFOCF; CF (CF3) OCF; CF3SO, F are more preferable.

[001634] The copolymer obtained from these monomers can be produced by a polymerization method developed for the homopolymerization and copolymerization of ethylene fluoride, particularly a general polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, a polymerization reaction can be carried out in the presence of a radical polymerization initiator such as a perfluorocarbon peroxide or an azo compound under the conditions of a temperature of 0 to 200ºC and a pressure of 0, 1 to 20 MPa using an inert solvent such as a perfluorohydrocarbon or a chlorofluorocarbon.

[001635] In the copolymerization above, the type of combination of

431/803 monomers above and their proportion are not particularly limited and are selected and determined depending on the type and quantity of the desired functional group to be imparted to the fluorine-containing polymer to be obtained. For example, when a fluorine-containing polymer containing only one carboxylic acid group is formed, at least one monomer must be selected from each of the first group and the second group described above and copolymerized. In addition, when a fluorine-containing polymer containing only one sulfonic acid group is formed, at least one monomer must be selected from each of the first group and the third group and copolymerized. In addition, when a fluorine-containing polymer with a carboxylic acid group and a sulfonic acid group is formed, at least one monomer must be selected from each of the first group, the second group and the third group described above and copolymerized. In that case, the target fluorine-containing polymer can also be obtained by separately preparing a copolymer comprising the monomers of the first group and the second group described above and a copolymer comprising the monomers of the first group and the third group described above, and then mixing the copolymers. The mixing ratio of the monomers is not particularly limited, and when the number of functional groups per unit of polymer is increased, the proportion of the selected monomers from the second and third groups described above should be increased.

[001636] The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, more preferably 0.6 to 1.5 mg equivalent / g. The total ion exchange capacity here refers to the exchange group equivalent per unit weight of the dry resin and can be measured by neutralization titration or the like.

[001637] In the membrane body 10 of the ion exchange membrane 1,

431/803 monomers above and their proportion are not particularly limited and are selected and determined depending on the type and quantity of the desired functional group to be imparted to the fluorine-containing polymer to be obtained. For example, when a fluorine-containing polymer containing only one carboxylic acid group is formed, at least one monomer must be selected from each of the first group and the second group described above and copolymerized. In addition, when a fluorine-containing polymer containing only one sulfonic acid group is formed, at least one monomer must be selected from each of the first group and the third group and copolymerized. In addition, when a fluorine-containing polymer with a carboxylic acid group and a sulfonic acid group is formed, at least one monomer must be selected from each of the first group, the second group and the third group described above and copolymerized. In that case, the target fluorine-containing polymer can also be obtained by separately preparing a copolymer comprising the monomers of the first group and the second group described above and a copolymer comprising the monomers of the first group and the third group described above, and then mixing the copolymers. The mixing ratio of the monomers is not particularly limited, and when the number of functional groups per unit of polymer is increased, the proportion of the selected monomers from the second and third groups described above should be increased.

[001636] The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, more preferably 0.6 to 1.5 mg equivalent / g. The total ion exchange capacity here refers to the exchange group equivalent per unit weight of the dry resin and can be measured by neutralization titration or the like.

[001637] In the membrane body 10 of the ion exchange membrane 1,

432/803 a layer of sulfonic acid 3 containing a polymer containing fluorine with a group of sulfonic acid and a layer of carboxylic acid 2 containing a polymer containing fluorine with a group of carboxylic acid are laminated. By providing the membrane body 10 with this layer configuration, the selective permeability for cations, such as sodium fons, can be further improved.

[001638] The ion exchange membrane | it is arranged in an electrolyzer in such a way that, generally, the sulfonic acid layer 3 is located on the anode side of the electrolyzer and the carboxylic acid layer 2 is located on the cathode side of the electrolyzer.

[001639] The sulfonic acid layer 3 is preferably made of a material with low electrical resistance and has a membrane thickness greater than that of the carboxylic acid layer 2 from the point of view of the membrane resistance. The membrane thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, more preferably 3 to 15 times that of the carboxylic acid layer 2.

[001640] The carboxylic acid layer 2 preferably has high anion exclusion properties, even if it has a small membrane thickness. The anion exclusion properties here refer to the property of trying to prevent anion intrusion and permeation into and through the ion exchange membrane 1. In order to increase the anion exclusion properties, it is effective to lay out a layer of carboxylic acid with a small ion exchange capacity to the sulfonic acid layer.

[001641] As the fluorine-containing polymer for use in the sulfonic acid-3 layer, a polymer obtained using CF; = CFOCF; CF (CF3) OCF; CF3SO, 3F as the monomer of the third group is preferred.

[001642] As the fluorine-containing polymer for use in the carboxylic acid-2 layer, a polymer obtained using CF; = CFOCF; CF (CF;) O (CF;); COOCH; as the monomer of the second

432/803 a layer of sulfonic acid 3 containing a polymer containing fluorine with a group of sulfonic acid and a layer of carboxylic acid 2 containing a polymer containing fluorine with a group of carboxylic acid are laminated. By providing the membrane body 10 with this layer configuration, the selective permeability for cations, such as sodium fons, can be further improved.

[001638] The ion exchange membrane | it is arranged in an electrolyzer in such a way that, generally, the sulfonic acid layer 3 is located on the anode side of the electrolyzer and the carboxylic acid layer 2 is located on the cathode side of the electrolyzer.

[001639] The sulfonic acid layer 3 is preferably made of a material with low electrical resistance and has a membrane thickness greater than that of the carboxylic acid layer 2 from the point of view of the membrane resistance. The membrane thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, more preferably 3 to 15 times that of the carboxylic acid layer 2.

[001640] The carboxylic acid layer 2 preferably has high anion exclusion properties, even if it has a small membrane thickness. The anion exclusion properties here refer to the property of trying to prevent anion intrusion and permeation into and through the ion exchange membrane 1. In order to increase the anion exclusion properties, it is effective to lay out a layer of carboxylic acid with a small ion exchange capacity to the sulfonic acid layer.

[001641] As the fluorine-containing polymer for use in the sulfonic acid-3 layer, a polymer obtained using CF; = CFOCF; CF (CF3) OCF; CF3SO, 3F as the monomer of the third group is preferred.

[001642] As the fluorine-containing polymer for use in the carboxylic acid-2 layer, a polymer obtained using CF; = CFOCF; CF (CF;) O (CF;); COOCH; as the monomer of the second

433/803 group. (Coating layer)

[001643] The ion exchange membrane preferably has a coating layer on at least one surface of the membrane body. As shown in Figure 109, on the ion exchange membrane 1, coating layers 11a and 11b are formed on both surfaces of the membrane body 10.

[001644] The coating layers contain particles of inorganic material and a binder.

[001645] The average particle size of the particles of inorganic material is preferably 0.90 µm or more. When the average particle size of the particles of inorganic material is 0.90 µm or more, the durability to impurities is greatly improved, in addition to the gas display. That is, increasing the average particle size of the particles of inorganic material, as well as satisfying the value of the specific surface area mentioned above, can achieve a particularly remarkable effect. Irregular inorganic material particles are preferable because the average particle size and specific surface area, as above, are satisfied. Particles of inorganic material obtained by melting and particles of inorganic material obtained by grinding ore can be used. Particles of inorganic material obtained by grinding raw ore can preferably be used.

[001646] The average particle size of particles of inorganic material can be 2 µm or less. When the average particle size of the particles of inorganic material is 2 µm or less, it is possible to avoid damage to the membrane due to the particles of inorganic material. The average particle size of the inorganic material particle is more preferably 0.90 to 1.2 µm.

[001647] Here, the average particle size can be measured by a

433/803 group. (Coating layer)

[001643] The ion exchange membrane preferably has a coating layer on at least one surface of the membrane body. As shown in Figure 109, on the ion exchange membrane 1, coating layers 11a and 11b are formed on both surfaces of the membrane body 10.

[001644] The coating layers contain particles of inorganic material and a binder.

[001645] The average particle size of the particles of inorganic material is preferably 0.90 µm or more. When the average particle size of the particles of inorganic material is 0.90 µm or more, the durability to impurities is greatly improved, in addition to the gas display. That is, increasing the average particle size of the particles of inorganic material, as well as satisfying the value of the specific surface area mentioned above, can achieve a particularly remarkable effect. Irregular inorganic material particles are preferable because the average particle size and specific surface area, as above, are satisfied. Particles of inorganic material obtained by melting and particles of inorganic material obtained by grinding ore can be used. Particles of inorganic material obtained by grinding raw ore can preferably be used.

[001646] The average particle size of particles of inorganic material can be 2 µm or less. When the average particle size of the particles of inorganic material is 2 µm or less, it is possible to avoid damage to the membrane due to the particles of inorganic material. The average particle size of the inorganic material particle is more preferably 0.90 to 1.2 µm.

[001647] Here, the average particle size can be measured by a

434/803 particle size analyzer (“SALD2200”, SHIMADZU CORPORATION).

[001648] The particles of inorganic material preferably have irregular shapes. Such shapes further improve resistance to impurities. Particles of inorganic material preferably have a wide particle size distribution.

[001649] Particles of inorganic material preferably contain at least one inorganic material selected from the group consisting of oxides of Group IV elements in the Periodic Table, nitrides of Group IV elements in the Periodic Table and carbides of Group IV elements in Periodic table. From the point of view of durability, the zirconium oxide particle is more preferable.

[001650] The particles of inorganic material are preferably particles of inorganic material produced by grinding the raw ore of the particles of inorganic material or particles of inorganic material, such as spherical particles with a uniform diameter, obtained by purification by melting the raw ore of the particles of inorganic material.

[001651] Examples of means for grinding raw ore include, but are not particularly limited to, ball mills, ball mills, colloid mills, conical mills, disc mills, roller mills, grain mills, hammer mills, granules, VSI mills, Wiley mills, laminators and jet mills. After grinding, the particles are preferably washed. As a washing method, the particles are preferably treated with acid. This treatment can reduce impurities, such as iron affixed to the surface of particles of inorganic material.

[001652] The coating layer preferably contains a binder. The binder is a component that forms the coating layers, retaining particles of inorganic material on the surface of the

434/803 particle size analyzer (“SALD2200”, SHIMADZU CORPORATION).

[001648] The particles of inorganic material preferably have irregular shapes. Such shapes further improve resistance to impurities. Particles of inorganic material preferably have a wide particle size distribution.

[001649] Particles of inorganic material preferably contain at least one inorganic material selected from the group consisting of oxides of Group IV elements in the Periodic Table, nitrides of Group IV elements in the Periodic Table and carbides of Group IV elements in Periodic table. From the point of view of durability, the zirconium oxide particle is more preferable.

[001650] The particles of inorganic material are preferably particles of inorganic material produced by grinding the raw ore of the particles of inorganic material or particles of inorganic material, such as spherical particles with a uniform diameter, obtained by purification by melting the raw ore of the particles of inorganic material.

[001651] Examples of means for grinding raw ore include, but are not particularly limited to, ball mills, ball mills, colloid mills, conical mills, disc mills, roller mills, grain mills, hammer mills, granules, VSI mills, Wiley mills, laminators and jet mills. After grinding, the particles are preferably washed. As a washing method, the particles are preferably treated with acid. This treatment can reduce impurities, such as iron affixed to the surface of particles of inorganic material.

[001652] The coating layer preferably contains a binder. The binder is a component that forms the coating layers, retaining particles of inorganic material on the surface of the

435/803 ion exchange membrane. The binder preferably contains a polymer containing fluorine from the point of view of durability to the electrolytic solution and electrolysis products.

[001653] As the binder, a fluorine-containing polymer with a carboxylic acid group or a sulfonic acid group is preferred, from the point of view of durability to the electrolyte solution and products of electrolysis and adhesion to the surface of the ion exchange membrane. When a coating layer is provided on a layer containing a fluorine-containing polymer with a sulfonic acid group (sulfonic acid layer), a fluorine-containing polymer with a sulfonic acid group is still preferably used as the binder of the coating layer. Alternatively, when a coating layer is provided on a layer containing a fluorine-containing polymer with a carboxylic acid group (carboxylic acid layer), a fluorine-containing polymer with a carboxylic acid group is still preferably used as the binder of the coating layer.

[001654] In the coating layer, the content of the particles of inorganic material is preferably 40 to 90% by weight, more preferably 50 to 90% by weight. The content of the binder is preferably 10 to 60% by weight, more preferably 10 to 50% by weight.

[001655] The density of distribution of the coating layer on the ion exchange membrane is preferably 0.05 to 2 mg per 1 µm. When the ion exchange membrane has roughness on its surface, the distribution density of the coating layer is preferably 0.5 to 2 mg per 1 in °.

[001656] As the method for forming the coating layer, which is not particularly limited, a known method can be used. An example is a method that includes spraying or the like of a coating liquid obtained by dispersing particles of inorganic material in a solution containing a binder.

435/803 ion exchange membrane. The binder preferably contains a polymer containing fluorine from the point of view of durability to the electrolytic solution and electrolysis products.

[001653] As the binder, a fluorine-containing polymer with a carboxylic acid group or a sulfonic acid group is preferred, from the point of view of durability to the electrolyte solution and products of electrolysis and adhesion to the surface of the ion exchange membrane. When a coating layer is provided on a layer containing a fluorine-containing polymer with a sulfonic acid group (sulfonic acid layer), a fluorine-containing polymer with a sulfonic acid group is still preferably used as the binder of the coating layer. Alternatively, when a coating layer is provided on a layer containing a fluorine-containing polymer with a carboxylic acid group (carboxylic acid layer), a fluorine-containing polymer with a carboxylic acid group is still preferably used as the binder of the coating layer.

[001654] In the coating layer, the content of the particles of inorganic material is preferably 40 to 90% by weight, more preferably 50 to 90% by weight. The content of the binder is preferably 10 to 60% by weight, more preferably 10 to 50% by weight.

[001655] The density of distribution of the coating layer on the ion exchange membrane is preferably 0.05 to 2 mg per 1 µm. When the ion exchange membrane has roughness on its surface, the distribution density of the coating layer is preferably 0.5 to 2 mg per 1 in °.

[001656] As the method for forming the coating layer, which is not particularly limited, a known method can be used. An example is a method that includes spraying or the like of a coating liquid obtained by dispersing particles of inorganic material in a solution containing a binder.

436/803 (Reinforcement core materials)

[001657] The ion exchange membrane preferably has reinforcement core materials arranged within the membrane body.

[001658] The reinforcement core materials are members that enhance the resistance and dimensional stability of the ion exchange membrane. By arranging the reinforcement core materials within the membrane body, particularly the expansion and contraction of the ion exchange membrane can be controlled in the desired range. Such an ion exchange membrane does not expand or contract more than necessary during electrolysis and the like and can maintain excellent dimensional stability in the long run.

[001659] The configuration of the reinforcement core materials is not particularly limited and, for example, the reinforcement core materials can be formed by spinning threads called reinforcement threads. The reinforcement threads here refer to threads that are members that make up the reinforcement core materials, can provide the desired dimensional stability and mechanical resistance to the ion exchange membrane and can be stably present in the ion exchange membrane. By using the reinforcement core materials obtained by spinning such reinforcement threads, better dimensional stability and mechanical resistance to the ion exchange membrane can be provided.

[001660] The material of the reinforcement core materials and the reinforcement threads used for them is not particularly limited, but is preferably a material resistant to acids, alkalis, etc., and a fiber comprising a fluorine-containing polymer is preferable because the long-term thermal resistance and chemical resistance are required.

[001661] Examples of the fluorine-containing polymer to be used in the reinforcement core materials include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers,

436/803 (Reinforcement core materials)

[001657] The ion exchange membrane preferably has reinforcement core materials arranged within the membrane body.

[001658] The reinforcement core materials are members that enhance the resistance and dimensional stability of the ion exchange membrane. By arranging the reinforcement core materials within the membrane body, particularly the expansion and contraction of the ion exchange membrane can be controlled in the desired range. Such an ion exchange membrane does not expand or contract more than necessary during electrolysis and the like and can maintain excellent dimensional stability in the long run.

[001659] The configuration of the reinforcement core materials is not particularly limited and, for example, the reinforcement core materials can be formed by spinning threads called reinforcement threads. The reinforcement threads here refer to threads that are members that make up the reinforcement core materials, can provide the desired dimensional stability and mechanical resistance to the ion exchange membrane and can be stably present in the ion exchange membrane. By using the reinforcement core materials obtained by spinning such reinforcement threads, better dimensional stability and mechanical resistance to the ion exchange membrane can be provided.

[001660] The material of the reinforcement core materials and the reinforcement threads used for them is not particularly limited, but is preferably a material resistant to acids, alkalis, etc., and a fiber comprising a fluorine-containing polymer is preferable because the long-term thermal resistance and chemical resistance are required.

[001661] Examples of the fluorine-containing polymer to be used in the reinforcement core materials include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers,

437/803 tetrafluoroethylene-ethylene (ETFE) copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, trifluorochlorethylene-ethylene copolymers and vinylidene fluoride (PVDF) polymers. Among these, fibers comprising polytetrafluoroethylene are preferably used from the point of view of heat resistance and chemical resistance.

[001662] The wire diameter of the reinforcement threads used for the reinforcement core materials is not particularly limited, but is preferably 20 to 300 deniers, more preferably 50 to 250 deniers. The weave density (tissue count per unit length) is preferably 5 to 50 / inch. The shape of the reinforcement core materials is not particularly limited, for example, a woven fabric, a non-woven fabric and a knitted fabric are used, but it is preferably in the form of a woven fabric. The thickness of the woven fabric to be used is preferably 30 to 250 µm, more preferably 30 to 150 µm.

[001663] As woven fabric or knitted fabric, monofilaments, multifilaments, or yarns thereof, a slit yarn, or the like, and various types of weaving methods, such as single weft, leno weft, knitted weft, weft, can be used cord and sirsaca, can be used.

[001664] The weft and the arrangement of the reinforcement core materials in the membrane body are not particularly limited, and the preferred arrangement can be suitably provided considering the size and shape of the ion exchange membrane, desired physical properties for the membrane of ion exchange, the environment of use and the like.

[001665] For example, the reinforcement core materials can be arranged along a predetermined direction of the membrane body, but from the point of view of dimensional stability, it is preferable that the reinforcement core materials are arranged over a predetermined first direction, and other reinforcement core materials along a second direction substantially perpendicular to the first direction. To

437/803 tetrafluoroethylene-ethylene (ETFE) copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, trifluorochlorethylene-ethylene copolymers and vinylidene fluoride (PVDF) polymers. Among these, fibers comprising polytetrafluoroethylene are preferably used from the point of view of heat resistance and chemical resistance.

[001662] The wire diameter of the reinforcement threads used for the reinforcement core materials is not particularly limited, but is preferably 20 to 300 deniers, more preferably 50 to 250 deniers. The weave density (tissue count per unit length) is preferably 5 to 50 / inch. The shape of the reinforcement core materials is not particularly limited, for example, a woven fabric, a non-woven fabric and a knitted fabric are used, but it is preferably in the form of a woven fabric. The thickness of the woven fabric to be used is preferably 30 to 250 µm, more preferably 30 to 150 µm.

[001663] As woven fabric or knitted fabric, monofilaments, multifilaments, or yarns thereof, a slit yarn, or the like, and various types of weaving methods, such as single weft, leno weft, knitted weft, weft, can be used cord and sirsaca, can be used.

[001664] The weft and the arrangement of the reinforcement core materials in the membrane body are not particularly limited, and the preferred arrangement can be suitably provided considering the size and shape of the ion exchange membrane, desired physical properties for the membrane of ion exchange, the environment of use and the like.

[001665] For example, the reinforcement core materials can be arranged along a predetermined direction of the membrane body, but from the point of view of dimensional stability, it is preferable that the reinforcement core materials are arranged over a predetermined first direction, and other reinforcement core materials along a second direction substantially perpendicular to the first direction. To

438/803 arranging the plurality of reinforcement core materials substantially orthogonally within the membrane body, it is possible to provide better dimensional stability and mechanical strength in several directions. For example, the arrangement in which reinforcement core materials arranged along the longitudinal direction (warp yarns) and reinforcement core materials arranged along the transverse direction (weft threads) are woven on the surface side of the body membrane is preferred. The arrangement is most preferably in the form of driven flat weft and woven fabric allowing the warps and wefts to alternately move between themselves and underneath each other, smooth weft in which two warps are woven into wefts while twisted, weft in a driven and woven basket by insertion in two or more warps arranged in parallel, wefts of the same or similar number, from the point of view of dimensional stability, mechanical resistance and ease of production.

[001666] It is preferred that, in particular, the reinforcement core materials are arranged along both directions, the MD (Machine Direction) and TD (Transversal Direction) of the ion exchange membrane. In other words, the reinforcement core materials are preferably single woven in MD and TD. Here, MD refers to the direction in which the membrane body and various core materials (for example, the reinforcement core materials, reinforcement wires and sacrificial wires described below) are transported in a production step of ion exchange membrane described later (flow direction) and TD refers to the direction substantially perpendicular to the MD. The threads woven along the MD are called MD threads, and the threads woven along the TD are called TD threads. Typically, the ion exchange membrane used for electrolysis is rectangular, and in many cases, the longitudinal direction is the MD, and the width direction is the TD. By weaving the reinforcement core materials that are MD yarns and the reinforcement core materials that are TD yarns, it is possible to give better

438/803 arranging the plurality of reinforcement core materials substantially orthogonally within the membrane body, it is possible to provide better dimensional stability and mechanical strength in several directions. For example, the arrangement in which reinforcement core materials arranged along the longitudinal direction (warp yarns) and reinforcement core materials arranged along the transverse direction (weft threads) are woven on the surface side of the body membrane is preferred. The arrangement is most preferably in the form of driven flat weft and woven fabric allowing the warps and wefts to alternately move between themselves and underneath each other, smooth weft in which two warps are woven into wefts while twisted, weft in a driven and woven basket by insertion in two or more warps arranged in parallel, wefts of the same or similar number, from the point of view of dimensional stability, mechanical resistance and ease of production.

[001666] It is preferred that, in particular, the reinforcement core materials are arranged along both directions, the MD (Machine Direction) and TD (Transversal Direction) of the ion exchange membrane. In other words, the reinforcement core materials are preferably single woven in MD and TD. Here, MD refers to the direction in which the membrane body and various core materials (for example, the reinforcement core materials, reinforcement wires and sacrificial wires described below) are transported in a production step of ion exchange membrane described later (flow direction) and TD refers to the direction substantially perpendicular to the MD. The threads woven along the MD are called MD threads, and the threads woven along the TD are called TD threads. Typically, the ion exchange membrane used for electrolysis is rectangular, and in many cases, the longitudinal direction is the MD, and the width direction is the TD. By weaving the reinforcement core materials that are MD yarns and the reinforcement core materials that are TD yarns, it is possible to give better

439/803 dimensional stability and mechanical resistance in many directions.

[001667] The range of arrangement of the reinforcement core materials is not particularly limited, and the preferred arrangement can be adequately provided considering the desired physical properties for the ion exchange membrane, the environment of use and the like.

[001668] The orifice ratio for the reinforcement core materials is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The orifice ratio is preferably 30% or more from the point of view of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the point of view of the mechanical strength of the ion exchange membrane.

[001669] The orifice ratio for reinforcement core materials refers to a ratio of a total area of a surface through which substances such as fons (an electrolyte solution and cations contained in it (for example, sodium fons)) they can pass (B) to the area of one of the surfaces of the membrane body (A) (B / A). The total surface area through which substances such as fons can pass (B) can refer to the total areas of regions in which the ion exchange membrane, cations, an electrolyte solution and the like are not blocked by the reinforcement core materials and similar substances contained in the ion exchange membrane.

[001670] Figure 110 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane. Figure 110, in which a portion of the ion exchange membrane is enlarged, shows only the arrangement of the reinforcement core materials 21 and 22 in the regions, omitting the illustration of the other members.

[001671] By subtracting the total area of the reinforcement core materials (C) from the area of the region surrounded by the reinforcement core materials 21 arranged along the longitudinal direction and the core materials of

439/803 dimensional stability and mechanical resistance in many directions.

[001667] The range of arrangement of the reinforcement core materials is not particularly limited, and the preferred arrangement can be adequately provided considering the desired physical properties for the ion exchange membrane, the environment of use and the like.

[001668] The orifice ratio for the reinforcement core materials is not particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The orifice ratio is preferably 30% or more from the point of view of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the point of view of the mechanical strength of the ion exchange membrane.

[001669] The orifice ratio for reinforcement core materials refers to a ratio of a total area of a surface through which substances such as fons (an electrolyte solution and cations contained in it (for example, sodium fons)) they can pass (B) to the area of one of the surfaces of the membrane body (A) (B / A). The total surface area through which substances such as fons can pass (B) can refer to the total areas of regions in which the ion exchange membrane, cations, an electrolyte solution and the like are not blocked by the reinforcement core materials and similar substances contained in the ion exchange membrane.

[001670] Figure 110 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane. Figure 110, in which a portion of the ion exchange membrane is enlarged, shows only the arrangement of the reinforcement core materials 21 and 22 in the regions, omitting the illustration of the other members.

[001671] By subtracting the total area of the reinforcement core materials (C) from the area of the region surrounded by the reinforcement core materials 21 arranged along the longitudinal direction and the core materials of

440/803 reinforcement 22 arranged along the transverse direction, the region including the area of the reinforcement core materials (A), the total area of regions through which substances such as fons can pass (B) in the area of the described region above (A) can be obtained. That is, the orifice ratio can be determined by the following formula (1): Orifice ratio = (B) / (A) = ((A) - (C)) / (A) ... (D

[001672] Among the materials of the reinforcement core, a particularly preferred form are stranded yarns or highly oriented monofilaments comprising PTFE from the point of view of chemical resistance and heat resistance. Specifically, reinforcement core materials forming a single web in which 50 to 300 denier ribbon yarns obtained by cutting a high strength porous sheet comprising PTFE into a ribbon form, or highly oriented 50 to 300 denier monofilaments are used comprising PTFE and having a weave density of 10 to 50 threads or monofilaments / inch and having a thickness in the range of 50 to 100 µm are more preferred. The orifice ratio of an ion exchange membrane comprising such reinforcement core materials is still preferably 60% or more.

[001673] Examples of the shape of the reinforcement threads include round threads and ribbon threads. (Continuous holes)

[001674] The ion exchange membrane preferably has continuous holes inside the membrane body.

[001675] Continuous holes refer to holes that can be flow paths for fons generated in electrolysis and an electrolyte solution. The continuous holes, which are tubular holes formed inside the membrane body, are formed by dissolving the sacrificial core materials (or sacrificial threads) described below. The shape, diameter or similar of the continuous holes can be controlled by selecting the shape or diameter of the

440/803 reinforcement 22 arranged along the transverse direction, the region including the area of the reinforcement core materials (A), the total area of regions through which substances such as fons can pass (B) in the area of the described region above (A) can be obtained. That is, the orifice ratio can be determined by the following formula (1): Orifice ratio = (B) / (A) = ((A) - (C)) / (A) ... (D

[001672] Among the materials of the reinforcement core, a particularly preferred form are stranded yarns or highly oriented monofilaments comprising PTFE from the point of view of chemical resistance and heat resistance. Specifically, reinforcement core materials forming a single web in which 50 to 300 denier ribbon yarns obtained by cutting a high strength porous sheet comprising PTFE into a ribbon form, or highly oriented 50 to 300 denier monofilaments are used comprising PTFE and having a weave density of 10 to 50 threads or monofilaments / inch and having a thickness in the range of 50 to 100 µm are more preferred. The orifice ratio of an ion exchange membrane comprising such reinforcement core materials is still preferably 60% or more.

[001673] Examples of the shape of the reinforcement threads include round threads and ribbon threads. (Continuous holes)

[001674] The ion exchange membrane preferably has continuous holes inside the membrane body.

[001675] Continuous holes refer to holes that can be flow paths for fons generated in electrolysis and an electrolyte solution. The continuous holes, which are tubular holes formed inside the membrane body, are formed by dissolving the sacrificial core materials (or sacrificial threads) described below. The shape, diameter or similar of the continuous holes can be controlled by selecting the shape or diameter of the

441/803 sacrifice core materials (sacrifice threads).

[001676] Forming the continuous holes inside the ion exchange membrane can guarantee the mobility of an electrolyte solution in electrolysis. The shape of the continuous holes is not particularly limited, but it may be the shape of the sacrificial core materials to be used for forming the continuous holes according to the production method described below.

[001677] The continuous holes are preferably formed so as to pass alternately through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcement core materials. With this structure, in a portion in which continuous holes are formed on the cathode side of the reinforcement core materials, ions (eg sodium fons) carried by the electrolyte solution with which the continuous holes are filled can also flow on the side of the cathode of the reinforcement core materials. As a result, the flow of cations is not interrupted and, therefore, it is possible to further reduce the electrical resistance of the ion exchange membrane.

[001678] The continuous holes can be formed along only a predetermined direction of the membrane body that constitutes the ion exchange membrane, but are preferably formed both in the longitudinal and in the transversal direction of the membrane body from the point of view of presenting a more stable electrolytic performance. [Production method]

[001679] A suitable example of a method for producing an ion exchange membrane includes a method including the following steps (1) to (6): Step (1): the step of producing a fluorine-containing polymer with an exchange group ionic or a precursor of the ion exchange group capable of forming an ion exchange group by hydrolysis, Step (2): the weaving step at least a plurality of

441/803 sacrifice core materials (sacrifice threads).

[001676] Forming the continuous holes inside the ion exchange membrane can guarantee the mobility of an electrolyte solution in electrolysis. The shape of the continuous holes is not particularly limited, but it may be the shape of the sacrificial core materials to be used for forming the continuous holes according to the production method described below.

[001677] The continuous holes are preferably formed so as to pass alternately through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcement core materials. With this structure, in a portion in which continuous holes are formed on the cathode side of the reinforcement core materials, ions (eg sodium fons) carried by the electrolyte solution with which the continuous holes are filled can also flow on the side of the cathode of the reinforcement core materials. As a result, the flow of cations is not interrupted and, therefore, it is possible to further reduce the electrical resistance of the ion exchange membrane.

[001678] The continuous holes can be formed along only a predetermined direction of the membrane body that constitutes the ion exchange membrane, but are preferably formed both in the longitudinal and in the transversal direction of the membrane body from the point of view of presenting a more stable electrolytic performance. [Production method]

[001679] A suitable example of a method for producing an ion exchange membrane includes a method including the following steps (1) to (6): Step (1): the step of producing a fluorine-containing polymer with an exchange group ionic or a precursor of the ion exchange group capable of forming an ion exchange group by hydrolysis, Step (2): the weaving step at least a plurality of

442/803 reinforcement core materials, as required, and sacrificial wires with a dissolving property in an acid or an alkali, and formation of continuous holes, to obtain a reinforcing material in which the sacrificial wires are arranged between the reinforcement core materials adjacent to each other, Step (3): the step of forming a fluorine-containing polymer film above with an ion exchange group or a precursor to the ion exchange group capable of forming an ion exchange group by hydrolysis , Step (4): the step of embedding the reinforcement materials above, as required, in the above film to obtain a membrane body within which the reinforcement materials are arranged, Step (5): the hydrolysis step of the body membrane obtained in step (4) (hydrolysis step), and Step (6): the step of providing a coating layer on the membrane body obtained in step (5) (application step).

[001680] Next, each of the steps will be described in detail.

Step (1): Fluorine-containing polymer production step

[001681] In step (1), the raw material monomers described in the first group for the third group above are used to produce a fluorine-containing polymer. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the raw material monomers must be adjusted in the production of the fluorine-containing polymer that forms the layers.

Step (2): Reinforcement materials production step

[001682] The reinforcement material is a woven fabric obtained by weaving reinforcement threads or the like. The reinforcement material is embedded in the membrane to form reinforcement core materials. When an ion exchange membrane with continuous holes is formed, the sacrificial threads are additionally woven into the reinforcement material. The quantity of the sacrificial threads contained in this case is preferably 10 to 80% by weight, more

442/803 reinforcement core materials, as required, and sacrificial wires with a dissolving property in an acid or an alkali, and formation of continuous holes, to obtain a reinforcing material in which the sacrificial wires are arranged between the reinforcement core materials adjacent to each other, Step (3): the step of forming a fluorine-containing polymer film above with an ion exchange group or a precursor to the ion exchange group capable of forming an ion exchange group by hydrolysis , Step (4): the step of embedding the reinforcement materials above, as required, in the above film to obtain a membrane body within which the reinforcement materials are arranged, Step (5): the hydrolysis step of the body membrane obtained in step (4) (hydrolysis step), and Step (6): the step of providing a coating layer on the membrane body obtained in step (5) (application step).

[001680] Next, each of the steps will be described in detail.

Step (1): Fluorine-containing polymer production step

[001681] In step (1), the raw material monomers described in the first group for the third group above are used to produce a fluorine-containing polymer. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the raw material monomers must be adjusted in the production of the fluorine-containing polymer that forms the layers.

Step (2): Reinforcement materials production step

[001682] The reinforcement material is a woven fabric obtained by weaving reinforcement threads or the like. The reinforcement material is embedded in the membrane to form reinforcement core materials. When an ion exchange membrane with continuous holes is formed, the sacrificial threads are additionally woven into the reinforcement material. The quantity of the sacrificial threads contained in this case is preferably 10 to 80% by weight, more

443/803 preferably 30 to 70% by weight based on the entire reinforcement material. Weaving the sacrificial yarns can also prevent the yarn from slipping the reinforcement core materials.

[001683] As sacrificial threads, which have solubility in the membrane production stage or under an electrolysis environment, rayon, polyethylene terephthalate (PET), cellulose, polyamide and the like are used. Also preferred are monofilaments or multifilaments having a thickness of 20 to 50 deniers and comprising polyvinyl alcohol and the like.

[001684] In step (2), the orifice ratio, the arrangement of the continuous holes and the like can be controlled by adjusting the arrangement of the reinforcement core materials and the sacrifice wires. Step (3): Film forming step

[001685] In step (3), the fluorine-containing polymer obtained in step (1) is formed into a film using an extruder. The film can be a single layer configuration, a two layer configuration of a sulfonic acid layer and a layer of carboxylic acid, as mentioned above, or a multilayer configuration of three layers or more.

[001686] Examples of the film-forming method include the following: a method in which a fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are formed separately in films; and a method in which the fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are coextruded into a composite film.

[001687] The number of each film can be more than one. Coextrusion of different films is preferred because of their contribution to an increase in adhesive strength at the interface.

443/803 preferably 30 to 70% by weight based on the entire reinforcement material. Weaving the sacrificial yarns can also prevent the yarn from slipping the reinforcement core materials.

[001683] As sacrificial threads, which have solubility in the membrane production stage or under an electrolysis environment, rayon, polyethylene terephthalate (PET), cellulose, polyamide and the like are used. Also preferred are monofilaments or multifilaments having a thickness of 20 to 50 deniers and comprising polyvinyl alcohol and the like.

[001684] In step (2), the orifice ratio, the arrangement of the continuous holes and the like can be controlled by adjusting the arrangement of the reinforcement core materials and the sacrifice wires. Step (3): Film forming step

[001685] In step (3), the fluorine-containing polymer obtained in step (1) is formed into a film using an extruder. The film can be a single layer configuration, a two layer configuration of a sulfonic acid layer and a layer of carboxylic acid, as mentioned above, or a multilayer configuration of three layers or more.

[001686] Examples of the film-forming method include the following: a method in which a fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are formed separately in films; and a method in which the fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are coextruded into a composite film.

[001687] The number of each film can be more than one. Coextrusion of different films is preferred because of their contribution to an increase in adhesive strength at the interface.

444/803 Stage (4): Stage of obtaining the membrane body

[001688] In step (4), the reinforcement material obtained in step (2) is embedded in the film obtained in step (3) to provide a membrane body including the reinforcement material therein.

[001689] Preferable examples of the method for forming a membrane body include (1) a method in which a fluorine-containing polymer with a precursor to the carboxylic acid group (e.g., carboxylate functional group) (hereinafter, a layer comprising the same is called the first layer) located on the cathode side and a fluorine-containing polymer with a precursor to the sulfonic acid group (eg, sulfonyl fluoride functional group) (hereinafter, a layer comprising the same is called the second layer) are formed into a film by a coextrusion method and, using a heat source and a vacuum source as needed, a reinforcement material and the second layer / first layer composite film are laminated in that order on breathable release paper resistant to heat in a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated by reduced pressure; and (11) a method in which, in addition to the composite film of the second layer / first layer, a fluorine-containing polymer with a precursor to the sulfonic acid group is formed separately in a film (the third layer) in advance and, using a heat source and a vacuum source as needed, the third layer film, the reinforcement core materials and the composite film comprising the second layer / first layer are laminated in that order on heat resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated under reduced pressure.

444/803 Stage (4): Stage of obtaining the membrane body

[001688] In step (4), the reinforcement material obtained in step (2) is embedded in the film obtained in step (3) to provide a membrane body including the reinforcement material therein.

[001689] Preferable examples of the method for forming a membrane body include (1) a method in which a fluorine-containing polymer with a precursor to the carboxylic acid group (e.g., carboxylate functional group) (hereinafter, a layer comprising the same is called the first layer) located on the cathode side and a fluorine-containing polymer with a precursor to the sulfonic acid group (eg, sulfonyl fluoride functional group) (hereinafter, a layer comprising the same is called the second layer) are formed into a film by a coextrusion method and, using a heat source and a vacuum source as needed, a reinforcement material and the second layer / first layer composite film are laminated in that order on breathable release paper resistant to heat in a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated by reduced pressure; and (11) a method in which, in addition to the composite film of the second layer / first layer, a fluorine-containing polymer with a precursor to the sulfonic acid group is formed separately in a film (the third layer) in advance and, using a heat source and a vacuum source as needed, the third layer film, the reinforcement core materials and the composite film comprising the second layer / first layer are laminated in that order on heat resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated under reduced pressure.

445/803

[001690] The coextrusion of the first layer and the second layer contributes to an increase in the adhesive strength at the interface.

[001691] The method including integration under reduced pressure is characterized by making the third layer in the reinforcement material thicker than that of the pressure method of applying pressure. In addition, since the reinforcement material is fixed on the inner surface of the membrane body, the method has a property capable of sufficiently retaining the mechanical resistance of the ion exchange membrane.

[001692] The lamination variations described here are exemplary, and coextrusion can be performed after a preferred lamination pattern (for example, the combination of layers) has been appropriately selected considering the desired layer configuration of the membrane body and physical properties, and the like.

[001693] In order to further improve the electrical properties of the ion exchange membrane, it is also possible to additionally interpose a fourth layer comprising a fluorine-containing polymer with a precursor of the carboxylic acid group and a precursor of the sulfonic acid group between the first layer and the second layer or using a fourth layer comprising a fluorine-containing polymer with a carboxylic acid group precursor and a sulfonic acid group precursor instead of the second layer.

[001694] The method for forming the fourth layer can be a method in which a fluorine-containing polymer with a carboxylic acid group precursor and a fluorine-containing polymer with a sulfonic acid group precursor are separately produced and then mixed or can be a method wherein a monomer with a precursor to the carboxylic acid group and a monomer with a precursor to the sulfonic acid group are copolymerized.

[001695] When the fourth layer is used as a component of the

445/803

[001690] The coextrusion of the first layer and the second layer contributes to an increase in the adhesive strength at the interface.

[001691] The method including integration under reduced pressure is characterized by making the third layer in the reinforcement material thicker than that of the pressure method of applying pressure. In addition, since the reinforcement material is fixed on the inner surface of the membrane body, the method has a property capable of sufficiently retaining the mechanical resistance of the ion exchange membrane.

[001692] The lamination variations described here are exemplary, and coextrusion can be performed after a preferred lamination pattern (for example, the combination of layers) has been appropriately selected considering the desired layer configuration of the membrane body and physical properties, and the like.

[001693] In order to further improve the electrical properties of the ion exchange membrane, it is also possible to additionally interpose a fourth layer comprising a fluorine-containing polymer with a precursor of the carboxylic acid group and a precursor of the sulfonic acid group between the first layer and the second layer or using a fourth layer comprising a fluorine-containing polymer with a carboxylic acid group precursor and a sulfonic acid group precursor instead of the second layer.

[001694] The method for forming the fourth layer can be a method in which a fluorine-containing polymer with a carboxylic acid group precursor and a fluorine-containing polymer with a sulfonic acid group precursor are separately produced and then mixed or can be a method wherein a monomer with a precursor to the carboxylic acid group and a monomer with a precursor to the sulfonic acid group are copolymerized.

[001695] When the fourth layer is used as a component of the

446/803 ion exchange membrane, a coextruded film of the first layer and the fourth layer is formed, moreover, the third layer and the second layer are formed separately in films, and lamination can be carried out by the method mentioned above. Alternatively, the three layers of the first layer / fourth layer / second layer can be simultaneously formed into a film by coextrusion.

[001696] In this case, the direction in which the extruded film flows is the MD. As mentioned above, it is possible to form a membrane body containing a fluorine-containing polymer with an ion exchange group in a reinforcement material.

[001697] Additionally, the ion exchange membrane preferably has protruding portions composed of the fluorine-containing polymer with a sulfonic acid group, that is, projections, on the surface side composed of the sulfonic acid layer. As a method for forming such projections, which is not particularly limited, one can also use a known method including forming projections on a resin surface. A specific example of the method is a method of embossing the surface of the membrane body. For example, the above projections can be formed using release paper embossed in advance when the composite film mentioned above, reinforcement material and the like are integrated. In the case where the projections are formed by embossing, the height and density of arrangement of the projections can be controlled by controlling the form of embossing to be transferred (shape of the release paper). (5) Hydrolysis step

[001698] In step (5), a step of hydrolysis of the membrane body obtained in step (4) is carried out to convert the precursor of the ion exchange group into an ion exchange group (hydrolysis step).

[001699] In step (5), it is also possible to form dissolution holes in the

446/803 ion exchange membrane, a coextruded film of the first layer and the fourth layer is formed, moreover, the third layer and the second layer are formed separately in films, and lamination can be carried out by the method mentioned above. Alternatively, the three layers of the first layer / fourth layer / second layer can be simultaneously formed into a film by coextrusion.

[001696] In this case, the direction in which the extruded film flows is the MD. As mentioned above, it is possible to form a membrane body containing a fluorine-containing polymer with an ion exchange group in a reinforcement material.

[001697] Additionally, the ion exchange membrane preferably has protruding portions composed of the fluorine-containing polymer with a sulfonic acid group, that is, projections, on the surface side composed of the sulfonic acid layer. As a method for forming such projections, which is not particularly limited, one can also use a known method including forming projections on a resin surface. A specific example of the method is a method of embossing the surface of the membrane body. For example, the above projections can be formed using release paper embossed in advance when the composite film mentioned above, reinforcement material and the like are integrated. In the case where the projections are formed by embossing, the height and density of arrangement of the projections can be controlled by controlling the form of embossing to be transferred (shape of the release paper). (5) Hydrolysis step

[001698] In step (5), a step of hydrolysis of the membrane body obtained in step (4) is carried out to convert the precursor of the ion exchange group into an ion exchange group (hydrolysis step).

[001699] In step (5), it is also possible to form dissolution holes in the

447/803 membrane body dissolving and removing the sacrifice wires included in the membrane body with acid or alkali. The sacrifice wires can remain in the continuous holes without being completely dissolved and removed. The sacrifice wires that remain in the continuous holes can be dissolved and removed by the electrolyte solution when the ion exchange membrane is subjected to electrolysis.

[001700] The sacrifice wire has solubility in acid or alkali in the production stage of an ion exchange membrane or under an electrolysis environment. The sacrifice wires are eluted to form continuous holes at the corresponding locations.

[001701] Step (5) can be carried out by immersing the membrane body obtained in step (4) in a hydrolysis solution containing acid or alkali. An example of the hydrolysis solution that can be used is a mixed solution containing KOH and dimethyl sulfoxide (DMSO).

[001702] The mixed solution preferably contains KOH of 2.5 to 4.0 Ne and DMSO of 25 to 35% by weight.

[001703] The temperature for hydrolysis is preferably 70 to 100 ° C. The higher the temperature, the greater the apparent thickness. The temperature is more preferably 75 to 100 ° C.

[001704] The time for hydrolysis is preferably 10 to 120 minutes. The longer the time, the greater the apparent thickness. The time is most preferably 20 to 120 minutes.

[001705] The step of forming continuous holes eluting the sacrificial wire will now be described in more detail. Figures 111 (a) and (b) are schematic views to explain a method for forming the continuous holes in the ion exchange membrane.

[001706] Figures 111 (a) and (b) show the reinforcement threads 52, the sacrifice threads 504a and the continuous holes 504 formed only by the sacrifice threads 504a, omitting the illustration of the other members, such as a body

447/803 membrane body dissolving and removing the sacrifice wires included in the membrane body with acid or alkali. The sacrifice wires can remain in the continuous holes without being completely dissolved and removed. The sacrifice wires that remain in the continuous holes can be dissolved and removed by the electrolyte solution when the ion exchange membrane is subjected to electrolysis.

[001700] The sacrifice wire has solubility in acid or alkali in the production stage of an ion exchange membrane or under an electrolysis environment. The sacrifice wires are eluted to form continuous holes at the corresponding locations.

[001701] Step (5) can be carried out by immersing the membrane body obtained in step (4) in a hydrolysis solution containing acid or alkali. An example of the hydrolysis solution that can be used is a mixed solution containing KOH and dimethyl sulfoxide (DMSO).

[001702] The mixed solution preferably contains KOH of 2.5 to 4.0 Ne and DMSO of 25 to 35% by weight.

[001703] The temperature for hydrolysis is preferably 70 to 100 ° C. The higher the temperature, the greater the apparent thickness. The temperature is more preferably 75 to 100 ° C.

[001704] The time for hydrolysis is preferably 10 to 120 minutes. The longer the time, the greater the apparent thickness. The time is most preferably 20 to 120 minutes.

[001705] The step of forming continuous holes eluting the sacrificial wire will now be described in more detail. Figures 111 (a) and (b) are schematic views to explain a method for forming the continuous holes in the ion exchange membrane.

[001706] Figures 111 (a) and (b) show the reinforcement threads 52, the sacrifice threads 504a and the continuous holes 504 formed only by the sacrifice threads 504a, omitting the illustration of the other members, such as a body

448/803 membrane.

[001707] Firstly, the reinforcement wires 52 constituting reinforcement core materials in the ion exchange membrane and the sacrifice wires 504a to form the continuous holes 504 in the ion exchange membrane are used as interlaced reinforcement materials. Then, in step (5), the sacrifice threads 504a are eluted to form continuous holes 504.

[001708] The above method is simple because the method for weaving reinforcement wires 52 and sacrifice wires 504a can be adjusted depending on the arrangement of the reinforcement core materials and the continuous holes in the membrane body of the ion exchange membrane.

[001709] Figure 111 (a) exemplifies the single fabric reinforcement material in which reinforcement threads 52 and sacrifice threads 504a are interwoven along the longitudinal and lateral direction on the paper, and the arrangement of the reinforcement 52 and the sacrifice wires 504a in the reinforcement material may vary as required. (6) Application stage

[001710] In step (6), a coating layer can be formed by preparing a coating liquid containing particles of inorganic material obtained by grinding raw ore or melting raw ore and a binder, applying the coating liquid on the surface of the ion exchange membrane obtained in step (5), and drying of the coating liquid.

[001711] A preferred binder is a binder obtained by hydrolysis of a fluorine-containing polymer with an ion exchange group precursor with an aqueous solution containing dimethylsulfoxide (DMSO) and potassium hydroxide (KOH) and then immersion of the polymer in hydrochloric acid to replace the counter-ion of the ion exchange group with H + (for example, a fluorine-containing polymer with a carboxyl group or a sulfo group). Thus, the polymer is more likely to dissolve in water or ethanol

448/803 membrane.

[001707] Firstly, the reinforcement wires 52 constituting reinforcement core materials in the ion exchange membrane and the sacrifice wires 504a to form the continuous holes 504 in the ion exchange membrane are used as interlaced reinforcement materials. Then, in step (5), the sacrifice threads 504a are eluted to form continuous holes 504.

[001708] The above method is simple because the method for weaving reinforcement wires 52 and sacrifice wires 504a can be adjusted depending on the arrangement of the reinforcement core materials and the continuous holes in the membrane body of the ion exchange membrane.

[001709] Figure 111 (a) exemplifies the single fabric reinforcement material in which reinforcement threads 52 and sacrifice threads 504a are interwoven along the longitudinal and lateral direction on the paper, and the arrangement of the reinforcement 52 and the sacrifice wires 504a in the reinforcement material may vary as required. (6) Application stage

[001710] In step (6), a coating layer can be formed by preparing a coating liquid containing particles of inorganic material obtained by grinding raw ore or melting raw ore and a binder, applying the coating liquid on the surface of the ion exchange membrane obtained in step (5), and drying of the coating liquid.

[001711] A preferred binder is a binder obtained by hydrolysis of a fluorine-containing polymer with an ion exchange group precursor with an aqueous solution containing dimethylsulfoxide (DMSO) and potassium hydroxide (KOH) and then immersion of the polymer in hydrochloric acid to replace the counter-ion of the ion exchange group with H + (for example, a fluorine-containing polymer with a carboxyl group or a sulfo group). Thus, the polymer is more likely to dissolve in water or ethanol

449/803 mentioned below, which is preferable.

[001712] This binder is dissolved in a mixed solution of water and ethanol. The volume ratio between water and ethanol is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 2: 1 to 1: 2. The particles of inorganic material are dispersed with a ball mill in the dissolution liquid thus obtained to provide a coating liquid. In this case, it is also possible to adjust the average particle size and the like of the particles by adjusting the time and speed of rotation during dispersion. The preferable amount of the particles of inorganic material and the binder to be mixed is as mentioned above.

[001713] The concentration of the particles of inorganic material and the binder in the coating liquid is not particularly limited, but a thin-coated liquid is preferable. This allows uniform application to the surface of the ion exchange membrane.

[001714] Additionally, a surfactant can be added to the dispersion when the particles of inorganic material are dispersed. Like the surfactant, nonionic surfactants are preferable and examples of them include HS-210, NS-210, P-210 and E-212 manufactured by NOF CORPORATION.

[001715] The coating liquid obtained is applied on the surface of the ion exchange membrane by spray application or roller coating, thus providing an ion exchange membrane. [Microporous membrane]

[001716] The microporous membrane of the present modality is not particularly limited as long as the membrane can be formed in a laminate with the electrolysis electrode, as mentioned above. Several microporous membranes can be used.

[001717] The porosity of the microporous membrane of the present modality is not particularly limited, but it can be from 20 to 90, for

449/803 mentioned below, which is preferable.

[001712] This binder is dissolved in a mixed solution of water and ethanol. The volume ratio between water and ethanol is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 2: 1 to 1: 2. The particles of inorganic material are dispersed with a ball mill in the dissolution liquid thus obtained to provide a coating liquid. In this case, it is also possible to adjust the average particle size and the like of the particles by adjusting the time and speed of rotation during dispersion. The preferable amount of the particles of inorganic material and the binder to be mixed is as mentioned above.

[001713] The concentration of the particles of inorganic material and the binder in the coating liquid is not particularly limited, but a thin-coated liquid is preferable. This allows uniform application to the surface of the ion exchange membrane.

[001714] Additionally, a surfactant can be added to the dispersion when the particles of inorganic material are dispersed. Like the surfactant, nonionic surfactants are preferable and examples of them include HS-210, NS-210, P-210 and E-212 manufactured by NOF CORPORATION.

[001715] The coating liquid obtained is applied on the surface of the ion exchange membrane by spray application or roller coating, thus providing an ion exchange membrane. [Microporous membrane]

[001716] The microporous membrane of the present modality is not particularly limited as long as the membrane can be formed in a laminate with the electrolysis electrode, as mentioned above. Several microporous membranes can be used.

[001717] The porosity of the microporous membrane of the present modality is not particularly limited, but it can be from 20 to 90, for

450/803 example, and is preferably 30 to 85. The porosity above can be calculated by the following formula: Porosity = (1 - (the weight of the membrane in a dry state) / (the weight calculated from the volume calculated from of the thickness, width and length of the membrane and the density of the membrane material)) x 100

[001718] The average pore size of the microporous membrane of the present embodiment is not particularly limited, and can be 0.01 µm to 1 µm, for example, preferably 0.05 µm to 5 µm. Regarding the average pore size, for example, the membrane is cut vertically in the direction of thickness, and the section is observed with an FE-SEM. The average pore size can be obtained by measuring the diameter of about 100 observed pores and averaging the measurements.

[001719] The thickness of the microporous membrane of the present embodiment is not particularly limited, and can be from 10 µm to 1000 µm, for example, preferably 50 µm to 600 µm. The above thickness can be measured using a micrometer (manufactured by Mitutoyo Corporation) or similar, for example.

[001720] Specific examples of the microporous membrane as mentioned above include Zirfon Perl UTP 500 manufactured by Agfa (also called Zirfon membrane in the present embodiment) and those described in International Publication No. WO 2013-183584 and International Publication No. WO 2016-203701.

[001721] In the present embodiment, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different EW (ion exchange capacity) than that of the first layer of ion exchange resin. In addition, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different functional group than that of the first layer of

450/803 example, and is preferably 30 to 85. The porosity above can be calculated by the following formula: Porosity = (1 - (the weight of the membrane in a dry state) / (the weight calculated from the volume calculated from of the thickness, width and length of the membrane and the density of the membrane material)) x 100

[001718] The average pore size of the microporous membrane of the present embodiment is not particularly limited, and can be 0.01 µm to 1 µm, for example, preferably 0.05 µm to 5 µm. Regarding the average pore size, for example, the membrane is cut vertically in the direction of thickness, and the section is observed with an FE-SEM. The average pore size can be obtained by measuring the diameter of about 100 observed pores and averaging the measurements.

[001719] The thickness of the microporous membrane of the present embodiment is not particularly limited, and can be from 10 µm to 1000 µm, for example, preferably 50 µm to 600 µm. The above thickness can be measured using a micrometer (manufactured by Mitutoyo Corporation) or similar, for example.

[001720] Specific examples of the microporous membrane as mentioned above include Zirfon Perl UTP 500 manufactured by Agfa (also called Zirfon membrane in the present embodiment) and those described in International Publication No. WO 2013-183584 and International Publication No. WO 2016-203701.

[001721] In the present embodiment, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different EW (ion exchange capacity) than that of the first layer of ion exchange resin. In addition, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different functional group than that of the first layer of

451/803 ion exchange resin. The ion exchange capacity can be adjusted by the functional group to be introduced, and functional groups that can be introduced are as mentioned above. (Water electrolysis)

[001722] The electrolyser in the present modality, like an electrolyser in the case of water electrolysis, has a configuration in which the ion exchange membrane in an electrolyser for use in the case of common salt electrolysis mentioned above is replaced by a microporous membrane. The raw material to be supplied, which is water, is different from that for the electrolyser in the case of electrolysis of the common salt mentioned above. As for the other components, components similar to those of the electrolyser in the case of electrolysis of common salt can also be used in the electrolyser in the case of water electrolysis. Since chlorine gas is generated in the anodic chamber in the case of common salt electrolysis, titanium is used as the material in the anodic chamber, but in the case of water electrolysis, only oxygen gas is generated in the anodic chamber. Thus, a material identical to that of the cathodic chamber can be used. An example of this is nickel. For the anode coating, the catalyst coating for oxygen generation is suitable. Examples of the catalyst coating include metals, oxides and hydroxides of the metals of the platinum group and metals of the transition metal group. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used. <Seventh modality>

[001723] Here, a seventh embodiment of the present invention will be described in detail with reference to Figures 112 to 122. [Method for producing the electrolyzer]

[001724] The method for producing an electrolyser according to the first aspect (hereinafter, simply called “first aspect”) of the seventh modality (hereinafter, simply called

451/803 ion exchange resin. The ion exchange capacity can be adjusted by the functional group to be introduced, and functional groups that can be introduced are as mentioned above. (Water electrolysis)

[001722] The electrolyser in the present modality, like an electrolyser in the case of water electrolysis, has a configuration in which the ion exchange membrane in an electrolyser for use in the case of common salt electrolysis mentioned above is replaced by a microporous membrane. The raw material to be supplied, which is water, is different from that for the electrolyser in the case of electrolysis of the common salt mentioned above. As for the other components, components similar to those of the electrolyser in the case of electrolysis of common salt can also be used in the electrolyser in the case of water electrolysis. Since chlorine gas is generated in the anodic chamber in the case of common salt electrolysis, titanium is used as the material in the anodic chamber, but in the case of water electrolysis, only oxygen gas is generated in the anodic chamber. Thus, a material identical to that of the cathodic chamber can be used. An example of this is nickel. For the anode coating, the catalyst coating for oxygen generation is suitable. Examples of the catalyst coating include metals, oxides and hydroxides of the metals of the platinum group and metals of the transition metal group. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used. <Seventh modality>

[001723] Here, a seventh embodiment of the present invention will be described in detail with reference to Figures 112 to 122. [Method for producing the electrolyzer]

[001724] The method for producing an electrolyser according to the first aspect (hereinafter, simply called “first aspect”) of the seventh modality (hereinafter, simply called

452/803 <Seventh modality>, simply called “the present modality”) is a method for producing a new electrolyzer by arranging a laminate comprising an electrolyte for electrolysis and a new membrane in an existing electrolyzer comprising an anode, a cathode that it is opposite the anode, a membrane that is fixed between the anode and the cathode, and an electrolyzer structure that supports the anode, cathode and membrane, the method comprising a step (A) of releasing a membrane fixation on the frame of the electrolyzer and a step (B) of replacing the membrane with the laminate after step (A).

[001725] As described above, according to the method for producing an electrolyzer according to the first aspect, it is possible to renew the electrode without removing each component from the outside of the electrolyzer frame, and it is possible to improve the work efficiency during the electrode renewal in an electrolyser.

[001726] A method for producing an electrolyzer according to a second aspect (hereinafter, also simply called the "second aspect") of the present modality is a method for producing a new electrolyzer by arranging an electrolysis electrode in an existing electrolyzer that comprises an anode, a cathode that is opposite the anode, a membrane that is fixed between the anode and the cathode, and an electrolyzer structure that supports the anode, cathode and membrane, the method comprising a release step (A) a fixation of the membrane on the electrolyzer frame and a step (B ') of electrode arrangement for electrolysis between the membrane and the anode or cathode after step (A).

[001727] As described above, also according to the method for producing an electrolyzer according to the second aspect, it is possible to renew the electrode without removing each component from the outside of the electrolyzer frame, and it is possible to improve the work efficiency during the electrode renewal in an electrolyser.

452/803 <Seventh modality>, simply called “the present modality”) is a method for producing a new electrolyzer by arranging a laminate comprising an electrolyte for electrolysis and a new membrane in an existing electrolyzer comprising an anode, a cathode that it is opposite the anode, a membrane that is fixed between the anode and the cathode, and an electrolyzer structure that supports the anode, cathode and membrane, the method comprising a step (A) of releasing a membrane fixation on the frame of the electrolyzer and a step (B) of replacing the membrane with the laminate after step (A).

[001725] As described above, according to the method for producing an electrolyzer according to the first aspect, it is possible to renew the electrode without removing each component from the outside of the electrolyzer frame, and it is possible to improve the work efficiency during the electrode renewal in an electrolyser.

[001726] A method for producing an electrolyzer according to a second aspect (hereinafter, also simply called the "second aspect") of the present modality is a method for producing a new electrolyzer by arranging an electrolysis electrode in an existing electrolyzer that comprises an anode, a cathode that is opposite the anode, a membrane that is fixed between the anode and the cathode, and an electrolyzer structure that supports the anode, cathode and membrane, the method comprising a release step (A) a fixation of the membrane on the electrolyzer frame and a step (B ') of electrode arrangement for electrolysis between the membrane and the anode or cathode after step (A).

[001727] As described above, also according to the method for producing an electrolyzer according to the second aspect, it is possible to renew the electrode without removing each component from the outside of the electrolyzer frame, and it is possible to improve the work efficiency during the electrode renewal in an electrolyser.

453/803

[001728] Next, when called the "method to produce an electrolyzer according to the present modality", the method to produce an electrolyzer according to the first aspect and the method to produce an electrolyzer according to the second aspect are incorporated .

[001729] In the method for producing a new electrolyzer according to the present modality, the existing electrolyzer comprises an anode, a cathode that is opposite the anode, a membrane that is arranged between the anode and the cathode, and an electrolyzer frame that supports the anode, cathode and membrane as constituent members. In other words, the existing electrolyzer comprises a membrane, an electrolytic cell and an electrolyzer frame that supports the membrane and the electrolytic cell. The existing electrolyzer is not particularly limited as long as it comprises the constituent members described above, and several known configurations can be used.

[001730] In the method to produce an electrolyzer according to the present modality, a new electrolyzer additionally comprises an electrode for electrolysis or a laminate, in addition to a member that has already served as an anode or cathode in the existing electrolyzer. That is, in the first aspect and in the second aspect, the “electrolysis electrode” arranged in the production of a new electrolyzer serves as an anode or cathode, and is separated from the cathode and anode in the existing electrolyzer. In the method for producing an electrolyzer in accordance with the present modality, even in the case where the electrolytic performance of the anode and / or cathode has deteriorated in association with the operation of the existing electrolyzer, the arrangement of a separate electrolysis electrode allows the characteristics anode and / or cathode are renewed. In the first aspect, in which a laminate is used, a new ion exchange membrane is arranged in combination and, thus, the characteristics of the ion exchange membrane with characteristics that have deteriorated in association with the operation can be renewed simultaneously. “Renew the features”

453/803

[001728] Next, when called the "method to produce an electrolyzer according to the present modality", the method to produce an electrolyzer according to the first aspect and the method to produce an electrolyzer according to the second aspect are incorporated .

[001729] In the method for producing a new electrolyzer according to the present modality, the existing electrolyzer comprises an anode, a cathode that is opposite the anode, a membrane that is arranged between the anode and the cathode, and an electrolyzer frame that supports the anode, cathode and membrane as constituent members. In other words, the existing electrolyzer comprises a membrane, an electrolytic cell and an electrolyzer frame that supports the membrane and the electrolytic cell. The existing electrolyzer is not particularly limited as long as it comprises the constituent members described above, and several known configurations can be used.

[001730] In the method to produce an electrolyzer according to the present modality, a new electrolyzer additionally comprises an electrode for electrolysis or a laminate, in addition to a member that has already served as an anode or cathode in the existing electrolyzer. That is, in the first aspect and in the second aspect, the “electrolysis electrode” arranged in the production of a new electrolyzer serves as an anode or cathode, and is separated from the cathode and anode in the existing electrolyzer. In the method for producing an electrolyzer in accordance with the present modality, even in the case where the electrolytic performance of the anode and / or cathode has deteriorated in association with the operation of the existing electrolyzer, the arrangement of a separate electrolysis electrode allows the characteristics anode and / or cathode are renewed. In the first aspect, in which a laminate is used, a new ion exchange membrane is arranged in combination and, thus, the characteristics of the ion exchange membrane with characteristics that have deteriorated in association with the operation can be renewed simultaneously. “Renew the features”

454/803 referred to herein means having characteristics comparable to the initial characteristics possessed by the existing electrolyzer before being operated or having characteristics superior to the initial characteristics.

[001731] In the method to produce an electrolyzer according to the present modality, the existing electrolyzer is assumed to be an “electrolyzer that has already been operated” and it is assumed that the new electrolyzer is an “electrolyzer that has not yet been operated” . That is, once an electrolyser produced as a new electrolyser is operated, the electrolyser becomes “the existing electrolyser in the present modality”. The arrangement of an electrolysis electrode or a laminate in this existing electrolyser provides "a new electrolyser of the present modality".

[001732] Hereinafter, a case of conducting common salt electrolysis using an ion exchange membrane as the membrane is taken as an example, and an embodiment of the electrolyzer will be described in detail. In the <Seventh modality> section, unless otherwise specified, "the electrolyzer in the present modality" incorporates both "the existing electrolyzer in the present modality" and "the new electrolyzer in the present modality". [Electrolytic cell]

[001733] First, the electrolytic cell will be described, which can be used as a constituent unit of the electrolyzer in the present modality. Figure 112 illustrates a cross-sectional view of an electrolytic cell 1.

[001734] The electrolytic cell 1 comprises an anodic chamber 10, a cathodic chamber 20, a partition wall 30 placed between the anodic chamber 10 and the cathodic chamber 20, an anode 11 placed in the anodic chamber and a cathode 21 placed in the cathodic chamber 20 As required, the electrolytic cell 1 has a substrate 18a and a reverse current absorbent layer 18b formed on the substrate 18a and can comprise a reverse current absorber 18 placed in the cathode chamber. Anode 11 and

454/803 referred to herein means having characteristics comparable to the initial characteristics possessed by the existing electrolyzer before being operated or having characteristics superior to the initial characteristics.

[001731] In the method to produce an electrolyzer according to the present modality, the existing electrolyzer is assumed to be an “electrolyzer that has already been operated” and it is assumed that the new electrolyzer is an “electrolyzer that has not yet been operated” . That is, once an electrolyser produced as a new electrolyser is operated, the electrolyser becomes “the existing electrolyser in the present modality”. The arrangement of an electrolysis electrode or a laminate in this existing electrolyser provides "a new electrolyser of the present modality".

[001732] Hereinafter, a case of conducting common salt electrolysis using an ion exchange membrane as the membrane is taken as an example, and an embodiment of the electrolyzer will be described in detail. In the <Seventh modality> section, unless otherwise specified, "the electrolyzer in the present modality" incorporates both "the existing electrolyzer in the present modality" and "the new electrolyzer in the present modality". [Electrolytic cell]

[001733] First, the electrolytic cell will be described, which can be used as a constituent unit of the electrolyzer in the present modality. Figure 112 illustrates a cross-sectional view of an electrolytic cell 1.

[001734] The electrolytic cell 1 comprises an anodic chamber 10, a cathodic chamber 20, a partition wall 30 placed between the anodic chamber 10 and the cathodic chamber 20, an anode 11 placed in the anodic chamber and a cathode 21 placed in the cathodic chamber 20 As required, the electrolytic cell 1 has a substrate 18a and a reverse current absorbent layer 18b formed on the substrate 18a and can comprise a reverse current absorber 18 placed in the cathode chamber. Anode 11 and

455/803 cathode 21 belonging to electrolytic cell 1 are electrically connected to each other.

In other words, the electrolytic cell 1 comprises the following cathode structure.

The cathode structure 40 comprises the cathode chamber 20, the cathode 21 placed in the cathode chamber 20 and the reverse current absorber 18 placed in the cathode chamber 20, the reverse current absorber 18 has the substrate 18a and the reverse current absorbent layer 18b on substrate 18a, as shown in Figure 116, and cathode 21 and reverse current absorbing layer 18b are electrically connected.

The cathodic chamber 20 also has a collector 23, a support 24 supporting the collector and an elastic metal body 22. The elastic metal body 22 is placed between the collector 23 and the cathode 21. The support 24 is placed between the collector 23 and the partition wall 30. The collector 23 is electrically connected to the cathode 21 through the elastic metal body 22. The partition wall 30 is electrically connected to the collector 23 through the support 24. Therefore, the partition wall 30, the support 24, the collector 23, the elastic metal body 22 and the cathode 21 are electrically connected.

Cathode 21 and reverse current absorbing layer 18b are electrically connected.

Cathode 21 and the reverse current absorbing layer can be directly connected or they can be indirectly connected through the collector, the support, the elastic metal body, the partition wall or the like.

The entire surface of cathode 21 is preferably covered with a layer of catalyst for the reduction reaction.

The electrical connection form can be a form in which the partition wall 30 and the support 24, the support 24 and the collector 23, and the collector 23 and the elastic metal body 22 are each directly attached and the cathode 21 it is laminated to the elastic metal body 22. Examples of a method for directly affixing these constituent components to each other include welding and the like.

Alternatively, the reverse current absorber 18, cathode 21 and collector 23 can be collectively called a cathode structure 40.

455/803 cathode 21 belonging to electrolytic cell 1 are electrically connected to each other.

In other words, the electrolytic cell 1 comprises the following cathode structure.

The cathode structure 40 comprises the cathode chamber 20, the cathode 21 placed in the cathode chamber 20 and the reverse current absorber 18 placed in the cathode chamber 20, the reverse current absorber 18 has the substrate 18a and the reverse current absorbent layer 18b on substrate 18a, as shown in Figure 116, and cathode 21 and reverse current absorbing layer 18b are electrically connected.

The cathodic chamber 20 also has a collector 23, a support 24 supporting the collector and an elastic metal body 22. The elastic metal body 22 is placed between the collector 23 and the cathode 21. The support 24 is placed between the collector 23 and the partition wall 30. The collector 23 is electrically connected to the cathode 21 through the elastic metal body 22. The partition wall 30 is electrically connected to the collector 23 through the support 24. Therefore, the partition wall 30, the support 24, the collector 23, the elastic metal body 22 and the cathode 21 are electrically connected.

Cathode 21 and reverse current absorbing layer 18b are electrically connected.

Cathode 21 and the reverse current absorbing layer can be directly connected or they can be indirectly connected through the collector, the support, the elastic metal body, the partition wall or the like.

The entire surface of cathode 21 is preferably covered with a layer of catalyst for the reduction reaction.

The electrical connection form can be a form in which the partition wall 30 and the support 24, the support 24 and the collector 23, and the collector 23 and the elastic metal body 22 are each directly attached and the cathode 21 it is laminated to the elastic metal body 22. Examples of a method for directly affixing these constituent components to each other include welding and the like.

Alternatively, the reverse current absorber 18, cathode 21 and collector 23 can be collectively called a cathode structure 40.

456/803

[001735] Figure 113 illustrates a cross-sectional view of two electrolytic cells 1 that are adjacent in the electrolyzer 4. Figure 114 shows an electrolyzer 4 as an existing electrolyzer. Figure 115 shows an electrolyzer assembly step 4 (different from steps (A) to (B) and steps (A) to (B ”)).

[001736] As shown in Figure 113, an electrolytic cell 1, a cation exchange membrane 2 and an electrolytic cell 1 are arranged in series in the order mentioned. An ion exchange membrane 2 is arranged between the anode chamber of an electrolytic cell 1 of the two adjacent electrolytic cells in the electrolyzer and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent to it are separated by the cation exchange membrane 2. As shown in Figure 114, the electrolyzer 4 is composed so that the plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2 is supported by a electrolyzer frame 8. That is, electrolyzer 4 is a bipolar electrolyzer that comprises the plurality of electrolytic cells 1 arranged in series and ion exchange membranes 2, each arranged between adjacent electrolytic cells 1, and the electrolyzer frame 8 that supports cells 1 and membranes 2. As shown in Figure 115, electrolyzer 4 is assembled arranging the plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2 and coupling the cells by means of a pressure device 5 to the electrolyzer frame 8. The electrolyzer frame is not particularly limited, as long as it is capable of supporting each of the members, as well as coupling the members, and several known configurations can be used. The device for coupling each of the members, possessed by the frame of the electrolyzer, is not particularly limited, and examples of it include hydraulic presses and devices that comprise a tie as a

456/803

[001735] Figure 113 illustrates a cross-sectional view of two electrolytic cells 1 that are adjacent in the electrolyzer 4. Figure 114 shows an electrolyzer 4 as an existing electrolyzer. Figure 115 shows an electrolyzer assembly step 4 (different from steps (A) to (B) and steps (A) to (B ”)).

[001736] As shown in Figure 113, an electrolytic cell 1, a cation exchange membrane 2 and an electrolytic cell 1 are arranged in series in the order mentioned. An ion exchange membrane 2 is arranged between the anode chamber of an electrolytic cell 1 of the two adjacent electrolytic cells in the electrolyzer and the cathode chamber of the other electrolytic cell 1. That is, the anode chamber 10 of the electrolytic cell 1 and the cathode chamber 20 of the electrolytic cell 1 adjacent to it are separated by the cation exchange membrane 2. As shown in Figure 114, the electrolyzer 4 is composed so that the plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2 is supported by a electrolyzer frame 8. That is, electrolyzer 4 is a bipolar electrolyzer that comprises the plurality of electrolytic cells 1 arranged in series and ion exchange membranes 2, each arranged between adjacent electrolytic cells 1, and the electrolyzer frame 8 that supports cells 1 and membranes 2. As shown in Figure 115, electrolyzer 4 is assembled arranging the plurality of electrolytic cells 1 connected in series through the ion exchange membrane 2 and coupling the cells by means of a pressure device 5 to the electrolyzer frame 8. The electrolyzer frame is not particularly limited, as long as it is capable of supporting each of the members, as well as coupling the members, and several known configurations can be used. The device for coupling each of the members, possessed by the frame of the electrolyzer, is not particularly limited, and examples of it include hydraulic presses and devices that comprise a tie as a

457/803 mechanism.

[001737] Electrolyser 4 has an anodic terminal 7 and a cathodic terminal 6 to be connected to a power supply. Anode 11 of electrolytic cell 1 located at the far end between the plurality of electrolytic cells 1 coupled in series in electrolyzer 4 is electrically connected to anode terminal 7. Cathode 21 of the electrolytic cell located at the opposite end to anode terminal 7 between the plurality of electrolytic cells 1 coupled in series in the electrolyzer 4 is electrically connected to the cathodic terminal 6. The electrical current during electrolysis flows from the side of the anodic terminal 7, through the anode and cathode of each electrolytic cell 1, towards the cathodic terminal 6. At the two ends of the coupled electrolytic cells 1, an electrolytic cell with only one anodic chamber (anode terminal cell) and an electrolytic cell with only one cathodic chamber (cathode terminal cell) can be arranged. In that case, anode terminal 7 is connected to the cell of the anode terminal, arranged at one end, and cathode terminal 6 is connected to the cell of the cathode terminal, arranged at the other end.

[001738] In the case of electrolytic brine, brine is provided for each anodic chamber 10 and pure water or an aqueous solution of low concentration sodium hydroxide is provided for each cathodic chamber 20. Each liquid is supplied from a supply tube of electrolytic solution (not shown in the Figure), through an electrolytic solution supply hose (not shown in the Figure), for each electrolytic cell 1. The electrolyte solution and electrolysis products are recovered from an electrolyte recovery tube (not shown in the figure). During electrolysis, the sodium ions in the brine migrate from the anode chamber 10 of the electrolytic cell 1, through the ion exchange membrane 2, to the cathode chamber 20 of the adjacent electrolytic cell 1. Thus, the electric current during electrolysis flows in the direction where electrolytic cells 1 are

457/803 mechanism.

[001737] Electrolyser 4 has an anodic terminal 7 and a cathodic terminal 6 to be connected to a power supply. Anode 11 of electrolytic cell 1 located at the far end between the plurality of electrolytic cells 1 coupled in series in electrolyzer 4 is electrically connected to anode terminal 7. Cathode 21 of the electrolytic cell located at the opposite end to anode terminal 7 between the plurality of electrolytic cells 1 coupled in series in the electrolyzer 4 is electrically connected to the cathodic terminal 6. The electrical current during electrolysis flows from the side of the anodic terminal 7, through the anode and cathode of each electrolytic cell 1, towards the cathodic terminal 6. At the two ends of the coupled electrolytic cells 1, an electrolytic cell with only one anodic chamber (anode terminal cell) and an electrolytic cell with only one cathodic chamber (cathode terminal cell) can be arranged. In that case, anode terminal 7 is connected to the cell of the anode terminal, arranged at one end, and cathode terminal 6 is connected to the cell of the cathode terminal, arranged at the other end.

[001738] In the case of electrolytic brine, brine is provided for each anodic chamber 10 and pure water or an aqueous solution of low concentration sodium hydroxide is provided for each cathodic chamber 20. Each liquid is supplied from a supply tube of electrolytic solution (not shown in the Figure), through an electrolytic solution supply hose (not shown in the Figure), for each electrolytic cell 1. The electrolyte solution and electrolysis products are recovered from an electrolyte recovery tube (not shown in the figure). During electrolysis, the sodium ions in the brine migrate from the anode chamber 10 of the electrolytic cell 1, through the ion exchange membrane 2, to the cathode chamber 20 of the adjacent electrolytic cell 1. Thus, the electric current during electrolysis flows in the direction where electrolytic cells 1 are

458/803 coupled in series. That is, the electric current flows, through the cation exchange membrane 2, from the anodic chamber 10 towards the cathodic chamber 20. As the brine is electrolyzed, chlorine gas is generated on the anode side 11, and sodium hydroxide (solute ) and hydrogen gas are generated on the cathode side

21. (Anodic chamber)

[001739] The anodic chamber 10 has anode 11 or the supply conductor of anode 11. The supply conductor is referred to here to mean a degraded electrode (i.e., the existing electrode), an electrode without a catalyst coating and the like. When the electrode for electrolysis in the present embodiment is inserted on the anode side, 11 serves as a feed conductor for the anode. When the electrode for electrolysis in the present embodiment is not inserted on the anode side, 11 serves as an anode. The anode chamber 10 preferably has an electrolyte solution supply unit on the anode side that provides an electrolyte solution for the anode chamber 10, a baffle plate which is arranged above the anode side electrolyte solution supply unit to be substantially parallel or oblique to a partition wall 30, and a liquid and gas separation unit on the anode side which is arranged above the baffle to separate the gas from the electrolytic solution including the mixed gas. (Anode)

[001740] When the electrode for electrolysis in the present modality is not inserted on the side of the anode, an anode 11 is provided in the frame of the anodic chamber 10 (that is, the anodic frame). Like anode 11, a metal electrode such as the so-called DSA (R) can be used. DSA is an electrode that includes a titanium substrate whose surface is covered with an oxide that contains ruthenium, iridium and titanium as components.

[001741] As a form, any perforated metal, fabric can be used

458/803 coupled in series. That is, the electric current flows, through the cation exchange membrane 2, from the anodic chamber 10 towards the cathodic chamber 20. As the brine is electrolyzed, chlorine gas is generated on the anode side 11, and sodium hydroxide (solute ) and hydrogen gas are generated on the cathode side

21. (Anodic chamber)

[001739] The anodic chamber 10 has anode 11 or the supply conductor of anode 11. The supply conductor is referred to here to mean a degraded electrode (i.e., the existing electrode), an electrode without a catalyst coating and the like. When the electrode for electrolysis in the present embodiment is inserted on the anode side, 11 serves as a feed conductor for the anode. When the electrode for electrolysis in the present embodiment is not inserted on the anode side, 11 serves as an anode. The anode chamber 10 preferably has an electrolyte solution supply unit on the anode side that provides an electrolyte solution for the anode chamber 10, a baffle plate which is arranged above the anode side electrolyte solution supply unit to be substantially parallel or oblique to a partition wall 30, and a liquid and gas separation unit on the anode side which is arranged above the baffle to separate the gas from the electrolytic solution including the mixed gas. (Anode)

[001740] When the electrode for electrolysis in the present modality is not inserted on the side of the anode, an anode 11 is provided in the frame of the anodic chamber 10 (that is, the anodic frame). Like anode 11, a metal electrode such as the so-called DSA (R) can be used. DSA is an electrode that includes a titanium substrate whose surface is covered with an oxide that contains ruthenium, iridium and titanium as components.

[001741] As a form, any perforated metal, fabric can be used

459/803 nonwoven, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like. (Anode feed conductor)

[001742] When the electrode for electrolysis in the present modality is inserted on the anode side, the anode 11 feeder conductor is provided in the anode chamber 10 frame. As the anode 11 feeder conductor, a metal electrode can be used , such as the so-called DSA (R), and titanium without catalyst coating can also be used. Alternatively, DSA with a thinner catalyst coating can also be used. In addition, a used anode can also be used.

[001743] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Anode side electrolyte solution supply unit)

[001744] The electrode solution supply unit on the anode side, which supplies the electrolyte solution to the anode chamber 10, is connected to the electrolyte solution supply tube. The electrolytic solution supply unit on the anode side is preferably arranged below the anode chamber 10. As the electrolytic solution supply unit on the anode side, for example, a tube can be used on the surface from which orifice portions are formed. (dispersion tube) and the like. Such a tube is most preferably arranged along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell. This tube is connected to an electrolytic solution supply tube (liquid supply nozzle) that supplies the electrolytic solution to the electrolytic cell 1. The electrolyte solution supplied from the liquid supply nozzle is transported with a tube into the electrolytic cell 1 and formed to

459/803 nonwoven, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like. (Anode feed conductor)

[001742] When the electrode for electrolysis in the present modality is inserted on the anode side, the anode 11 feeder conductor is provided in the anode chamber 10 frame. As the anode 11 feeder conductor, a metal electrode can be used , such as the so-called DSA (R), and titanium without catalyst coating can also be used. Alternatively, DSA with a thinner catalyst coating can also be used. In addition, a used anode can also be used.

[001743] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Anode side electrolyte solution supply unit)

[001744] The electrode solution supply unit on the anode side, which supplies the electrolyte solution to the anode chamber 10, is connected to the electrolyte solution supply tube. The electrolytic solution supply unit on the anode side is preferably arranged below the anode chamber 10. As the electrolytic solution supply unit on the anode side, for example, a tube can be used on the surface from which orifice portions are formed. (dispersion tube) and the like. Such a tube is most preferably arranged along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell. This tube is connected to an electrolytic solution supply tube (liquid supply nozzle) that supplies the electrolytic solution to the electrolytic cell 1. The electrolyte solution supplied from the liquid supply nozzle is transported with a tube into the electrolytic cell 1 and formed to

460/803 from the orifice portions provided on the surface of the tube into the anode chamber 10. The arrangement of the tube along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell is preferable because the electrolyte solution can be uniformly supplied to inside the anodic chamber

10. (Liquid and gas separation unit on the anode side)

[001745] The liquid and gas separation unit on the anode side is preferably arranged above the baffle plate. The liquid and gas separation unit on the anode side has the function of separating the produced gas such as chlorine gas from the electrolytic solution during electrolysis. Unless otherwise specified, above means the upper direction in electrolytic cell 1 in Figure 112, and below means the lower direction in electrolytic cell 1 in Figure 112.

[001746] During electrolysis, the produced gas generated in electrolytic cell 1 and the electrolytic solution form a mixed phase (mixed gas-liquid phase), which is then emitted out of the system. Subsequently, pressure fluctuations within the electrolytic cell 1 cause vibration, which can result in physical damage to the ion exchange membrane. In order to avoid this event, the electrolytic cell 1 in the present embodiment is preferably provided with a liquid and gas separation unit on the anode side to separate the gas from the liquid. The liquid and gas separation unit on the anode side is preferably provided with an anti-foam plate to eliminate bubbles. When the flow of the mixed gas-liquid phase passes through the antifoam plate, the bubbles burst, thus allowing the electrolyte solution and the gas to be separated. As a result, vibration during electrolysis can be avoided. (Baffle plate)

[001747] The baffle plate is preferably arranged above the electrolyte solution supply unit on the anode side and arranged

460/803 from the orifice portions provided on the surface of the tube into the anode chamber 10. The arrangement of the tube along the surface of anode 11 and parallel to the bottom 19 of the electrolytic cell is preferable because the electrolyte solution can be uniformly supplied to inside the anodic chamber

10. (Liquid and gas separation unit on the anode side)

[001745] The liquid and gas separation unit on the anode side is preferably arranged above the baffle plate. The liquid and gas separation unit on the anode side has the function of separating the produced gas such as chlorine gas from the electrolytic solution during electrolysis. Unless otherwise specified, above means the upper direction in electrolytic cell 1 in Figure 112, and below means the lower direction in electrolytic cell 1 in Figure 112.

[001746] During electrolysis, the produced gas generated in electrolytic cell 1 and the electrolytic solution form a mixed phase (mixed gas-liquid phase), which is then emitted out of the system. Subsequently, pressure fluctuations within the electrolytic cell 1 cause vibration, which can result in physical damage to the ion exchange membrane. In order to avoid this event, the electrolytic cell 1 in the present embodiment is preferably provided with a liquid and gas separation unit on the anode side to separate the gas from the liquid. The liquid and gas separation unit on the anode side is preferably provided with an anti-foam plate to eliminate bubbles. When the flow of the mixed gas-liquid phase passes through the antifoam plate, the bubbles burst, thus allowing the electrolyte solution and the gas to be separated. As a result, vibration during electrolysis can be avoided. (Baffle plate)

[001747] The baffle plate is preferably arranged above the electrolyte solution supply unit on the anode side and arranged

461/803 substantially parallel or obliquely to the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anodic chamber 10. When the baffle plate is provided, it is possible to make the electrolyte solution (brine or similar) circulate internally in the anodic chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged in such a way as to separate the space in the vicinity of anode 11 from the space near the partition wall 30. From such a point of view, the baffle plate is preferably placed so as to be opposite the surface of anode 11 and the surface of the dividing wall 30. In the space next to the anode divided by the deflector plate, as the electrolysis progresses, the concentration of the electrolytic solution (brine concentration) is reduced and the gas produced, such as chlorine gas is generated. This results in a difference in specific gas-liquid gravity between the space near anode 11 and the space near the dividing wall 30 divided by the deflector plate. By using the difference, it is possible to promote the internal circulation of the electrolytic solution in the anodic chamber 10 to thus make the distribution of concentration of the electrolytic solution in the anodic chamber 10 more uniform.

[001748] Although not shown in Figure 112, a collector can be additionally provided inside the anodic chamber 10. The material and configuration of such a collector can be the same as the cathode chamber collector mentioned below. In anode chamber 10, anode 11 per se can also serve as a collector. (Partition wall)

[001749] The partition wall 30 is arranged between the anodic chamber 10 and the cathodic chamber 20. The partition wall 30 can be called a separator, and the anodic chamber 10 and the cathodic chamber 20 are divided by the partition wall 30. Like the wall partition 30, one known as an electrolysis separator can be used, and an example of this includes a wall

461/803 substantially parallel or obliquely to the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolyte solution in the anodic chamber 10. When the baffle plate is provided, it is possible to make the electrolyte solution (brine or similar) circulate internally in the anodic chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably arranged in such a way as to separate the space in the vicinity of anode 11 from the space near the partition wall 30. From such a point of view, the baffle plate is preferably placed so as to be opposite the surface of anode 11 and the surface of the dividing wall 30. In the space next to the anode divided by the deflector plate, as the electrolysis progresses, the concentration of the electrolytic solution (brine concentration) is reduced and the gas produced, such as chlorine gas is generated. This results in a difference in specific gas-liquid gravity between the space near anode 11 and the space near the dividing wall 30 divided by the deflector plate. By using the difference, it is possible to promote the internal circulation of the electrolytic solution in the anodic chamber 10 to thus make the distribution of concentration of the electrolytic solution in the anodic chamber 10 more uniform.

[001748] Although not shown in Figure 112, a collector can be additionally provided inside the anodic chamber 10. The material and configuration of such a collector can be the same as the cathode chamber collector mentioned below. In anode chamber 10, anode 11 per se can also serve as a collector. (Partition wall)

[001749] The partition wall 30 is arranged between the anodic chamber 10 and the cathodic chamber 20. The partition wall 30 can be called a separator, and the anodic chamber 10 and the cathodic chamber 20 are divided by the partition wall 30. Like the wall partition 30, one known as an electrolysis separator can be used, and an example of this includes a wall

462/803 partition formed by welding a plate comprising nickel beside the cathode and a plate comprising titanium beside the anode. (Cathodic chamber)

[001750] In the cathodic chamber 20, when the electrode for electrolysis in the present modality is inserted on the cathode side, 21 serves as a cathode supply conductor. When the electrolysis electrode in the present embodiment is not inserted on the cathode side, 21 it serves as a cathode. When a reverse current absorber is included, the cathode or cathode supply conductor 21 is electrically connected to the reverse current absorber. The cathode chamber 20, similarly to the anode chamber 10, preferably has an electrolytic solution supply unit on the cathode side and a liquid and gas separation unit on the cathode side. Among the components that make up the cathodic chamber 20, components similar to those that make up the anode chamber 10 will not be described. (Cathode)

[001751] When the electrode for electrolysis in the present embodiment is not inserted on the side of the cathode, a cathode 21 is provided in the frame of the cathodic chamber 20 (that is, the cathodic frame). Cathode 21 preferably has a nickel substrate and a catalyst layer that covers the nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include metals such as Ru, C, Si, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, y-alloying, composite dispersion / galvanization, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as

462/803 partition formed by welding a plate comprising nickel beside the cathode and a plate comprising titanium beside the anode. (Cathodic chamber)

[001750] In the cathodic chamber 20, when the electrode for electrolysis in the present modality is inserted on the cathode side, 21 serves as a cathode supply conductor. When the electrolysis electrode in the present embodiment is not inserted on the cathode side, 21 it serves as a cathode. When a reverse current absorber is included, the cathode or cathode supply conductor 21 is electrically connected to the reverse current absorber. The cathode chamber 20, similarly to the anode chamber 10, preferably has an electrolytic solution supply unit on the cathode side and a liquid and gas separation unit on the cathode side. Among the components that make up the cathodic chamber 20, components similar to those that make up the anode chamber 10 will not be described. (Cathode)

[001751] When the electrode for electrolysis in the present embodiment is not inserted on the side of the cathode, a cathode 21 is provided in the frame of the cathodic chamber 20 (that is, the cathodic frame). Cathode 21 preferably has a nickel substrate and a catalyst layer that covers the nickel substrate. Examples of the components of the catalyst layer on the nickel substrate include metals such as Ru, C, Si, P, S, AI, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb , Mo, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd , Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, y-alloying, composite dispersion / galvanization, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as

463/803 required. Cathode 21 can be subjected to a reduction treatment as needed. As the cathode 21 substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[001752] As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Cathode supply conductor)

[001753] When the electrode for electrolysis in the present embodiment is inserted on the side of the cathode, a cathode 21 supply conductor is provided in the cathode chamber 20 frame. The cathode 21 supply conductor can be covered with a catalytic component. The catalytic component can be a component that is originally used as the cathode and remains. Examples of the catalyst layer components include metals such as Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh , Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, I, Gd, Tb, Dy , Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, alloy galvanizing, composite dispersion / galvanizing, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Nickel, nickel alloys and nickel or stainless galvanized iron without catalyst coating can be used. As the cathode 21 feed conductor substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[001754] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by

463/803 required. Cathode 21 can be subjected to a reduction treatment as needed. As the cathode 21 substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[001752] As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by knitted metal lines and the like can be used. (Cathode supply conductor)

[001753] When the electrode for electrolysis in the present embodiment is inserted on the side of the cathode, a cathode 21 supply conductor is provided in the cathode chamber 20 frame. The cathode 21 supply conductor can be covered with a catalytic component. The catalytic component can be a component that is originally used as the cathode and remains. Examples of the catalyst layer components include metals such as Ru, C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Rh , Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, I, Gd, Tb, Dy , Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides. Examples of the method for forming the catalyst layer include galvanizing, alloy galvanizing, composite dispersion / galvanizing, CVD, PVD, pyrolysis and spraying. These methods can be used in combination. The catalyst layer can have a plurality of layers and a plurality of elements, as needed. Nickel, nickel alloys and nickel or stainless galvanized iron without catalyst coating can be used. As the cathode 21 feed conductor substrate, nickel, nickel alloys and nickel or stainless galvanized iron can be used.

[001754] As a form, any perforated metal, non-woven fabric, foamy metal, expanded metal, porous metal sheet formed by electroforming, the so-called woven mesh produced by

464/803 knitted metal and the like. (Reverse current absorbing layer)

[001755] A material with a less noble redox potential than the element's redox potential for the catalyst layer of the cathode mentioned above can be selected as a material for the reverse current absorbing layer. Examples of it include nickel and iron. (Collector)

[001756] The cathodic chamber 20 preferably comprises the collector

23. Collector 23 improves the efficiency of the current collection. In the present embodiment, the collector 23 is a porous plate and is preferably arranged substantially parallel to the surface of the cathode 21.

[001757] The collector 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. Collector 23 can be a mixture, alloy or composite oxide of these metals. The collector 23 can have any shape, as long as the shape allows the function of the collector and can have a plate or network shape. (Elastic metal body)

[001758] Placing the elastic metal body 22 between the collector 23 and the cathode 21 presses each cathode 21 of the plurality of electrolytic cells 1 connected in series to the ion exchange membrane 2 to reduce the distance between each anode 11 and each cathode 21. Then, it is possible to reduce the voltage to be applied entirely through the plurality of electrolytic cells 1 connected in series. Reducing the voltage reduces energy consumption. With the elastic metal body 22 in place, the pressure caused by the elastic metal body 22 allows the electrolysis electrode to be held steadily in place when the laminate including the electrolysis electrode in the present embodiment is placed in the electrolytic cell.

[001759] As the elastic metal body 22, spring members such as spiral springs and coils and mats can be used

464/803 knitted metal and the like. (Reverse current absorbing layer)

[001755] A material with a less noble redox potential than the element's redox potential for the catalyst layer of the cathode mentioned above can be selected as a material for the reverse current absorbing layer. Examples of it include nickel and iron. (Collector)

[001756] The cathodic chamber 20 preferably comprises the collector

23. Collector 23 improves the efficiency of the current collection. In the present embodiment, the collector 23 is a porous plate and is preferably arranged substantially parallel to the surface of the cathode 21.

[001757] The collector 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. Collector 23 can be a mixture, alloy or composite oxide of these metals. The collector 23 can have any shape, as long as the shape allows the function of the collector and can have a plate or network shape. (Elastic metal body)

[001758] Placing the elastic metal body 22 between the collector 23 and the cathode 21 presses each cathode 21 of the plurality of electrolytic cells 1 connected in series to the ion exchange membrane 2 to reduce the distance between each anode 11 and each cathode 21. Then, it is possible to reduce the voltage to be applied entirely through the plurality of electrolytic cells 1 connected in series. Reducing the voltage reduces energy consumption. With the elastic metal body 22 in place, the pressure caused by the elastic metal body 22 allows the electrolysis electrode to be held steadily in place when the laminate including the electrolysis electrode in the present embodiment is placed in the electrolytic cell.

[001759] As the elastic metal body 22, spring members such as spiral springs and coils and mats can be used

465/803 cushioning. As the elastic metal body 22, a suitable one can be used appropriately, taking into account a tension to pressure the ion exchange membrane and the like. The elastic metal body 22 can be provided on the surface of the collector 23 on the side of the cathode chamber 20 or it can be provided on the surface of the partition wall on the side of the anode chamber 10. Both chambers are normally divided in such a way that the cathode chamber 20 it becomes smaller than the anodic chamber 10. Thus, from the point of view of the strength of the frame and the like, the elastic metal body 22 is preferably provided between the collector 23 and the cathode 21 in the anodic chamber

20. The elastic metal body 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. (Support)

[001760] The cathodic chamber 20 preferably comprises the support 24 that electrically connects the collector 23 to the partition wall 30. This can achieve an efficient current flow.

[001761] The support 24 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. The support 24 can have any shape as long as the support can support the collector 23 and can have a rod, plate or network shape. The support 24 has a plate shape, for example. A plurality of supports 24 is arranged between the partition wall 30 and the collector 23. The plurality of supports 24 are aligned in such a way that their surfaces are in parallel with each other. The supports 24 are arranged substantially perpendicular to the partition wall 30 and the collector 23. (Gasket on the anode side and gasket on the cathode side)

[001762] The anode-side gasket is preferably arranged on the surface of the structure that constitutes the anode chamber 10. The cathode-side gasket is preferably arranged on the surface of the structure that constitutes the cathodic chamber 20. The electrolytic cells are connected to each other other than

465/803 cushioning. As the elastic metal body 22, a suitable one can be used appropriately, taking into account a tension to pressure the ion exchange membrane and the like. The elastic metal body 22 can be provided on the surface of the collector 23 on the side of the cathode chamber 20 or it can be provided on the surface of the partition wall on the side of the anode chamber 10. Both chambers are normally divided in such a way that the cathode chamber 20 it becomes smaller than the anodic chamber 10. Thus, from the point of view of the strength of the frame and the like, the elastic metal body 22 is preferably provided between the collector 23 and the cathode 21 in the anodic chamber

20. The elastic metal body 23 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. (Support)

[001760] The cathodic chamber 20 preferably comprises the support 24 that electrically connects the collector 23 to the partition wall 30. This can achieve an efficient current flow.

[001761] The support 24 preferably comprises an electrically conductive metal, such as nickel, iron, copper, silver and titanium. The support 24 can have any shape as long as the support can support the collector 23 and can have a rod, plate or network shape. The support 24 has a plate shape, for example. A plurality of supports 24 is arranged between the partition wall 30 and the collector 23. The plurality of supports 24 are aligned in such a way that their surfaces are in parallel with each other. The supports 24 are arranged substantially perpendicular to the partition wall 30 and the collector 23. (Gasket on the anode side and gasket on the cathode side)

[001762] The anode-side gasket is preferably arranged on the surface of the structure that constitutes the anode chamber 10. The cathode-side gasket is preferably arranged on the surface of the structure that constitutes the cathodic chamber 20. The electrolytic cells are connected to each other other than

466/803 such that the anode-side gasket included in an electrolytic cell and the cathode-side gasket of an electrolytic cell adjacent to the cell sandwich the ion exchange membrane 2 (see Figure 113). These gaskets can make the connection points airtight when the plurality of electrolytic cells 1 is connected in series through the ion exchange membrane 2.

[001763] The gaskets form a seal between the ion exchange membrane and the electrolytic cells. Specific examples of gaskets include picture frame rubber sheets, in the center of which a hole portion is formed. Gaskets are required to be resistant to corrosive electrolyte solutions or gas produced and to be usable for a long period. Thus, with regard to chemical resistance and hardness, vulcanized products and products cross-linked with ethylene-propylene-diene rubber peroxide (EPDM rubber) and ethylene-propylene rubber (EPM rubber) are normally used as gaskets. Alternatively, gaskets from which the region to be in contact with liquid (liquid contact portion) with a fluorine-containing resin such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers can be used as needed. Such gaskets may have an orifice portion so as not to inhibit the flow of the electrolyte solution, and the shape of the orifice portion is not particularly limited. For example, a picture frame gasket is affixed with an adhesive or similar along the peripheral edge of each hole portion of the anodic chamber frame that constitutes the anodic chamber 10 or the cathodic chamber frame that constitutes the cathodic chamber 20. So, for example, in the case where the two electrolytic cells 1 are connected via the ion exchange membrane 2 (see Figure 113), each electrolytic cell 1 to which the gasket is attached must be tightened via the ion exchange membrane 2. This tightening can prevent the electrolyte solution, alkali metal hydroxide, chlorine gas,

466/803 such that the anode-side gasket included in an electrolytic cell and the cathode-side gasket of an electrolytic cell adjacent to the cell sandwich the ion exchange membrane 2 (see Figure 113). These gaskets can make the connection points airtight when the plurality of electrolytic cells 1 is connected in series through the ion exchange membrane 2.

[001763] The gaskets form a seal between the ion exchange membrane and the electrolytic cells. Specific examples of gaskets include picture frame rubber sheets, in the center of which a hole portion is formed. Gaskets are required to be resistant to corrosive electrolyte solutions or gas produced and to be usable for a long period. Thus, with regard to chemical resistance and hardness, vulcanized products and products cross-linked with ethylene-propylene-diene rubber peroxide (EPDM rubber) and ethylene-propylene rubber (EPM rubber) are normally used as gaskets. Alternatively, gaskets from which the region to be in contact with liquid (liquid contact portion) with a fluorine-containing resin such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) copolymers can be used as needed. Such gaskets may have an orifice portion so as not to inhibit the flow of the electrolyte solution, and the shape of the orifice portion is not particularly limited. For example, a picture frame gasket is affixed with an adhesive or similar along the peripheral edge of each hole portion of the anodic chamber frame that constitutes the anodic chamber 10 or the cathodic chamber frame that constitutes the cathodic chamber 20. So, for example, in the case where the two electrolytic cells 1 are connected via the ion exchange membrane 2 (see Figure 113), each electrolytic cell 1 to which the gasket is attached must be tightened via the ion exchange membrane 2. This tightening can prevent the electrolyte solution, alkali metal hydroxide, chlorine gas,

467/803 hydrogen and the like, generated from electrolysis, escape from electrolytic cells 1. [Laminate]

[001764] In the method for producing an electrolyzer according to the present modality, the electrolysis electrode can be used as a laminate of a membrane, such as an ion exchange membrane or a microporous membrane. That is, the laminate in the present modality comprises the electrode for electrolysis and a new membrane. The new membrane is not particularly limited as long as it is separated from the membrane in the existing electrolyzer, and several known "membranes" can be used. The material, shape, physical and similar properties of the new membrane may be similar to those of the membrane in the existing electrolyzer. Specific examples of the electrolysis electrode and the membrane will be detailed below. (Step (A)

[001765] In step (A) in the first aspect, the membrane fixation is released in the electrolyzer frame. “In the electrolyzer frame” means that step (A) is performed as long as a state is maintained in which the electrolytic cell (that is, the member comprising the anode and cathode) and the membrane are supported by the frame of the electrolyzer, and an aspect in which the electrolytic cell is removed from the electrolyzer frame is excluded. Examples of a method for releasing a membrane fixation include, but are not limited to, a method in which pressure by a pressure device in the electrolyzer frame is released to form an interstice between the electrolytic cell and the membrane in order to allow the membrane to be removable to the outside of the electrolyzer frame. In step (A), the membrane fixation is preferably released on the electrolyzer frame by sliding the anode and cathode towards the arrangement, respectively. The operation allows the membrane to be removable for the

467/803 hydrogen and the like, generated from electrolysis, escape from electrolytic cells 1. [Laminate]

[001764] In the method for producing an electrolyzer according to the present modality, the electrolysis electrode can be used as a laminate of a membrane, such as an ion exchange membrane or a microporous membrane. That is, the laminate in the present modality comprises the electrode for electrolysis and a new membrane. The new membrane is not particularly limited as long as it is separated from the membrane in the existing electrolyzer, and several known "membranes" can be used. The material, shape, physical and similar properties of the new membrane may be similar to those of the membrane in the existing electrolyzer. Specific examples of the electrolysis electrode and the membrane will be detailed below. (Step (A)

[001765] In step (A) in the first aspect, the membrane fixation is released in the electrolyzer frame. “In the electrolyzer frame” means that step (A) is performed as long as a state is maintained in which the electrolytic cell (that is, the member comprising the anode and cathode) and the membrane are supported by the frame of the electrolyzer, and an aspect in which the electrolytic cell is removed from the electrolyzer frame is excluded. Examples of a method for releasing a membrane fixation include, but are not limited to, a method in which pressure by a pressure device in the electrolyzer frame is released to form an interstice between the electrolytic cell and the membrane in order to allow the membrane to be removable to the outside of the electrolyzer frame. In step (A), the membrane fixation is preferably released on the electrolyzer frame by sliding the anode and cathode towards the arrangement, respectively. The operation allows the membrane to be removable for the

468/803 outside the electrolyzer frame without removing the electrolytic cell from the outside of the electrolyzer frame. [Step (B)]

[001766] In step (B) in the first aspect, the membrane in the existing electrolyser is replaced by a laminate after step (A). Examples of the replacement method include, but are not particularly limited to, a method in which an interstice is formed between the electrolytic cell and the ion exchange membrane, then the existing membrane to be renewed is removed, and then a laminate is inserted into the interstice. Through the method, a laminate can be arranged on the surface of the anode or cathode of the existing electrolyzer, and the characteristics of the ion exchange membrane and the anode and / or cathode can be renewed.

[001767] After step (B) is carried out, the laminate is preferably fixed on the frame of the electrolyzer, pressing from the anode and cathode. Specifically, after the membrane is replaced by the laminate, the existing electrolyzer, the laminate and the members in the existing electrolyzer, such as the electrolytic cell, can be coupled by pressing again by means of the pressure device. Through the method, a laminate can be attached to the surface of the anode or cathode in the existing electrolyzer.

[001768] A specific example of steps (A) to (B) in the first aspect will be described based on Figures 117 (A) and (B). First, pressure by a pressure device 5 is released, and a plurality of electrolytic cells 1 and ion exchange membranes 2 are slid in the direction of arrangement thereof. This allows an S interstice to be formed between the electrolytic cell 1 and the ion exchange membrane 2 without removing the electrolytic cell 1 to the outside of the electrolyzer frame 8, and the ion exchange membrane 2 becoming removable to the outside of the electrolyzer frame 8. Subsequently, the ion exchange membrane 2 to be replaced from the

468/803 outside the electrolyzer frame without removing the electrolytic cell from the outside of the electrolyzer frame. [Step (B)]

[001766] In step (B) in the first aspect, the membrane in the existing electrolyser is replaced by a laminate after step (A). Examples of the replacement method include, but are not particularly limited to, a method in which an interstice is formed between the electrolytic cell and the ion exchange membrane, then the existing membrane to be renewed is removed, and then a laminate is inserted into the interstice. Through the method, a laminate can be arranged on the surface of the anode or cathode of the existing electrolyzer, and the characteristics of the ion exchange membrane and the anode and / or cathode can be renewed.

[001767] After step (B) is carried out, the laminate is preferably fixed on the frame of the electrolyzer, pressing from the anode and cathode. Specifically, after the membrane is replaced by the laminate, the existing electrolyzer, the laminate and the members in the existing electrolyzer, such as the electrolytic cell, can be coupled by pressing again by means of the pressure device. Through the method, a laminate can be attached to the surface of the anode or cathode in the existing electrolyzer.

[001768] A specific example of steps (A) to (B) in the first aspect will be described based on Figures 117 (A) and (B). First, pressure by a pressure device 5 is released, and a plurality of electrolytic cells 1 and ion exchange membranes 2 are slid in the direction of arrangement thereof. This allows an S interstice to be formed between the electrolytic cell 1 and the ion exchange membrane 2 without removing the electrolytic cell 1 to the outside of the electrolyzer frame 8, and the ion exchange membrane 2 becoming removable to the outside of the electrolyzer frame 8. Subsequently, the ion exchange membrane 2 to be replaced from the

469/803 an existing electrolyzer is removed from the electrolyzer frame 8, and a laminate 9 from a new ion exchange membrane 2a and an electrolysis electrode 100 is inserted between adjacent electrolytic cells 1 (i.e., the S-gap). In this way, laminate 9 is arranged between adjacent electrolytic cells 1, and these components are supported by the frame of the electrolyzer 8. Then, the plurality of electrolytic cells 1 and laminate 9 are coupled by being pressed in the direction of arrangement a through the pressure device 5. (Step (A ”))

[001769] Also in step (A ') in the second aspect, the membrane fixation is released in the electrolyzer frame, as in the first aspect. Also in step (A '), the membrane fixation is preferably released on the electrolyzer frame by sliding the anode and cathode towards the arrangement, respectively. The operation allows the membrane to be removable to the outside of the electrolyzer frame without removing the electrolytic cell from the outside of the electrolyzer frame. [Step (B ')]

[001770] In step (B ') in the second aspect, an electrolysis electrode is arranged between the membrane and the anode or cathode after step (A). Examples of the method for arranging an electrolysis electrode include, but are not particularly limited to, a method in which, for example, an interstitium is formed between the electrolytic cell and the ion exchange membrane, and then an electrolysis electrode is inserted into the interstitium. . Through the method, the electrolysis electrode can be arranged on the surface of the anode or cathode in the existing electrolyzer, and the characteristics of the anode or cathode can be renewed.

[001771] After step (B ') is performed, the electrolysis electrode is preferably attached to the electrolyzer frame, pressing from the anode and cathode. Specifically, after the electrolysis electrode is

469/803 an existing electrolyzer is removed from the electrolyzer frame 8, and a laminate 9 from a new ion exchange membrane 2a and an electrolysis electrode 100 is inserted between adjacent electrolytic cells 1 (i.e., the S-gap). In this way, laminate 9 is arranged between adjacent electrolytic cells 1, and these components are supported by the frame of the electrolyzer 8. Then, the plurality of electrolytic cells 1 and laminate 9 are coupled by being pressed in the direction of arrangement a through the pressure device 5. (Step (A ”))

[001769] Also in step (A ') in the second aspect, the membrane fixation is released in the electrolyzer frame, as in the first aspect. Also in step (A '), the membrane fixation is preferably released on the electrolyzer frame by sliding the anode and cathode towards the arrangement, respectively. The operation allows the membrane to be removable to the outside of the electrolyzer frame without removing the electrolytic cell from the outside of the electrolyzer frame. [Step (B ')]

[001770] In step (B ') in the second aspect, an electrolysis electrode is arranged between the membrane and the anode or cathode after step (A). Examples of the method for arranging an electrolysis electrode include, but are not particularly limited to, a method in which, for example, an interstitium is formed between the electrolytic cell and the ion exchange membrane, and then an electrolysis electrode is inserted into the interstitium. . Through the method, the electrolysis electrode can be arranged on the surface of the anode or cathode in the existing electrolyzer, and the characteristics of the anode or cathode can be renewed.

[001771] After step (B ') is performed, the electrolysis electrode is preferably attached to the electrolyzer frame, pressing from the anode and cathode. Specifically, after the electrolysis electrode is

470/803 arranged on the surface of the anode or cathode in the existing electrolyser, the electrolysis electrode and the members in the existing electrolyser, such as the electrolytic cell, can be coupled by pressing again by means of the pressure device. Through the method, a laminate can be attached to the surface of the anode or cathode in the existing electrolyzer.

[001772] A specific example of steps (A ') to (B') in the second aspect will be described based on Figures 118 (A) and (B). First, pressure by a pressure device 5 is released, and a plurality of electrolytic cells 1 and ion exchange membranes 2 are slid in the direction of arrangement thereof. This allows an interstitial S to form between the electrolytic cell 1 and the ion exchange membrane 2 without removing the electrolytic cell 1 to the outside of the electrolyzer frame 8. Then, the electrolysis electrode 100 is inserted between the electrolytic cells 1 (or that is, in the interstice S). In this way, the electrolyte electrode 100 is arranged between the adjacent electrolytic cells 1, and these components are supported by the electrolyzer frame 8. Then, the plurality of electrolytic cells 1 and the electrolyte electrode 100 are coupled by being pressed in the direction of arrangement a by means of pressure device 5.

[001773] In step (B) in the first aspect, the laminate is preferably attached to the surface of at least one of the anodes and cathodes at a temperature at which the laminate does not melt.

[001774] The "temperature at which the laminate does not melt" can be identified as the softening point of the new membrane. The temperature may vary depending on the material constituting the membrane, but it is preferably 0 to 100 ° C, more preferably 5 to 80 ° C, even more preferably 10 to 50 ° C.

[001775] The fixation described above is preferably performed under normal pressure.

[001776] In addition, the laminate is preferably obtained by integrating the

470/803 arranged on the surface of the anode or cathode in the existing electrolyser, the electrolysis electrode and the members in the existing electrolyser, such as the electrolytic cell, can be coupled by pressing again by means of the pressure device. Through the method, a laminate can be attached to the surface of the anode or cathode in the existing electrolyzer.

[001772] A specific example of steps (A ') to (B') in the second aspect will be described based on Figures 118 (A) and (B). First, pressure by a pressure device 5 is released, and a plurality of electrolytic cells 1 and ion exchange membranes 2 are slid in the direction of arrangement thereof. This allows an interstitial S to form between the electrolytic cell 1 and the ion exchange membrane 2 without removing the electrolytic cell 1 to the outside of the electrolyzer frame 8. Then, the electrolysis electrode 100 is inserted between the electrolytic cells 1 (or that is, in the interstice S). In this way, the electrolyte electrode 100 is arranged between the adjacent electrolytic cells 1, and these components are supported by the electrolyzer frame 8. Then, the plurality of electrolytic cells 1 and the electrolyte electrode 100 are coupled by being pressed in the direction of arrangement a by means of pressure device 5.

[001773] In step (B) in the first aspect, the laminate is preferably attached to the surface of at least one of the anodes and cathodes at a temperature at which the laminate does not melt.

[001774] The "temperature at which the laminate does not melt" can be identified as the softening point of the new membrane. The temperature may vary depending on the material constituting the membrane, but it is preferably 0 to 100 ° C, more preferably 5 to 80 ° C, even more preferably 10 to 50 ° C.

[001775] The fixation described above is preferably performed under normal pressure.

[001776] In addition, the laminate is preferably obtained by integrating the

471/803 electrode for electrolysis and the new membrane at a temperature where the membrane does not melt and is then used in step (B).

[001777] As a specific method for the above integration, which is not particularly limited, all types of methods, with the exception of typical methods for membrane fusion, such as thermal compression, can be used. A preferable example is a method in which a liquid is interposed between an electrolysis electrode mentioned below and the membrane and the surface tension of the liquid is used to integrate the electrode and the membrane. [Electrode for electrolysis]

[001778] In the method for producing an electrolyzer according to the present modality, the electrolyte for electrolysis is not particularly limited, as long as the electrode can be used for electrolysis. The electrolysis electrode can be an electrode that serves as a cathode in the electrolyzer or it can be an electrode that serves as an anode. As the material, shape and similar of the electrolysis electrode, suitable ones can be appropriately selected, taking into account the electrolyzer and the like. Hereafter, preferable aspects of the electrolysis electrode in the present embodiment will be described, but these are merely exemplary preferable aspects for a case where the electrode is integrated with a new membrane to form a laminate in the first aspect. Electrodes for electrolysis, in addition to the aspects mentioned below, can be properly used.

[001779] The electrolysis electrode in the present embodiment has a force applied per unit mass-unit area of preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mg: in?), even more preferably less than 1.5 N / (mgcm?), even more preferably 1.2 N / mg-cm? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing good property

471/803 electrode for electrolysis and the new membrane at a temperature where the membrane does not melt and is then used in step (B).

[001777] As a specific method for the above integration, which is not particularly limited, all types of methods, with the exception of typical methods for membrane fusion, such as thermal compression, can be used. A preferable example is a method in which a liquid is interposed between an electrolysis electrode mentioned below and the membrane and the surface tension of the liquid is used to integrate the electrode and the membrane. [Electrode for electrolysis]

[001778] In the method for producing an electrolyzer according to the present modality, the electrolyte for electrolysis is not particularly limited, as long as the electrode can be used for electrolysis. The electrolysis electrode can be an electrode that serves as a cathode in the electrolyzer or it can be an electrode that serves as an anode. Like the material, shape and the like of the electrolysis electrode, suitable ones can be appropriately selected, taking into account the electrolyser and the like. Hereafter, preferable aspects of the electrolysis electrode in the present embodiment will be described, but these are merely exemplary preferable aspects for a case where the electrode is integrated with a new membrane to form a laminate in the first aspect. Electrodes for electrolysis, in addition to the aspects mentioned below, can be properly used.

[001779] The electrolysis electrode in the present embodiment has a force applied per unit mass-unit area of preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mg: in?), even more preferably less than 1.5 N / (mgcm?), even more preferably 1.2 N / mg-cm? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing good property

472/803 of manipulation is provided and has a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a supply conductor (a degraded electrode and an electrode without catalyst coating) and the like. Is the applied force even more preferably 1.1 N / mg-cm? or less, even more preferably 1.10 N / mge? or less, particularly preferably 1.0 N / m? or less, especially preferably 1.00 N / mg-cm? or less.

[001780] From the point of view of further improving electrolytic performance, the strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: in?) Or more, even more preferably 0.1 N / mg: cm? or more, even more preferably 0.14 N / (mg: cm?) or more. By force it is even more preferably 0.2 N / (mg: cm?) Or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 m x 2.5 m).

[001781] The applied force described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness, arithmetic mean surface roughness and the like, for example. More specifically, for example, a higher opening ratio tends to lead to a lower applied force, and a lower opening ratio tends to lead to a higher applied force.

[001782] Is the mass per unit preferably 48 mg / cm? or less, more preferably 30 mg / cm? or less, even more preferably 20 mg / cm? or less from the point of view of allowing a good manipulation property, having a good adhesive force for a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a conductive conductor without catalyst coating, and economy , and in addition it is preferably 15 mg / em? or less from a comprehensive point of view including handling, grip and economy properties. The lower limit value is not particularly limited, but

472/803 of manipulation is provided and has a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a supply conductor (a degraded electrode and an electrode without catalyst coating) and the like. Is the applied force even more preferably 1.1 N / mg-cm? or less, even more preferably 1.10 N / mge? or less, particularly preferably 1.0 N / m? or less, especially preferably 1.00 N / mg-cm? or less.

[001780] From the point of view of further improving electrolytic performance, the strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: in?) Or more, even more preferably 0.1 N / mg: cm? or more, even more preferably 0.14 N / (mg: cm?) or more. By force it is even more preferably 0.2 N / (mg: cm?) Or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 m x 2.5 m).

[001781] The applied force described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness, arithmetic mean surface roughness and the like, for example. More specifically, for example, a higher opening ratio tends to lead to a lower applied force, and a lower opening ratio tends to lead to a higher applied force.

[001782] Is the mass per unit preferably 48 mg / cm? or less, more preferably 30 mg / cm? or less, even more preferably 20 mg / cm? or less from the point of view of allowing a good manipulation property, having a good adhesive force for a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode, a conductive conductor without catalyst coating, and economy , and in addition it is preferably 15 mg / em? or less from a comprehensive point of view including handling, grip and economy properties. The lower limit value is not particularly limited, but

473/803 on the order of 1 mg / em ?, for example.

[001783] The mass per unit area described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness and the like, for example. More specifically, for example, when the thickness is constant, a larger opening ratio tends to lead to a smaller mass per unit area, and a smaller opening ratio tends to lead to a mass per unit area greater.

[001784] The applied force can be measured by the methods (1) or (11) described below, which are as detailed in the Examples. As for the applied force, the value obtained by measuring the method (1) (also called “the applied force (1)”) and the value obtained by measuring the method (ii) (also called “the applied force (2) ”) Can be the same or different, and any of the values is preferably less than 1.5 N / (mg: -ecm?). [Method (i)]

[001785] A nickel plate obtained by stripping processing with 320 grain size alumina (1.2 mm thick, 200 square mm), an ion exchange membrane that is obtained by applying particles of inorganic material and a binder on both surfaces of a perfluorocarbon polymer membrane into which an ion exchange group (170 square mm, the detail of the ion exchange membrane referred to here is as described in the Examples) and an electrode sample (130 mm square) ) are rolled in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. The arithmetic mean roughness of the surface (Ra) of the nickel plate after blasting treatment is 0.5 to 0.8 µm. The specific method for calculating the arithmetic mean surface roughness (Ra) is as described in the Examples.

[001786] Under conditions of temperature of 23 + 2ºC and relative humidity

473/803 on the order of 1 mg / em ?, for example.

[001783] The mass per unit area described above can be within the range described above, appropriately adjusting an opening ratio described below, electrode thickness and the like, for example. More specifically, for example, when the thickness is constant, a larger opening ratio tends to lead to a smaller mass per unit area, and a smaller opening ratio tends to lead to a mass per unit area greater.

[001784] The applied force can be measured by the methods (1) or (11) described below, which are as detailed in the Examples. As for the applied force, the value obtained by measuring the method (1) (also called “the applied force (1)”) and the value obtained by measuring the method (ii) (also called “the applied force (2) ”) Can be the same or different, and any of the values is preferably less than 1.5 N / (mg: -ecm?). [Method (i)]

[001785] A nickel plate obtained by stripping processing with 320 grain size alumina (1.2 mm thick, 200 square mm), an ion exchange membrane that is obtained by applying particles of inorganic material and a binder on both surfaces of a perfluorocarbon polymer membrane into which an ion exchange group (170 square mm, the detail of the ion exchange membrane referred to here is as described in the Examples) and an electrode sample (130 mm square) ) are rolled in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. The arithmetic mean roughness of the surface (Ra) of the nickel plate after blasting treatment is 0.5 to 0.8 µm. The specific method for calculating the arithmetic mean surface roughness (Ra) is as described in the Examples.

[001786] Under conditions of temperature of 23 + 2ºC and relative humidity

474/803 of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the load when the electrode sample is raised by 10 mm in a vertical direction is measured. This measurement is repeated three times and the average value is calculated.

[001787] This average value is divided by the area of the overlapping portion of the electrode sample and the ion exchange membrane and the mass of the portion that overlaps the ion exchange membrane in the electrode sample to calculate the force applied per unit of mass- area unit (1) (N / mg-ecm?).

[001788] The force applied per unit mass-unit area (1) obtained by method (i) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg: -em? or less. The strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg: cm?) Or more than the point view of further improving electrolytic performance, and furthermore, it is even more preferably 0.14 N / (mgcm?), even more preferably 0.2 N / (mg: cm?) or more from the point of view of facilitating further manipulation in a large size (for example, a size of 1.5 mx2.5M). [Method (i1)]

474/803 of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the load when the electrode sample is raised by 10 mm in a vertical direction is measured. This measurement is repeated three times and the average value is calculated.

[001787] This average value is divided by the area of the overlapping portion of the electrode sample and the ion exchange membrane and the mass of the portion that overlaps the ion exchange membrane in the electrode sample to calculate the force applied per unit of mass- area unit (1) (N / mg-ecm?).

[001788] The force applied per unit mass-unit area (1) obtained by method (i) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg: -em? or less. The strength is preferably greater than 0.005 N / (mg: in?), More preferably 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg: cm?) Or more than the point view of further improving electrolytic performance, and furthermore, it is even more preferably 0.14 N / (mgcm?), even more preferably 0.2 N / (mg: cm?) or more from the point of view of facilitating further manipulation in a large size (for example, a size of 1.5 mx2.5M). [Method (i1)]

475/803

[001789] A nickel plate obtained by stripping processing with grain size 320 alumina (1.2 mm thickness, 200 square mm, a nickel plate similar to the method (1) above) and an electrode sample ( 130 mm square) is laminated in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the load when the electrode sample is raised by 10 mm in a vertical direction it is measured. This measurement is repeated three times and the average value is calculated.

[001790] This average value is divided by the area of the overlapping portion of the electrode sample and the nickel plate and the mass of the electrode sample in the portion that overlaps the nickel plate to calculate the adhesive force per unit mass-unit of area (2) (N / mg: -cm?).

[001791] The force applied per unit mass-unit area (2) obtained by method (ii) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg: cm? or less. In addition, the force is preferably greater than 0.005 N / (mg: cm?), More preferably

475/803

[001789] A nickel plate obtained by stripping processing with grain size 320 alumina (1.2 mm thickness, 200 square mm, a nickel plate similar to the method (1) above) and an electrode sample ( 130 mm square) is laminated in that order. After that laminate is sufficiently immersed in pure water, the excess water deposited on the laminate surface is removed to obtain a sample for measurement. Under conditions of temperature of 23 + 2ºC and relative humidity of 30 + 5%, only the electrode sample in this sample for measurement is raised in a vertical direction at 10 mm / minute using a tensile and compression testing machine, and the load when the electrode sample is raised by 10 mm in a vertical direction it is measured. This measurement is repeated three times and the average value is calculated.

[001790] This average value is divided by the area of the overlapping portion of the electrode sample and the nickel plate and the mass of the electrode sample in the portion that overlaps the nickel plate to calculate the adhesive force per unit mass-unit of area (2) (N / mg: -cm?).

[001791] The force applied per unit mass-unit area (2) obtained by method (ii) is preferably 1.6 N / (mg: in?) Or less, more preferably less than 1.6 N / (mgem) ?), even more preferably less than 1.5 N / (mg: ecm?), even more preferably 1.2 N / mg-em? or less, even more preferably 1.20 N / mg: cm? or less from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode and a feed conductor without catalyst coating. The applied force is even more preferably 1.1 N / mg: ecm? or less, even more preferably 1.10 N / mg: cm? or less, particularly preferably 1.0 N / mg-cm? or less, especially preferably 1.00 N / mg: cm? or less. In addition, the force is preferably greater than 0.005 N / (mg: cm?), More preferably

476/803 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg-em?) Or more from the point of view of further improving electrolytic performance, and it is even more preferably 0.14 N / (mg: cm?) Or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx2.5 m).

[001792] The electrolyte electrode in the present embodiment preferably includes an electrode electrode substrate and a catalyst layer. The substrate thickness for the electrolysis electrode (gauge thickness) is, but is not particularly limited to, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less , even more preferably 125 µm or less, even more preferably 120 µm or less, even more preferably 100 µm or less from the point of view of enabling a good handling property to be provided, having a good adhesive strength to a membrane, such as a ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, be able to be properly laminated on a roll and folded satisfactorily, facilitating handling in one size large (for example, a size of 1.5 mx 2.5 Mm), and is even more preferably 50 µm or less from the point of view of a handling and economy property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001793] In the method to produce an electrolyzer according to the present modality, in order to integrate a new membrane and the electrolyte for electrolysis, a liquid is preferably interposed between them. Like the liquid, any liquid, such as water and organic solvents, can be used as long as the liquid generates a surface tension. The higher the voltage

476/803 0.08 N / (mg: cm?) Or more, even more preferably 0.1 N / (mg-em?) Or more from the point of view of further improving electrolytic performance, and it is even more preferably 0.14 N / (mg: cm?) Or more from the point of view of facilitating further handling in a large size (for example, a size of 1.5 mx2.5 m).

[001792] The electrolyte electrode in the present embodiment preferably includes an electrode electrode substrate and a catalyst layer. The substrate thickness for the electrolysis electrode (gauge thickness) is, but is not particularly limited to, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less , even more preferably 125 µm or less, even more preferably 120 µm or less, even more preferably 100 µm or less from the point of view of enabling a good handling property to be provided, having a good adhesive strength to a membrane, such as a ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, be able to be properly laminated on a roll and folded satisfactorily, facilitating handling in one size large (for example, a size of 1.5 mx 2.5 Mm), and is even more preferably 50 µm or less from the point of view of a handling and economy property. The lower limit value is not particularly limited, but is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001793] In the method to produce an electrolyzer according to the present modality, in order to integrate a new membrane and the electrolyte for electrolysis, a liquid is preferably interposed between them. Like the liquid, any liquid, such as water and organic solvents, can be used as long as the liquid generates a surface tension. The higher the voltage

477/803 surface of the liquid, the greater the force applied between the new membrane and the electrolysis electrode. Thus, a liquid with a higher surface tension is preferred. Examples of the liquid include the following (the numerical value in parentheses is the surface tension of the liquid at 20ºC): hexane (20.44 mN / m), acetone (23.30 mN / m), methanol (24.00 mN / m ), ethanol (24.05 mN / m), ethylene glycol (50.21 mN / m) and water (72.76 mN / m).

[001794] A liquid with a high surface tension allows the new membrane and the electrolysis electrode to be integrated (to be a laminate), and the renewal of the electrode tends to be easier. The liquid between the new membrane and the electrolysis electrode may be present in an amount such that both adhere to each other by surface tension. As a result, after the laminate is placed in an electrolytic cell, the liquid, if mixed in the electrolytic solution, does not affect the electrolysis itself due to the small amount of the liquid.

[001795] From a practical point of view, a liquid with a surface tension of 24 mN / m to 80 mN / m, such as ethanol, ethylene glycol and water, is preferably used as the liquid. Particularly preferred is water or an aqueous alkaline solution prepared by dissolving caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate or the like in water. Alternatively, the surface tension can be adjusted by allowing these liquids to contain a surfactant. When a surfactant is contained, the adhesion between the new membrane and the electrolysis electrode varies to allow the handling property to be adjusted. The surfactant is not particularly limited and ionic and non-ionic surfactants can be used.

[001796] The proportion measured by the following method (2) of the electrode for electrolysis in the present modality is not particularly limited, but it is

477/803 surface of the liquid, the greater the force applied between the new membrane and the electrolysis electrode. Thus, a liquid with a higher surface tension is preferred. Examples of the liquid include the following (the numerical value in parentheses is the surface tension of the liquid at 20ºC): hexane (20.44 mN / m), acetone (23.30 mN / m), methanol (24.00 mN / m ), ethanol (24.05 mN / m), ethylene glycol (50.21 mN / m) and water (72.76 mN / m).

[001794] A liquid with a high surface tension allows the new membrane and the electrolysis electrode to be integrated (to be a laminate), and the renewal of the electrode tends to be easier. The liquid between the new membrane and the electrolysis electrode may be present in an amount such that both adhere to each other by surface tension. As a result, after the laminate is placed in an electrolytic cell, the liquid, if mixed in the electrolytic solution, does not affect the electrolysis itself due to the small amount of the liquid.

[001795] From a practical point of view, a liquid with a surface tension of 24 mN / m to 80 mN / m, such as ethanol, ethylene glycol and water, is preferably used as the liquid. Particularly preferred is water or an aqueous alkaline solution prepared by dissolving caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate or the like in water. Alternatively, the surface tension can be adjusted by allowing these liquids to contain a surfactant. When a surfactant is contained, the adhesion between the new membrane and the electrolysis electrode varies to allow the handling property to be adjusted. The surfactant is not particularly limited and ionic and non-ionic surfactants can be used.

[001796] The proportion measured by the following method (2) of the electrode for electrolysis in the present modality is not particularly limited, but it is

478/803 preferably 90% or more, more preferably 92% or more from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and more preferably 95% or more from the point of view of facilitating further handling in a large size (for example, a size of 1 , 5 mx 2.5 m). The upper limit value is 100%. [Method (2)]

[001797] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 280 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001798] The proportion measured by the following method (3) of the electrolysis electrode in the present embodiment is not particularly limited, but is preferably 75% or more, more preferably 80% or more from the point of view of allowing a good handling property be provided, have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating and can be properly laminated in a roll is satisfactorily folded, and is most preferably 90% or more of the

478/803 preferably 90% or more, more preferably 92% or more from the point of view of allowing a good handling property to be provided and having a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and more preferably 95% or more from the point of view of facilitating further handling in a large size (for example, a size of 1 , 5 mx 2.5 m). The upper limit value is 100%. [Method (2)]

[001797] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 280 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001798] The proportion measured by the following method (3) of the electrolysis electrode in the present embodiment is not particularly limited, but is preferably 75% or more, more preferably 80% or more from the point of view of allowing a good handling property be provided, have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating and can be properly laminated in a roll is satisfactorily folded, and is most preferably 90% or more of the

479/803 seen to facilitate further handling in a large size (for example, a size of 1.5 m x 2.5 m). The upper limit value is 100%. [Method (3)]

[001799] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 145 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001800] The electrolysis electrode in the present embodiment preferably has, but is not particularly limited to, a porous structure and an aperture ratio or void ratio of 5 to 90% or less from the point of view of enabling a good handling property, have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and prevent the accumulation of gas from being generated during electrolysis. The opening ratio is more preferably 10 to 80% or less, more preferably 20 to 75%.

[001801] The opening ratio is a proportion of the opening portions per unit volume. The calculation method may differ depending on whether the opening portions in submicron size are considered or that only visible openings are considered. In this modality, a volume V is calculated from the values of gauge thickness, width

479/803 seen to facilitate further handling in a large size (for example, a size of 1.5 m x 2.5 m). The upper limit value is 100%. [Method (3)]

[001799] An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in that order. The laminate is placed on a curved surface of a polyethylene tube (outside diameter: 145 mm) so that the electrode sample in that laminate is positioned outside under conditions of a temperature of 23 + 2ºC and a relative humidity of 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, the proportion (%) of a area of a portion where the ion exchange membrane (170 mm square) is in close contact with the electrode sample.

[001800] The electrolysis electrode in the present embodiment preferably has, but is not particularly limited to, a porous structure and an aperture ratio or void ratio of 5 to 90% or less from the point of view of enabling a good handling property, have a good adhesive strength to a membrane such as an ion exchange membrane and a microporous membrane, a degraded electrode (feed conductor), and an electrode (feed conductor) without catalyst coating, and prevent the accumulation of gas from being generated during electrolysis. The opening ratio is more preferably 10 to 80% or less, more preferably 20 to 75%.

[001801] The opening ratio is a proportion of the opening portions per unit volume. The calculation method may differ depending on whether the opening portions in submicron size are considered or that only visible openings are considered. In this modality, a volume V is calculated from the values of gauge thickness, width

480/803 and electrode length and, in addition, a weight W is measured to thereby allow an aperture ratio A to be calculated using the following formula.

A = (1- (W / (YV xp)) x 100

[001802] p is the density of the electrode material (g / cm?). For example, nickel p is 8.908 g / em ”, and titanium p is 4.506 g / em ?. The opening ratio can be appropriately adjusted by changing the area of metal to be drilled per unit area in the case of perforated metal, changing the SW (short diameter), LW (long diameter) and feed values in the case of expanded metal, changing the metal fiber line diameter and mesh number in the case of mesh, changing the pattern of a photoresist to be used in the case of electroforming, changing the diameter of the metal fiber and fiber density in the case of non-woven fabric, changing the mold to form voids in the case of foamed metal or similar.

[001803] Hereinafter, a more specific modality of the electrode for electrolysis will be described in the present modality.

[001804] The electrolysis electrode according to the present embodiment preferably includes a substrate for electrolysis electrode and a layer of catalyst. The catalyst layer can be composed of a plurality of layers, as shown below, or it can be a single layer configuration.

[001805] As shown in Figure 119, an electrolysis electrode 100 according to the present embodiment includes an electrode electrode substrate 10 and a pair of first layers 20 with which both surfaces of the electrode substrate for electrolysis 10 are covered. . The entire electrolyte electrode substrate 10 is preferably covered with the first 20 layers. This coating is likely to improve the activity of the catalyst and the durability of the electrolysis electrode. A first layer 20 can be laminated only on one surface of the substrate to

480/803 and electrode length and, in addition, a weight W is measured to thereby allow an aperture ratio A to be calculated using the following formula.

A = (1- (W / (YV xp)) x 100

[001802] p is the density of the electrode material (g / cm?). For example, nickel p is 8.908 g / em ”, and titanium p is 4.506 g / em ?. The opening ratio can be appropriately adjusted by changing the area of metal to be drilled per unit area in the case of perforated metal, changing the SW (short diameter), LW (long diameter) and feed values in the case of expanded metal, changing the metal fiber line diameter and mesh number in the case of mesh, changing the pattern of a photoresist to be used in the case of electroforming, changing the diameter of the metal fiber and fiber density in the case of non-woven fabric, changing the mold to form voids in the case of foamed metal or similar.

[001803] Hereinafter, a more specific modality of the electrode for electrolysis will be described in the present modality.

[001804] The electrolysis electrode according to the present embodiment preferably includes a substrate for electrolysis electrode and a layer of catalyst. The catalyst layer can be composed of a plurality of layers, as shown below, or it can be a single layer configuration.

[001805] As shown in Figure 119, an electrolysis electrode 100 according to the present embodiment includes an electrode electrode substrate 10 and a pair of first layers 20 with which both surfaces of the electrode substrate for electrolysis 10 are covered. . The entire electrolyte electrode substrate 10 is preferably covered with the first 20 layers. This coating is likely to improve the activity of the catalyst and the durability of the electrolysis electrode. A first layer 20 can be laminated only on one surface of the substrate to

481/803 electrode for electrolysis 10.

[001806] Also as shown in Figure 119, the surfaces of the first layers 20 can be covered with the second layers 30. The first entire layers 20 are preferably covered by the second layers 30. Alternatively, a second layer 30 can be laminated to only one surface of the first layer 20. (Electrode substrate for electrolysis)

[001807] As an electrode substrate for electrolysis 10, for example, nickel, nickel alloys, stainless steel or valve metals including titanium can be used, although not limited to them. The substrate 10 preferably contains at least one element selected from nickel (Ni) and titanium (Ti).

[001808] When stainless steel is used in a high-concentration aqueous alkaline solution, iron and chromium are eluted and the electrical conductivity of stainless steel is about one tenth that of nickel. In view of the above, a substrate containing nickel (Ni) is preferable as a substrate for the electrolysis electrode.

[001809] Alternatively, when the electrode substrate for electrolysis 10 is used in a high concentration saline solution close to saturation under an atmosphere in which chlorine gas is generated, the substrate material for electrode 10 is also preferably titanium with high corrosion resistance.

[001810] The shape of the electrode substrate for electrolysis 10 is not particularly limited, and a shape suitable for the purpose can be selected. As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. Among these, a perforated metal or expanded metal is preferable. Electroforming is a technique to produce a

481/803 electrode for electrolysis 10.

[001806] Also as shown in Figure 119, the surfaces of the first layers 20 can be covered with the second layers 30. The first entire layers 20 are preferably covered by the second layers 30. Alternatively, a second layer 30 can be laminated to only one surface of the first layer 20. (Electrode substrate for electrolysis)

[001807] As an electrode substrate for electrolysis 10, for example, nickel, nickel alloys, stainless steel or valve metals including titanium can be used, although not limited to them. The substrate 10 preferably contains at least one element selected from nickel (Ni) and titanium (Ti).

[001808] When stainless steel is used in a high-concentration aqueous alkaline solution, iron and chromium are eluted and the electrical conductivity of stainless steel is about one tenth that of nickel. In view of the above, a substrate containing nickel (Ni) is preferable as a substrate for the electrolysis electrode.

[001809] Alternatively, when the electrode substrate for electrolysis 10 is used in a high concentration saline solution close to saturation under an atmosphere in which chlorine gas is generated, the substrate material for electrode 10 is also preferably titanium with high corrosion resistance.

[001810] The shape of the electrode substrate for electrolysis 10 is not particularly limited, and a shape suitable for the purpose can be selected. As a form, any perforated metal, non-woven fabric, foamed metal, expanded metal, porous metal foil formed by electroforming, the so-called woven mesh produced by knitted metal threads and the like can be used. Among these, a perforated metal or expanded metal is preferable. Electroforming is a technique to produce a

482/803 thin metal film with a precise pattern using photolithography and electroplating in combination. It is a method that includes the formation of a pattern on a substrate with a photoresist and electroplating of the portion not protected by the resistance to provide a thin metal film.

[001811] As for the shape of the substrate for the electrolysis electrode, an appropriate specification depends on the distance between the anode and the cathode in the electrolyzer. In the case where the distance between the anode and the cathode is finite, a form of expanded metal or perforated metal can be used, and in the case of a so-called zero-interstitial electrolyzer, in which the ion exchange membrane is in contact with the electrode, a woven mesh produced by fine knitted threads, wire mesh, foamy metal, non-woven metallic fabric, expanded metal, perforated metal, porous metal foil and the like can be used, although not limited to it.

[001812] Examples of the electrode substrate for electrolysis 10 include a porous metallic foil, a wire mesh, a nonwoven metal fabric, a perforated metal, an expanded metal and a foamy metal.

[001813] As plate material before being processed into a perforated metal or expanded metal, laminated plate materials and electrolytic sheets are preferred. An electrolytic sheet is preferably still subjected to a galvanizing treatment using the same element as its base material, such as after-treatment, to thereby form roughness and one or both surfaces.

[001814] The thickness of the electrode substrate for electrolysis 10 is, as mentioned above, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less, even more preferably 125 one or less, even more preferably 120 µm or less, even more preferably 100 µm or less, and even more preferably 50 µm or less from the point of view of a handling and economical property. THE

482/803 thin metal film with a precise pattern using photolithography and electroplating in combination. It is a method that includes the formation of a pattern on a substrate with a photoresist and electroplating of the portion not protected by the resistance to provide a thin metal film.

[001811] As for the shape of the substrate for the electrolysis electrode, an appropriate specification depends on the distance between the anode and the cathode in the electrolyzer. In the case where the distance between the anode and the cathode is finite, a form of expanded metal or perforated metal can be used, and in the case of a so-called zero-interstitial electrolyzer, in which the ion exchange membrane is in contact with the electrode, a woven mesh produced by fine knitted threads, wire mesh, foamy metal, non-woven metallic fabric, expanded metal, perforated metal, porous metal foil and the like can be used, although not limited to it.

[001812] Examples of the electrode substrate for electrolysis 10 include a porous metallic foil, a wire mesh, a nonwoven metal fabric, a perforated metal, an expanded metal and a foamy metal.

[001813] As plate material before being processed into a perforated metal or expanded metal, laminated plate materials and electrolytic sheets are preferred. An electrolytic sheet is preferably still subjected to a galvanizing treatment using the same element as its base material, such as after-treatment, to thereby form roughness and one or both surfaces.

[001814] The thickness of the electrode substrate for electrolysis 10 is, as mentioned above, preferably 300 µm or less, more preferably 205 µm or less, more preferably 155 µm or less, even more preferably 135 µm or less, even more preferably 125 one or less, even more preferably 120 µm or less, even more preferably 100 µm or less, and even more preferably 50 µm or less from the point of view of a handling and economical property. THE

483/803 lower limit value is not particularly limited, but it is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001815] In the electrode substrate for electrolysis, the residual stress during processing is preferably relaxed by annealing the electrode substrate for electrolysis in an oxidizing atmosphere. It is preferable to form roughness using a steel grid, alumina powder or similar on the surface of the electrode substrate for electrolysis followed by an acid treatment to increase the surface area of the electrode, in order to improve the adhesion to a catalyst layer with which the surface is covered. Alternatively, it is preferable to give a galvanizing treatment using the same element as the substrate to increase the surface area.

[001816] In order to place the first layer 20 in close contact with the surface of the electrolyte electrode substrate 10, the electrode electrode substrate 10 is preferably subjected to an increase in surface area treatment. Examples of the treatment of increasing the surface area include a pickling treatment using a cut wire, steel grid, alumina grid or similar, an acid treatment using sulfuric acid or hydrochloric acid, and a galvanizing treatment using the same element as the of the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 µm to 50 µm, more preferably 0.1 to 10 µm, even more preferably 0.1 to 8 µm.

[001817] Next, a case will be described in which the electrode for electrolysis in the present modality is used as an anode for electrolysis of common salt. (First layer)

[001818] In Figure 119, a first layer 20 as a catalyst layer contains at least one of the ruthenium oxides, iridium oxides and titanium oxides. Examples of ruthenium oxide include RuO; Examples of

483/803 lower limit value is not particularly limited, but it is 1 µm, for example, preferably 5 µm, more preferably 15 µm.

[001815] In the electrode substrate for electrolysis, the residual stress during processing is preferably relaxed by annealing the electrode substrate for electrolysis in an oxidizing atmosphere. It is preferable to form roughness using a steel grid, alumina powder or similar on the surface of the electrode substrate for electrolysis followed by an acid treatment to increase the surface area of the electrode, in order to improve the adhesion to a catalyst layer with which the surface is covered. Alternatively, it is preferable to give a galvanizing treatment using the same element as the substrate to increase the surface area.

[001816] In order to place the first layer 20 in close contact with the surface of the electrolyte electrode substrate 10, the electrode electrode substrate 10 is preferably subjected to an increase in surface area treatment. Examples of the treatment of increasing the surface area include a pickling treatment using a cut wire, steel grid, alumina grid or similar, an acid treatment using sulfuric acid or hydrochloric acid, and a galvanizing treatment using the same element as the of the substrate. The arithmetic mean surface roughness (Ra) of the substrate surface is not particularly limited, but is preferably 0.05 µm to 50 µm, more preferably 0.1 to 10 µm, even more preferably 0.1 to 8 µm.

[001817] Next, a case will be described in which the electrode for electrolysis in the present mode is used as an anode for electrolysis of common salt. (First layer)

[001818] In Figure 119, a first layer 20 as a catalyst layer contains at least one of the ruthenium oxides, iridium oxides and titanium oxides. Examples of ruthenium oxide include RuO; Examples of

484/803 iridium oxide include IrO ,. Examples of titanium oxide include TiO,; The first layer 20 preferably contains two oxides: a ruthenium oxide and a titanium oxide or three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide. This makes the first layer 20 more stable and further improves adhesion with the second layer 30.

[001819] When the first layer 20 contains two oxides: a ruthenium oxide and a titanium oxide, the first layer 20 preferably contains 1 to 9 mol, more preferably 1 to 4 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition ratio of the two oxides in this range, the electrode for electrolysis 100 has excellent durability.

[001820] When the first layer 20 contains three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide, the first layer 20 preferably contains 0.2 to 3 mol, more preferably 0.3 to 2.5 mol of iridium oxide based on 1 mol of ruthenium oxide contained in the first layer 20. The first layer 20 preferably contains 0.3 to 8 mol, more preferably 1 to 7 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition of the three oxides in this range, the electrode for electrolysis 100 has excellent durability.

[001821] When the first layer 20 contains at least two of a ruthenium oxide, an iridium oxide and a titanium oxide, these oxides preferably form a solid solution. The formation of the solid oxide solution allows the electrolysis electrode 100 to have excellent durability.

[001822] In addition to the compositions described above, oxides of various compositions can be used provided that at least one oxide of a ruthenium oxide, an iridium oxide and titanium oxide is contained. For example, an oxide coating called DSA (R), which contains ruthenium, iridium,

484/803 iridium oxide include IrO ,. Examples of titanium oxide include TiO,; The first layer 20 preferably contains two oxides: a ruthenium oxide and a titanium oxide or three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide. This makes the first layer 20 more stable and further improves adhesion with the second layer 30.

[001819] When the first layer 20 contains two oxides: a ruthenium oxide and a titanium oxide, the first layer 20 preferably contains 1 to 9 mol, more preferably 1 to 4 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition ratio of the two oxides in this range, the electrode for electrolysis 100 has excellent durability.

[001820] When the first layer 20 contains three oxides: a ruthenium oxide, an iridium oxide and a titanium oxide, the first layer 20 preferably contains 0.2 to 3 mol, more preferably 0.3 to 2.5 mol of iridium oxide based on 1 mol of ruthenium oxide contained in the first layer 20. The first layer 20 preferably contains 0.3 to 8 mol, more preferably 1 to 7 mol of titanium oxide based on 1 mol of the oxide of ruthenium contained in the first layer 20. With the composition of the three oxides in this range, the electrode for electrolysis 100 has excellent durability.

[001821] When the first layer 20 contains at least two of a ruthenium oxide, an iridium oxide and a titanium oxide, these oxides preferably form a solid solution. The formation of the solid oxide solution allows the electrolysis electrode 100 to have excellent durability.

[001822] In addition to the compositions described above, oxides of various compositions can be used provided that at least one oxide of a ruthenium oxide, an iridium oxide and titanium oxide is contained. For example, an oxide coating called DSA (R), which contains ruthenium, iridium,

485/803 tantalum, niobium, titanium, tin, cobalt, manganese, platinum and the like, can be used as a first layer 20.

[001823] The first layer 20 does not have to be a single layer and can include a plurality of layers. For example, the first layer 20 can include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 µm, more preferably 0.1 to 8 µm. (Second layer)

[001824] The second layer 30 preferably contains ruthenium and titanium. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001825] The second layer 30 preferably contains a palladium oxide, a solid solution of a palladium and platinum oxide, or an alloy of palladium and platinum. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001826] A second thicker layer 30 can maintain the electrolytic performance for a longer period, but from an economic point of view, the thickness is preferably 0.05 to 3 µm.

[001827] Next, a case will be described in which the electrolyte electrode in the present modality is used as a cathode for electrolysis of common salt. (First layer)

[001828] Examples of components of the first layer 20 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Tn, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[001829] The first layer 20 may or may not contain at least one of the metals of the platinum group, metal oxides of the platinum group, hydroxides

485/803 tantalum, niobium, titanium, tin, cobalt, manganese, platinum and the like, can be used as a first layer 20.

[001823] The first layer 20 does not have to be a single layer and can include a plurality of layers. For example, the first layer 20 can include a layer containing three oxides and a layer containing two oxides. The thickness of the first layer 20 is preferably 0.05 to 10 µm, more preferably 0.1 to 8 µm. (Second layer)

[001824] The second layer 30 preferably contains ruthenium and titanium. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001825] The second layer 30 preferably contains a palladium oxide, a solid solution of a palladium and platinum oxide, or an alloy of palladium and platinum. This allows the chlorine overvoltage immediately after electrolysis to be reduced.

[001826] A second thicker layer 30 can maintain the electrolytic performance for a longer period, but from an economic point of view, the thickness is preferably 0.05 to 3 µm.

[001827] Next, a case will be described in which the electrode for electrolysis in the present modality is used as a cathode for electrolysis of common salt. (First layer)

[001828] Examples of components of the first layer 20 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Tn, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[001829] The first layer 20 may or may not contain at least one of the metals of the platinum group, metal oxides of the platinum group, hydroxides

486/803 platinum group metal and alloys containing a platinum group metal.

[001830] When the first layer 20 contains at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides, and alloys containing a platinum group metal, the metals of the platinum group platinum, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal preferably contain at least one platinum group metal of platinum, palladium, rhodium, ruthenium and iridium.

[001831] Like the platinum group metal, platinum is preferably contained.

[001832] Like the metal oxide of the platinum group, a ruthenium oxide is preferably contained.

[001833] Like the metal hydroxide of the platinum group, a ruthenium hydroxide is preferably contained.

[001834] As the metal alloy of the platinum group, a platinum alloy with nickel, iron and cobalt is preferably contained.

[001835] In addition, as needed, an oxide or hydroxide of a lanthanide element is preferably contained as a second component. This allows the electrolysis electrode 100 to have excellent durability.

[001836] As the oxide or hydroxide of a lanthanide element, at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium and dysprosium is preferably contained.

[001837] Furthermore, as needed, an oxide or hydroxide of a transition metal is preferably contained as a third component.

[001838] The addition of the third component allows the electrode for electrolysis 100 to have greater durability and for the electrolysis voltage to be

486/803 platinum group metal and alloys containing a platinum group metal.

[001830] When the first layer 20 contains at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides, and alloys containing a platinum group metal, the metals of the platinum group platinum, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal preferably contain at least one platinum group metal of platinum, palladium, rhodium, ruthenium and iridium.

[001831] Like the platinum group metal, platinum is preferably contained.

[001832] Like the metal oxide of the platinum group, a ruthenium oxide is preferably contained.

[001833] Like the metal hydroxide of the platinum group, a ruthenium hydroxide is preferably contained.

[001834] As the metal alloy of the platinum group, a platinum alloy with nickel, iron and cobalt is preferably contained.

[001835] In addition, as needed, an oxide or hydroxide of a lanthanide element is preferably contained as a second component. This allows the electrolysis electrode 100 to have excellent durability.

[001836] As the oxide or hydroxide of a lanthanide element, at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium and dysprosium is preferably contained.

[001837] Furthermore, as needed, an oxide or hydroxide of a transition metal is preferably contained as a third component.

[001838] The addition of the third component allows the electrode for electrolysis 100 to have greater durability and for the electrolysis voltage to be

487/803 reduced.

[001839] Examples of a preferable combination include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + Platinum + Palladium, Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + cobalt, ruthenium + samarium + zinc, ruthenium + samarium + gallium, ruthenium + samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + nickel uel + palladium, platinum + nickel + ruthenium, platinum and nickel alloys, platinum and cobalt alloys, and platinum and iron alloys.

[001840] When platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal are not contained, the main component of the catalyst is preferably the nickel element.

[001841] At least one of the nickel metals, oxides and hydroxides is preferably contained.

[001842] As the second component, a transition metal can be added. As the second component to be added, at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper and carbon is preferably contained.

[001843] Examples of a preferable combination include nickel + tin, nickel + titanium, nickel + molybdenum and nickel + cobalt.

[001844] As required, an intermediate layer can be

487/803 reduced.

[001839] Examples of a preferable combination include ruthenium only, ruthenium + nickel, ruthenium + cerium, ruthenium + lanthanum, ruthenium + lanthanum + platinum, ruthenium + lanthanum + palladium, ruthenium + praseodymium, ruthenium + praseodymium + platinum, ruthenium + praseodymium + Platinum + Palladium, Ruthenium + Neodymium, Ruthenium + Neodymium + Platinum, Ruthenium + Neodymium + Manganese, Ruthenium + Neodymium + Iron, Ruthenium + Neodymium + Cobalt, Ruthenium + Neodymium + Zinc, Ruthenium + Neodymium + Gallium, Ruthenium + Neodymium ruthenium + neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + samarium + iron, ruthenium + cobalt, ruthenium + samarium + zinc, ruthenium + samarium + gallium, ruthenium + samarium + sulfur, ruthenium + samarium + lead, ruthenium + samarium + nickel, platinum + cerium, platinum + palladium + cerium, platinum + palladium + lanthanum + cerium, platinum + iridium, platinum + palladium, platinum + iridium + palladium, platinum + nickel uel + palladium, platinum + nickel + ruthenium, platinum and nickel alloys, platinum and cobalt alloys, and platinum and iron alloys.

[001840] When platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal are not contained, the main component of the catalyst is preferably the nickel element.

[001841] At least one of the nickel metals, oxides and hydroxides is preferably contained.

[001842] As the second component, a transition metal can be added. As the second component to be added, at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper and carbon is preferably contained.

[001843] Examples of a preferable combination include nickel + tin, nickel + titanium, nickel + molybdenum and nickel + cobalt.

[001844] As required, an intermediate layer can be

488/803 placed between the first layer 20 and the electrode substrate for electrolysis

10. The durability of the electrolysis electrode 100 can be improved by placing the intermediate layer.

[001845] As the intermediate layer, those having affinity for both the first layer 20 and the electrode substrate for electrolysis 10 are preferred. As the intermediate layer, nickel oxides, platinum group metals, metal oxides are preferable of the platinum group and metal hydroxides of the platinum group. The intermediate layer can be formed by applying and cooking a solution containing a component that forms the intermediate layer. Alternatively, a surface oxide layer can also be formed by subjecting a substrate to a heat treatment at a temperature of 300 to 600ºC in an air atmosphere. In addition, the layer can be formed by a known method, such as a thermal spray method and an ion galvanizing method. (Second layer)

[001846] Examples of components of the first layer 30 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[001847] The first layer 30 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal. Examples of a preferable combination of elements contained in the second layer include the combinations listed for the first layer. The combination of the first layer and the second layer can be a combination in which the compositions are the same and the composition reasons are different or can be a combination of different

488/803 placed between the first layer 20 and the electrode substrate for electrolysis

10. The durability of the electrolysis electrode 100 can be improved by placing the intermediate layer.

[001845] As the intermediate layer, those having affinity for both the first layer 20 and the electrode substrate for electrolysis 10 are preferred. As the intermediate layer, nickel oxides, platinum group metals, metal oxides are preferable of the platinum group and metal hydroxides of the platinum group. The intermediate layer can be formed by applying and cooking a solution containing a component that forms the intermediate layer. Alternatively, a surface oxide layer can also be formed by subjecting a substrate to a heat treatment at a temperature of 300 to 600ºC in an air atmosphere. In addition, the layer can be formed by a known method, such as a thermal spray method and an ion galvanizing method. (Second layer)

[001846] Examples of components of the first layer 30 as a catalyst layer include metals such as C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and metal oxides and hydroxides.

[001847] The first layer 30 may or may not contain at least one of the platinum group metals, platinum group metal oxides, platinum group metal hydroxides and alloys containing a platinum group metal. Examples of a preferable combination of elements contained in the second layer include the combinations listed for the first layer. The combination of the first layer and the second layer can be a combination in which the compositions are the same and the composition reasons are different or can be a combination of different

489/803 compositions.

[001848] As the thickness of the catalyst layer, the total thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 µm to 20 µm. With a thickness of 0.01 µm or more, the catalyst layer can sufficiently serve as the catalyst. With a thickness of 20 µm or less, it is possible to form a robust catalyst layer that is unlikely to fall off the substrate. The thickness is more preferably 0.05 µm to 15 µm. The thickness is more preferably 0.1 µm to 10 µm. The thickness is even more preferably 0.2 µm to 8 µm.

[001849] The thickness of the electrode, i.e. the total thickness of the electrode substrate for electrolysis and the catalyst layer is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, even more preferably 150 one or less, particularly - preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less with respect to the electrode handling property. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably one or more. The thickness of the electrode can be determined by measurement with a digital thickness gauge (Mitutoyo Corporation, minimum scale 0.001 mm). The thickness of the electrode substrate for electrolysis is measured in the same way as the thickness of the electrode. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.

489/803 compositions.

[001848] As the thickness of the catalyst layer, the total thickness of the formed catalyst layer and the intermediate layer is preferably 0.01 µm to 20 µm. With a thickness of 0.01 µm or more, the catalyst layer can sufficiently serve as the catalyst. With a thickness of 20 µm or less, it is possible to form a robust catalyst layer that is unlikely to fall off the substrate. The thickness is more preferably 0.05 µm to 15 µm. The thickness is more preferably 0.1 µm to 10 µm. The thickness is even more preferably 0.2 µm to 8 µm.

[001849] The thickness of the electrode, i.e. the total thickness of the electrode substrate for electrolysis and the catalyst layer is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, even more preferably 150 one or less, particularly - preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less with respect to the electrode handling property. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably one or more. The thickness of the electrode can be determined by measurement with a digital thickness gauge (Mitutoyo Corporation, minimum scale 0.001 mm). The thickness of the electrode substrate for electrolysis is measured in the same way as the thickness of the electrode. The thickness of the catalyst layer can be determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.

490/803

[001850] In the method for producing an electrolyzer according to the present modality, the electrolysis electrode preferably contains at least one catalytic component selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V , Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N , O, SI, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy from the point of view of achieving sufficient electrolytic performance.

[001851] In the present modality, from the point of view that the electrolysis electrode, if it is an electrode with a wide region of elastic deformation, can provide a better handling property and has a better adhesive force to a membrane as an exchange membrane ionic and a microporous membrane, a degraded electrode, a feed conductor without any catalyst coating, and the like, the electrode thickness for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, still more preferably 150 µm or less, particularly preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably 20 µm or more. In the present modality, “having a wide region of elastic deformation” means that when an electrolysis electrode is wound to form a wound body, it is unlikely that distortion derived from the winding will occur after the wound state is released. The electrode thickness

490/803

[001850] In the method for producing an electrolyzer according to the present modality, the electrolysis electrode preferably contains at least one catalytic component selected from the group consisting of Ru, Rh, Pd, Ir, Pt, Au, Ti, V , Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ag, Ta, W, Re, Os, Al, In, Sn, Sb, Ga, Ge, B, C, N , O, SI, P, S, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and Dy from the point of view of achieving sufficient electrolytic performance.

[001851] In the present modality, from the point of view that the electrolysis electrode, if it is an electrode with a wide region of elastic deformation, can provide a better handling property and has a better adhesive force to a membrane as an exchange membrane ionic and a microporous membrane, a degraded electrode, a feed conductor without any catalyst coating, and the like, the electrode thickness for electrolysis is preferably 315 µm or less, more preferably 220 µm or less, more preferably 170 µm or less, still more preferably 150 µm or less, particularly preferably 145 µm or less, even more preferably 140 µm or less, even more preferably 138 µm or less, even more preferably 135 µm or less. A thickness of 135 µm or less can provide good handling properties. In addition, from a point of view similar to the above, the thickness is preferably 130 µm or less, more preferably less than 130 µm, more preferably 115 µm or less, even more preferably 65 µm or less. The lower limit value is not particularly limited, but is preferably 1 µm or more, more preferably 5 µm or more for practical reasons, more preferably 20 µm or more. In the present modality, “having a wide region of elastic deformation” means that when an electrolysis electrode is wound to form a wound body, it is unlikely that distortion derived from the winding will occur after the wound state is released. The electrode thickness

491/803 for electrolysis refers, when a catalyst layer mentioned below is included, to the total thickness of both the electrolysis electrode substrate and the catalyst layer. (Method to produce electrode for electrolysis)

[001852] Next, an embodiment of the method for producing the electrolysis electrode 100 will be described in detail.

[001853] In the present embodiment, the electrolysis electrode 100 can be produced by forming the first layer 20, preferably the second layer 30, on the electrode electrode substrate by a method such as cooking a coating film under an oxygen atmosphere ( pyrolysis) or ion galvanizing, galvanizing or thermal spraying. The production method of the present embodiment as mentioned can achieve a high productivity of the electrode for electrolysis 100. Specifically, a catalyst layer is formed on the electrode substrate for electrolysis by an application step to apply a coating liquid containing a catalyst, a drying step to dry the coating liquid and a pyrolysis step to perform pyrolysis. Pyrolysis here means that a metal salt that is to be a precursor is decomposed by heating into a metal or metal oxide and a gaseous substance. The decomposition product depends on the metal species to be used, the type of salt and the atmosphere under which pyrolysis is carried out, and many metals tend to form oxides in an oxidizing atmosphere. In an industrial electrode production process, pyrolysis is usually carried out in air, and a metal oxide or metal hydroxide is formed in many cases. (Formation of the first anode layer) (Application stage)

[001854] The first layer 20 is obtained by applying a solution in which at least one metallic salt of ruthenium, iridium and titanium is dissolved (first coating liquid) in the electrode substrate for electrolysis and

491/803 for electrolysis refers, when a catalyst layer mentioned below is included, to the total thickness of both the electrolysis electrode substrate and the catalyst layer. (Method to produce electrode for electrolysis)

[001852] Next, an embodiment of the method for producing the electrolysis electrode 100 will be described in detail.

[001853] In the present embodiment, the electrolysis electrode 100 can be produced by forming the first layer 20, preferably the second layer 30, on the electrode electrode substrate by a method such as cooking a coating film under an oxygen atmosphere ( pyrolysis) or ion galvanizing, galvanizing or thermal spraying. The production method of the present embodiment as mentioned can achieve a high productivity of the electrode for electrolysis 100. Specifically, a catalyst layer is formed on the electrode substrate for electrolysis by an application step to apply a coating liquid containing a catalyst, a drying step to dry the coating liquid and a pyrolysis step to perform pyrolysis. Pyrolysis here means that a metal salt that is to be a precursor is decomposed by heating into a metal or metal oxide and a gaseous substance. The decomposition product depends on the metal species to be used, the type of salt and the atmosphere under which pyrolysis is carried out, and many metals tend to form oxides in an oxidizing atmosphere. In an industrial electrode production process, pyrolysis is usually carried out in air, and a metal oxide or metal hydroxide is formed in many cases. (Formation of the first anode layer) (Application stage)

[001854] The first layer 20 is obtained by applying a solution in which at least one metallic salt of ruthenium, iridium and titanium is dissolved (first coating liquid) in the electrode substrate for electrolysis and

492/803 then pyrolysis (cooking) of the coating liquid in the presence of oxygen. The ruthenium, iridium and titanium content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001855] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[001856] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a method of brushing the first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[001857] After being applied to the electrode substrate for electrolysis 100, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and

492/803 then pyrolysis (cooking) of the coating liquid in the presence of oxygen. The ruthenium, iridium and titanium content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001855] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[001856] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a method of brushing the first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[001857] After being applied to the electrode substrate for electrolysis 100, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and

493/803 pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001858] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the second layer)

[001859] The second layer 30, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second liquid of first layer 20 and then pyrolyzing the coating liquid in the presence of oxygen. (Formation of the first cathode layer by the pyrolysis method) (Application stage)

[001860] The first layer 20 is obtained by applying a solution in which metal salts of various combinations are dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the coating liquid in the presence of oxygen. The metal content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001861] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. Like the solvent, it is

493/803 pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001858] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a predetermined thickness. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the second layer)

[001859] The second layer 30, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second liquid of first layer 20 and then pyrolyzing the coating liquid in the presence of oxygen. (Formation of the first cathode layer by the pyrolysis method) (Application stage)

[001860] The first layer 20 is obtained by applying a solution in which metal salts of various combinations are dissolved (first coating liquid) in the electrode substrate for electrolysis and then pyrolysis (cooking) of the coating liquid in the presence of oxygen. The metal content in the first coating liquid is substantially equivalent to that of the first layer 20.

[001861] Metal salts can be chlorides, nitrates, sulfates, metal alkoxides and any other forms. The solvent of the first coating liquid can be selected depending on the type of the metal salt, and water and alcohols such as butanol can be used. Like the solvent, it is

494/803 water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[001862] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[001863] After being applied to the electrode substrate for electrolysis 10, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001864] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a thickness

494/803 water or a mixed solvent of water and an alcohol is preferable. The total concentration of metal in the first coating liquid in which the metal salts are dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in association with the thickness of the coating film to be formed by a single coating .

[001862] Examples of a method used as the method for applying the first coating liquid to the electrode substrate for electrolysis 10 include a method of immersing the electrode substrate for electrolysis 10 in the first coating liquid, a brushing method of first coating liquid, a lamination method using a sponge roller impregnated with the first coating liquid and an electrostatic coating method in which the electrode substrate for electrolysis 10 and the first coating liquid are charged in an opposite manner and spraying is realized. Among these, the lamination method or electrostatic coating method, which has excellent industrial productivity, is preferable. (Drying step and pyrolysis step)

[001863] After being applied to the electrode substrate for electrolysis 10, the first coating liquid is dried at a temperature of 10 to 90ºC and pyrolyzed in a baking oven heated to 350 to 650ºC. Between drying and pyrolysis, preliminary cooking at 100 to 350ºC can be carried out as needed. Drying, preliminary cooking and pyrolysis temperature can be appropriately selected depending on the composition and type of solvent of the first coating liquid. A longer period of pyrolysis time per step is preferable, but from the standpoint of electrode productivity, 3 to 60 minutes is preferred, 5 to 20 minutes is more preferable.

[001864] The application, drying and pyrolysis cycle described above is repeated to form a covering (the first layer 20) up to a thickness

495/803 predetermined. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the intermediate layer)

[001865] The intermediate layer, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound or a platinum compound (second coating liquid) to the substrate and then pyrolyzing the coating liquid in the presence of oxygen. Alternatively, an intermediate layer of nickel oxide can be formed on the surface of the substrate just by heating the substrate, without applying a solution on it. (Formation of the first cathode layer by ion galvanizing)

[001866] The first layer 20 can also be formed by ion plating.

[001867] An example includes a method in which the substrate is fixed in a chamber and the metal ruthenium target is irradiated with an electron beam. Evaporated metallic ruthenium particles are positively charged to the plasma in the chamber to deposit on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and deposits of ruthenium as ruthenium oxide in the substrate. (Formation of the first cathode layer by galvanizing)

[001868] The first layer 20 can also be formed by a method of galvanization.

[001869] For example, when the substrate is used as a cathode and subjected to electrolytic galvanization in an electrolytic solution containing nickel and tin, nickel and tin alloy galvanization can be formed. (Formation of the first cathode layer by thermal spray)

[001870] The first layer 20 can also be formed by thermal spraying.

495/803 predetermined. After the first layer 20 is formed and then additionally post-baked for a long period, as needed, it can further improve the stability of the first layer 20. (Formation of the intermediate layer)

[001865] The intermediate layer, which is formed as needed, is obtained, for example, by applying a solution containing a palladium compound or a platinum compound (second coating liquid) to the substrate and then pyrolyzing the coating liquid in the presence of oxygen. Alternatively, an intermediate layer of nickel oxide can be formed on the surface of the substrate just by heating the substrate, without applying a solution on it. (Formation of the first cathode layer by ion galvanizing)

[001866] The first layer 20 can also be formed by ion plating.

[001867] An example includes a method in which the substrate is fixed in a chamber and the metal ruthenium target is irradiated with an electron beam. Evaporated metallic ruthenium particles are positively charged to the plasma in the chamber to deposit on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and deposits of ruthenium as ruthenium oxide in the substrate. (Formation of the first cathode layer by galvanizing)

[001868] The first layer 20 can also be formed by a method of galvanization.

[001869] For example, when the substrate is used as a cathode and subjected to electrolytic galvanization in an electrolytic solution containing nickel and tin, nickel and tin alloy galvanization can be formed. (Formation of the first cathode layer by thermal spray)

[001870] The first layer 20 can also be formed by thermal spraying.

496/803

[001871] As an example, the nickel oxide particles sprayed by plasma on the substrate can form a catalyst layer in which the metal nickel and nickel oxide are mixed.

[001872] Hereinafter, an ion exchange membrane according to an aspect of the membrane will be described in detail. [Ion exchange membrane]

[001873] The ion exchange membrane is not particularly limited as long as the membrane can be laminated with the electrolysis electrode, and several ion exchange membranes can be used. In the method for producing an electrolyzer according to the present embodiment, an ion exchange membrane is preferably used which has a membrane body containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and a coating layer provided with at least least one surface of the membrane body. It is preferable that the coating layer contains particles of inorganic material and a binder, and the specific surface area of the coating layer is 0.1 to 10 mº / g. The ion exchange membrane that has such a structure has a small influence of the gas generated during electrolysis on electrolytic performance and tends to exert stable electrolytic performance.

[001874] The membrane of a perfluorocarbon polymer into which an ion exchange group is introduced described above includes a layer of sulfonic acid with an ion exchange group derived from a sulfo group (a group represented by -SO3 ', here also called a "sulfonic acid group") or a layer of carboxylic acid with an ion exchange group derived from a carboxyl group (a group represented by -CO ;, here also called a "carboxylic acid group"). From the point of view of strength and dimensional stability, reinforcement core materials are preferably included.

[001875] The particles of inorganic material and binder will be

496/803

[001871] As an example, the nickel oxide particles sprayed by plasma on the substrate can form a catalyst layer in which the metal nickel and nickel oxide are mixed.

[001872] Hereinafter, an ion exchange membrane according to an aspect of the membrane will be described in detail. [Ion exchange membrane]

[001873] The ion exchange membrane is not particularly limited as long as the membrane can be laminated with the electrolysis electrode, and several ion exchange membranes can be used. In the method for producing an electrolyzer according to the present embodiment, an ion exchange membrane is preferably used which has a membrane body containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and a coating layer provided with at least least one surface of the membrane body. It is preferable that the coating layer contains particles of inorganic material and a binder, and the specific surface area of the coating layer is 0.1 to 10 mº / g. The ion exchange membrane that has such a structure has a small influence of the gas generated during electrolysis on electrolytic performance and tends to exert stable electrolytic performance.

[001874] The membrane of a perfluorocarbon polymer into which an ion exchange group is introduced described above includes a layer of sulfonic acid with an ion exchange group derived from a sulfo group (a group represented by -SO3 ', here also called a "sulfonic acid group") or a layer of carboxylic acid with an ion exchange group derived from a carboxyl group (a group represented by -CO ;, here also called a "carboxylic acid group"). From the point of view of strength and dimensional stability, reinforcement core materials are preferably included.

[001875] The particles of inorganic material and binder will be

497/803 described in detail in the coating layer description section below.

[001876] Figure 120 illustrates a schematic cross-sectional view showing an ion exchange membrane modality. An ion exchange membrane | it has a membrane body 10 containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and coating layers 11a and 11b formed on both surfaces of the membrane body 10.

[001877] In the ion exchange membrane 1, the membrane body 10 comprises a layer of sulfonic acid 3 with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called an “acid group sulfonic ”) and a layer of carboxylic acid 2 with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a“ carboxylic acid group ”), and the core materials of reinforcement 4 intensifies strength and dimensional stability. The ion exchange membrane 1, comprising the sulfonic acid layer 3 and the carboxylic acid layer 2, is suitably used as an anion exchange membrane.

[001878] The ion exchange membrane can include the sulfonic acid layer or the carboxylic acid layer. The ion exchange membrane may not necessarily be reinforced by reinforcement core materials, and the arrangement of the reinforcement core materials is not limited to the example in Figure 120. (Membrane body)

[001879] First, the membrane body 10 which constitutes the ion exchange membrane 1 will be described.

[001880] The membrane body 10 must be one that has the function of selectively allowing cations to permeate and comprises a hydrocarbon polymer or a fluorine-containing polymer with an ion exchange group. Its configuration and material are not particularly limited, and

497/803 described in detail in the coating layer description section below.

[001876] Figure 120 illustrates a schematic cross-sectional view showing an ion exchange membrane modality. An ion exchange membrane | it has a membrane body 10 containing a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group and coating layers 11a and 11b formed on both surfaces of the membrane body 10.

[001877] In the ion exchange membrane 1, the membrane body 10 comprises a layer of sulfonic acid 3 with an ion exchange group derived from a sulfo group (a group represented by -SO3-, here also called an “acid group sulfonic ”) and a layer of carboxylic acid 2 with an ion exchange group derived from a carboxyl group (a group represented by -CO; -, here also called a“ carboxylic acid group ”), and the core materials of reinforcement 4 intensifies strength and dimensional stability. The ion exchange membrane 1, comprising the sulfonic acid layer 3 and the carboxylic acid layer 2, is suitably used as an anion exchange membrane.

[001878] The ion exchange membrane can include the sulfonic acid layer or the carboxylic acid layer. The ion exchange membrane may not necessarily be reinforced by reinforcement core materials, and the arrangement of the reinforcement core materials is not limited to the example in Figure 120. (Membrane body)

[001879] First, the membrane body 10 which constitutes the ion exchange membrane 1 will be described.

[001880] The membrane body 10 must be one that has the function of selectively allowing cations to permeate and comprises a hydrocarbon polymer or a fluorine-containing polymer with an ion exchange group. Its configuration and material are not particularly limited, and

498/803 favorites can be selected appropriately.

[001881] The hydrocarbon polymer or fluorine-containing polymer with an ion exchange group in the membrane body 10 can be obtained from a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group precursor capable of forming a group of ion exchange by hydrolysis or similar. Specifically, for example, after a polymer comprising a fluorinated hydrocarbon backbone that has, as a pendant side chain, a group convertible into an ion exchange group by hydrolysis or similar (precursor to the ion exchange group), and is processable by melting (hereinafter called "fluorine-containing polymer (a)" in some cases), be used to prepare a precursor to the membrane body 10, the membrane body 10 can be obtained by converting the precursor to the ion exchange group in an ion exchange group.

[001882] The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. The fluorine-containing polymer (a) can also be produced by homopolymerizing a monomer selected from any of the following first group, the following second group and the following third group.

[001883] Examples of the monomers of the first group include vinyl fluoride compounds. Examples of the vinyl fluoride compounds include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and perfluoralkyl vinyl ethers. Particularly when the ion exchange membrane is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoro monomer, and a perfluoro monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and perfluoralkylvinyl ethers is preferable.

498/803 favorites can be selected appropriately.

[001881] The hydrocarbon polymer or fluorine-containing polymer with an ion exchange group in the membrane body 10 can be obtained from a hydrocarbon polymer or fluorine-containing polymer with an ion exchange group precursor capable of forming a group of ion exchange by hydrolysis or similar. Specifically, for example, after a polymer comprising a fluorinated hydrocarbon backbone that has, as a pendant side chain, a group convertible into an ion exchange group by hydrolysis or similar (precursor to the ion exchange group), and is processable by melting (hereinafter called "fluorine-containing polymer (a)" in some cases), be used to prepare a precursor to the membrane body 10, the membrane body 10 can be obtained by converting the precursor to the ion exchange group in an ion exchange group.

[001882] The fluorine-containing polymer (a) can be produced, for example, by copolymerizing at least one monomer selected from the following first group and at least one monomer selected from the following second group and / or the following third group. The fluorine-containing polymer (a) can also be produced by homopolymerizing a monomer selected from any of the following first group, the following second group and the following third group.

[001883] Examples of the monomers of the first group include vinyl fluoride compounds. Examples of the vinyl fluoride compounds include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene and perfluoralkyl vinyl ethers. Particularly when the ion exchange membrane is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoro monomer, and a perfluoro monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and perfluoralkylvinyl ethers is preferable.

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[001884] Examples of the monomers of the second group include vinyl compounds with a functional group convertible into an ion exchange group of the carboxylic acid type (carboxylic acid group). Examples of vinyl compounds with a functional group convertible to a carboxylic acid group include monomers represented by CF = CF (OCF; CYF); - O (CZF) .- COOR, where s represents an integer from 0 to 2, t represents an integer from 1 to 12, Y and Z each independently represent F or CF; 3, and R represents a lower alkyl group (a lower alkyl group is an alkyl group with 1 to 3 carbon atoms, for example).

[001885] Among them, compounds represented by CF; = CF (OCF; CYF), - O (CF2) n-COOR are preferable. Where n represents an integer from 0 to 2, m represents an integer from 1 to 4, Y represents F or CF; 3, and R represents CH3, CoHs, or C3H ;.

[001886] When the ion exchange membrane is used as a cation exchange membrane for alkaline electrolysis, a perfluoro compound is preferably at least used as the monomer, but the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis and, therefore, the alkyl group (R) need not be a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[001887] Of the monomers above, the monomers shown below are more preferable than the monomers of the second group: CF; = CFOCF; -CF (CF;) OCF; COOCH ;, CF; = CFOCF; CF (CF3) O (CF3) -COOCH ;, CF; = CF [OCF3-CF (CF3) 12O (CF>) - COOCH ;, CF; = CFOCF; CF (CF3) O (CF3); 5COOCH ;, CF3 = CFO (CF3); COOCH; , and CF; = CFO (CF;); COOCH ;.

[001888] Examples of the monomers of the third group include vinyl compounds with a functional group convertible into a group of

499/803

[001884] Examples of the monomers of the second group include vinyl compounds with a functional group convertible into an ion exchange group of the carboxylic acid type (carboxylic acid group). Examples of vinyl compounds with a functional group convertible to a carboxylic acid group include monomers represented by CF = CF (OCF; CYF); - O (CZF) .- COOR, where s represents an integer from 0 to 2, t represents an integer from 1 to 12, Y and Z each independently represent F or CF; 3, and R represents a lower alkyl group (a lower alkyl group is an alkyl group with 1 to 3 carbon atoms, for example).

[001885] Among them, compounds represented by CF; = CF (OCF; CYF), - O (CF2) n-COOR are preferable. Where n represents an integer from 0 to 2, m represents an integer from 1 to 4, Y represents F or CF; 3, and R represents CH3, CoHs, or C3H ;.

[001886] When the ion exchange membrane is used as a cation exchange membrane for alkaline electrolysis, a perfluoro compound is preferably at least used as the monomer, but the alkyl group (see R above) of the ester group is lost from the polymer at the time of hydrolysis and, therefore, the alkyl group (R) need not be a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

[001887] Of the monomers above, the monomers shown below are more preferable than the monomers of the second group: CF; = CFOCF; -CF (CF;) OCF; COOCH ;, CF; = CFOCF; CF (CF3) O (CF3) -COOCH ;, CF; = CF [OCF3-CF (CF3) 12O (CF>) - COOCH ;, CF; = CFOCF; CF (CF3) O (CF3); 5COOCH ;, CF3 = CFO (CF3); COOCH; , and CF; = CFO (CF;); COOCH ;.

[001888] Examples of the monomers of the third group include vinyl compounds with a functional group convertible into a group of

500/803 ion exchange of the sulfone type (sulfonic acid group). As vinyl compounds with a functional group convertible to a sulfonic acid group, for example, monomers represented by CF; = CFO-X-CF; -SO, F are preferred, where X represents a perfluoroalkylene group. Specific examples of these include the monomers represented below: CF; = CFOCFCFSOF, CF; = CFOCFCF (CF3) OCF3CF3SO »xF, CF; = CFOCF: CF (CF3) OCF; CFCF3SO) F, CF3 = CF (CF3); SOF, CF3 = CFO [CF; CF (CF3) O] 1CF.CFE3SOF, and CF. = CFOCF; CF (CF; OCF3) OCF; CFSO »xF.

[001889] Among them, CF = CFOCF; CF (CF3) OCF; CF; CFSO0.F = and CF; = CFOCF; CF (CF3) OCF; CF3SO, F are more preferable.

[001890] The copolymer obtained from these monomers can be produced by a polymerization method developed for homopolymerization and copolymerization of ethylene fluoride, particularly a general polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, a polymerization reaction can be carried out in the presence of a radical polymerization initiator such as a perfluorocarbon peroxide or an azo compound under the conditions of a temperature of 0 to 200ºC and a pressure of 0, 1 to 20 MPa using an inert solvent such as a perfluorohydrocarbon or a chlorofluorocarbon.

[001891] In the above copolymerization, the type of combination of the above monomers and their proportion are not particularly limited and are selected and determined depending on the type and quantity of the desired functional group to be imparted to the fluorine-containing polymer to be obtained. For example, when a fluorine-containing polymer containing only one carboxylic acid group is formed, at least one monomer must be selected from each of the first and second groups described above and

500/803 ion exchange of the sulfone type (sulfonic acid group). As vinyl compounds with a functional group convertible to a sulfonic acid group, for example, monomers represented by CF; = CFO-X-CF; -SO, F are preferred, where X represents a perfluoroalkylene group. Specific examples of these include the monomers represented below: CF; = CFOCFCFSOF, CF; = CFOCFCF (CF3) OCF3CF3SO »xF, CF; = CFOCF: CF (CF3) OCF; CFCF3SO) F, CF3 = CF (CF3); SOF, CF3 = CFO [CF; CF (CF3) O] 1CF.CFE3SOF, and CF. = CFOCF; CF (CF; OCF3) OCF; CFSO »xF.

[001889] Among them, CF = CFOCF; CF (CF3) OCF; CF; CFSO0.F = and CF; = CFOCF; CF (CF3) OCF; CF3SO, F are more preferable.

[001890] The copolymer obtained from these monomers can be produced by a polymerization method developed for homopolymerization and copolymerization of ethylene fluoride, particularly a general polymerization method used for tetrafluoroethylene. For example, in a non-aqueous method, a polymerization reaction can be carried out in the presence of a radical polymerization initiator such as a perfluorocarbon peroxide or an azo compound under the conditions of a temperature of 0 to 200ºC and a pressure of 0, 1 to 20 MPa using an inert solvent such as a perfluorohydrocarbon or a chlorofluorocarbon.

[001891] In the above copolymerization, the type of combination of the above monomers and their proportion are not particularly limited and are selected and determined depending on the type and quantity of the desired functional group to be imparted to the fluorine-containing polymer to be obtained. For example, when a fluorine-containing polymer containing only one carboxylic acid group is formed, at least one monomer must be selected from each of the first and second groups described above and

501/803 copolymerized. In addition, when a fluorine-containing polymer containing only one sulfonic acid group is formed, at least one monomer must be selected from each of the first group and the third group and copolymerized. In addition, when a fluorine-containing polymer with a carboxylic acid group and a sulfonic acid group is formed, at least one monomer must be selected from each of the first group, the second group and the third group described above and copolymerized. In that case, the target fluorine-containing polymer can also be obtained by separately preparing a copolymer comprising the monomers of the first group and the second group described above and a copolymer comprising the monomers of the first group and the third group described above, and then mixing the copolymers. The mixing ratio of the monomers is not particularly limited, and when the number of functional groups per unit of polymer is increased, the proportion of the selected monomers from the second and third groups described above should be increased.

[001892] The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, more preferably 0.6 to 1.5 mg equivalent / g. The total ion exchange capacity here refers to the exchange group equivalent per unit weight of the dry resin and can be measured by neutralization titration or the like.

[001893] In membrane body 10 of ion exchange membrane 1, a layer of sulfonic acid 3 containing a polymer containing fluorine with a group of sulfonic acid and a layer of carboxylic acid 2 containing a polymer containing fluorine with a group of carboxylic acid are laminated. By providing the membrane body 10 with this layer configuration, the selective permeability for cations, such as sodium fons, can be further improved.

501/803 copolymerized. In addition, when a fluorine-containing polymer containing only one sulfonic acid group is formed, at least one monomer must be selected from each of the first group and the third group and copolymerized. In addition, when a fluorine-containing polymer with a carboxylic acid group and a sulfonic acid group is formed, at least one monomer must be selected from each of the first group, the second group and the third group described above and copolymerized. In that case, the target fluorine-containing polymer can also be obtained by separately preparing a copolymer comprising the monomers of the first group and the second group described above and a copolymer comprising the monomers of the first group and the third group described above, and then mixing the copolymers. The mixing ratio of the monomers is not particularly limited, and when the number of functional groups per unit of polymer is increased, the proportion of the selected monomers from the second and third groups described above should be increased.

[001892] The total ion exchange capacity of the fluorine-containing copolymer is not particularly limited, but is preferably 0.5 to 2.0 mg equivalent / g, more preferably 0.6 to 1.5 mg equivalent / g. The total ion exchange capacity here refers to the exchange group equivalent per unit weight of the dry resin and can be measured by neutralization titration or the like.

[001893] In membrane body 10 of ion exchange membrane 1, a layer of sulfonic acid 3 containing a polymer containing fluorine with a group of sulfonic acid and a layer of carboxylic acid 2 containing a polymer containing fluorine with a group of carboxylic acid are laminated. By providing the membrane body 10 with this layer configuration, the selective permeability for cations, such as sodium fons, can be further improved.

502/803

[001894] The ion exchange membrane | it is arranged in an electrolyzer in such a way that, generally, the sulfonic acid layer 3 is located on the anode side of the electrolyzer and the carboxylic acid layer 2 is located on the cathode side of the electrolyzer.

[001895] The sulfonic acid layer 3 is preferably made of a material with low electrical resistance and has a membrane thickness greater than that of the carboxylic acid layer 2 from the point of view of the membrane resistance. The membrane thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, more preferably 3 to 15 times that of the carboxylic acid layer 2.

[001896] The carboxylic acid layer 2 preferably has high anion exclusion properties, even if it has a small membrane thickness. The anion exclusion properties here refer to the property of trying to prevent anion intrusion and permeation into and through the ion exchange membrane 1. In order to increase the anion exclusion properties, it is effective to lay out a layer of carboxylic acid with a small ion exchange capacity to the sulfonic acid layer.

[001897] As the fluorine-containing polymer for use in the sulfonic acid layer 3, a polymer obtained using CF; = CFOCF; CF (CF3) OCF; CF3SO, 3F as the monomer of the third group is preferred.

[001898] As the fluorine-containing polymer for use in the carboxylic acid-2 layer, a polymer obtained using CF; = CFOCF; CF (CF3) O (CF;); COOCH; as the monomer of the second group. (Coating layer)

[001899] The ion exchange membrane preferably has a coating layer on at least one surface of the membrane body. As shown in Figure 120, on the ion exchange membrane 1, coating layers 11a and 11b are formed on both surfaces of the

502/803

[001894] The ion exchange membrane | it is arranged in an electrolyzer in such a way that, generally, the sulfonic acid layer 3 is located on the anode side of the electrolyzer and the carboxylic acid layer 2 is located on the cathode side of the electrolyzer.

[001895] The sulfonic acid layer 3 is preferably made of a material with low electrical resistance and has a membrane thickness greater than that of the carboxylic acid layer 2 from the point of view of the membrane resistance. The membrane thickness of the sulfonic acid layer 3 is preferably 2 to 25 times, more preferably 3 to 15 times that of the carboxylic acid layer 2.

[001896] The carboxylic acid layer 2 preferably has high anion exclusion properties, even if it has a small membrane thickness. The anion exclusion properties here refer to the property of trying to prevent anion intrusion and permeation into and through the ion exchange membrane 1. In order to increase the anion exclusion properties, it is effective to lay out a layer of carboxylic acid with a small ion exchange capacity to the sulfonic acid layer.

[001897] As the fluorine-containing polymer for use in the sulfonic acid layer 3, a polymer obtained using CF; = CFOCF; CF (CF3) OCF; CF3SO, 3F as the monomer of the third group is preferred.

[001898] As the fluorine-containing polymer for use in the carboxylic acid-2 layer, a polymer obtained using CF; = CFOCF; CF (CF3) O (CF;); COOCH; as the monomer of the second group. (Coating layer)

[001899] The ion exchange membrane preferably has a coating layer on at least one surface of the membrane body. As shown in Figure 120, on the ion exchange membrane 1, coating layers 11a and 11b are formed on both surfaces of the

503/803 membrane 10.

[001900] The coating layers contain particles of inorganic material and a binder.

[001901] The average particle size of the particles of inorganic material is preferably 0.90 µm or more. When the average particle size of the particles of inorganic material is 0.90 µm or more, the durability to impurities is greatly improved, in addition to the gas display. That is, increasing the average particle size of the particles of inorganic material, as well as satisfying the value of the specific surface area mentioned above, can achieve a particularly remarkable effect. Irregular inorganic material particles are preferable because the average particle size and specific surface area, as above, are satisfied. Particles of inorganic material obtained by melting and particles of inorganic material obtained by grinding ore can be used. Particles of inorganic material obtained by grinding raw ore can preferably be used.

[001902] The average particle size of the particles of inorganic material can be 2 µm or less. When the average particle size of the particles of inorganic material is 2 µm or less, it is possible to avoid damage to the membrane due to the particles of inorganic material. The average particle size of the inorganic material particle is more preferably 0.90 to 1.2 µm.

[001903] Here, the average particle size can be measured by a particle size analyzer (“SALD2200”, SHIMADZU CORPORATION).

[001904] The particles of inorganic material preferably have irregular shapes. Such shapes further improve resistance to impurities. Particles of inorganic material preferably have a wide particle size distribution.

503/803 membrane 10.

[001900] The coating layers contain particles of inorganic material and a binder.

[001901] The average particle size of the particles of inorganic material is preferably 0.90 µm or more. When the average particle size of the particles of inorganic material is 0.90 µm or more, the durability to impurities is greatly improved, in addition to the gas display. That is, increasing the average particle size of the particles of inorganic material, as well as satisfying the value of the specific surface area mentioned above, can achieve a particularly remarkable effect. Irregular inorganic material particles are preferable because the average particle size and specific surface area, as above, are satisfied. Particles of inorganic material obtained by melting and particles of inorganic material obtained by grinding ore can be used. Particles of inorganic material obtained by grinding raw ore can preferably be used.

[001902] The average particle size of the particles of inorganic material can be 2 µm or less. When the average particle size of the particles of inorganic material is 2 µm or less, it is possible to avoid damage to the membrane due to the particles of inorganic material. The average particle size of the inorganic material particle is more preferably 0.90 to 1.2 µm.

[001903] Here, the average particle size can be measured by a particle size analyzer (“SALD2200”, SHIMADZU CORPORATION).

[001904] The particles of inorganic material preferably have irregular shapes. Such shapes further improve resistance to impurities. Particles of inorganic material preferably have a wide particle size distribution.

504/803

[001905] Particles of inorganic material preferably contain at least one inorganic material selected from the group consisting of oxides of Group IV elements in the Periodic Table, nitrides of Group IV elements in the Periodic Table and carbides of Group IV elements in Periodic table. From the point of view of durability, the zirconium oxide particle is more preferable.

[001906] The particles of inorganic material are preferably particles of inorganic material produced by grinding the raw ore of the particles of inorganic material or particles of inorganic material, such as spherical particles with a uniform diameter, obtained by purification by melting the raw ore of the particles of inorganic material.

[001907] Examples of means for grinding raw ore include, but are not particularly limited to, ball mills, ball mills, colloid mills, conical mills, disc mills, roller mills, grain mills, hammer mills, granules, VSI mills, Wiley mills, laminators and jet mills. After grinding, the particles are preferably washed. As a washing method, the particles are preferably treated with acid. This treatment can reduce impurities, such as iron affixed to the surface of particles of inorganic material.

[001908] The coating layer preferably contains a binder. The binder is a component that forms the coating layers retaining particles of inorganic material on the surface of the ion exchange membrane. The binder preferably contains a polymer containing fluorine from the point of view of durability to the electrolytic solution and electrolysis products.

[001909] As a binder, a fluorine-containing polymer with a carboxylic acid group or a sulfonic acid group is preferred, from the point of view of durability to the electrolyte solution and products of electrolysis and adhesion

504/803

[001905] Particles of inorganic material preferably contain at least one inorganic material selected from the group consisting of oxides of Group IV elements in the Periodic Table, nitrides of Group IV elements in the Periodic Table and carbides of Group IV elements in Periodic table. From the point of view of durability, the zirconium oxide particle is more preferable.

[001906] The particles of inorganic material are preferably particles of inorganic material produced by grinding the raw ore of the particles of inorganic material or particles of inorganic material, such as spherical particles with a uniform diameter, obtained by purification by melting the raw ore of the particles of inorganic material.

[001907] Examples of means for grinding raw ore include, but are not particularly limited to, ball mills, ball mills, colloid mills, conical mills, disc mills, roller mills, grain mills, hammer mills, granules, VSI mills, Wiley mills, laminators and jet mills. After grinding, the particles are preferably washed. As a washing method, the particles are preferably treated with acid. This treatment can reduce impurities, such as iron affixed to the surface of particles of inorganic material.

[001908] The coating layer preferably contains a binder. The binder is a component that forms the coating layers retaining particles of inorganic material on the surface of the ion exchange membrane. The binder preferably contains a polymer containing fluorine from the point of view of durability to the electrolytic solution and electrolysis products.

[001909] As a binder, a fluorine-containing polymer with a carboxylic acid group or a sulfonic acid group is preferred, from the point of view of durability to the electrolyte solution and products of electrolysis and adhesion

505/803 on the surface of the ion exchange membrane. When a coating layer is provided on a layer containing a fluorine-containing polymer with a sulfonic acid group (sulfonic acid layer), a fluorine-containing polymer with a sulfonic acid group is still preferably used as the binder of the coating layer. Alternatively, when a coating layer is provided on a layer containing a fluorine-containing polymer with a carboxylic acid group (carboxylic acid layer), a fluorine-containing polymer with a carboxylic acid group is still preferably used as the binder of the coating layer.

[001910] In the coating layer, the content of the particles of inorganic material is preferably 40 to 90% by weight, more preferably 50 to 90% by weight. The content of the binder is preferably 10 to 60% by weight, more preferably 10 to 50% by weight.

[001911] The density of distribution of the coating layer on the ion exchange membrane is preferably 0.05 to 2 mg per 1 µm. When the ion exchange membrane has roughness on its surface, the distribution density of the coating layer is preferably 0.5 to 2 mg per 1 in °.

[001912] As the method for forming the coating layer, which is not particularly limited, a known method can be used. An example is a method that includes spraying or the like of a coating liquid obtained by dispersing particles of inorganic material in a solution containing a binder. (Reinforcement core materials)

[001913] The ion exchange membrane preferably has reinforcement core materials arranged within the membrane body.

[001914] The reinforcement core materials are members that enhance the resistance and dimensional stability of the ion exchange membrane. When arranging the reinforcement core materials within the body of the

505/803 on the surface of the ion exchange membrane. When a coating layer is provided on a layer containing a fluorine-containing polymer with a sulfonic acid group (sulfonic acid layer), a fluorine-containing polymer with a sulfonic acid group is still preferably used as the binder of the coating layer. Alternatively, when a coating layer is provided on a layer containing a fluorine-containing polymer with a carboxylic acid group (carboxylic acid layer), a fluorine-containing polymer with a carboxylic acid group is still preferably used as the binder of the coating layer.

[001910] In the coating layer, the content of the particles of inorganic material is preferably 40 to 90% by weight, more preferably 50 to 90% by weight. The content of the binder is preferably 10 to 60% by weight, more preferably 10 to 50% by weight.

[001911] The density of distribution of the coating layer on the ion exchange membrane is preferably 0.05 to 2 mg per 1 µm. When the ion exchange membrane has roughness on its surface, the distribution density of the coating layer is preferably 0.5 to 2 mg per 1 in °.

[001912] As the method for forming the coating layer, which is not particularly limited, a known method can be used. An example is a method that includes spraying or the like of a coating liquid obtained by dispersing particles of inorganic material in a solution containing a binder. (Reinforcement core materials)

[001913] The ion exchange membrane preferably has reinforcement core materials arranged within the membrane body.

[001914] The reinforcement core materials are members that enhance the resistance and dimensional stability of the ion exchange membrane. When arranging the reinforcement core materials within the body of the

506/803 membrane, particularly the expansion and contraction of the ion exchange membrane can be controlled in the desired range. Such an ion exchange membrane does not expand or contract more than necessary during electrolysis and the like and can maintain excellent dimensional stability in the long run.

[001915] The configuration of the reinforcement core materials is not particularly limited and, for example, the reinforcement core materials can be formed by spinning threads called reinforcement threads. The reinforcement threads here refer to threads that are members that make up the reinforcement core materials, can provide the desired dimensional stability and mechanical resistance to the ion exchange membrane and can be stably present in the ion exchange membrane. By using the reinforcement core materials obtained by spinning such reinforcement threads, better dimensional stability and mechanical resistance to the ion exchange membrane can be provided.

[001916] The material of the reinforcement core materials and the reinforcement yarns used for them is not particularly limited, but is preferably a material resistant to acids, alkalis, etc., and a fiber comprising a fluorine-containing polymer is preferable because the long-term thermal resistance and chemical resistance are required.

[001917] Examples of the fluorine-containing polymer to be used in the reinforcement core materials include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroethyl vinyl ether (PFA) copolymers, tetrafluoroethylene-ethylene (ETFE) copolymers, tetrafluoroethylene-copolymers, hexetrafluoroethylene and copolymers. trifluorochlorethylene-ethylene and polymers of vinylidene fluoride (PVDF). Among these, fibers comprising polytetrafluoroethylene are preferably used from the point of view of heat resistance and chemical resistance.

[001918] The wire diameter of the reinforcement wires used for the materials

506/803 membrane, particularly the expansion and contraction of the ion exchange membrane can be controlled in the desired range. Such an ion exchange membrane does not expand or contract more than necessary during electrolysis and the like and can maintain excellent dimensional stability in the long run.

[001915] The configuration of the reinforcement core materials is not particularly limited and, for example, the reinforcement core materials can be formed by spinning threads called reinforcement threads. The reinforcement threads here refer to threads that are members that make up the reinforcement core materials, can provide the desired dimensional stability and mechanical resistance to the ion exchange membrane and can be stably present in the ion exchange membrane. By using the reinforcement core materials obtained by spinning such reinforcement threads, better dimensional stability and mechanical resistance to the ion exchange membrane can be provided.

[001916] The material of the reinforcement core materials and the reinforcement yarns used for them is not particularly limited, but is preferably a material resistant to acids, alkalis, etc., and a fiber comprising a fluorine-containing polymer is preferable because the long-term thermal resistance and chemical resistance are required.

[001917] Examples of the fluorine-containing polymer to be used in the reinforcement core materials include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroethyl vinyl ether (PFA) copolymers, tetrafluoroethylene-ethylene (ETFE) copolymers, tetrafluoroethylene-copolymers, hexetrafluoroethylene and copolymers. trifluorochlorethylene-ethylene and polymers of vinylidene fluoride (PVDF). Among these, fibers comprising polytetrafluoroethylene are preferably used from the point of view of heat resistance and chemical resistance.

[001918] The wire diameter of the reinforcement wires used for the materials

507/803 of the reinforcement core is not particularly limited, but is preferably 20 to 300 deniers, more preferably 50 to 250 deniers. The weave density (tissue count per unit length) is preferably 5 to 50 / inch. The shape of the reinforcement core materials is not particularly limited, for example, a woven fabric, a non-woven fabric and a knitted fabric are used, but it is preferably in the form of a woven fabric. The thickness of the woven fabric to be used is preferably 30 to 250 µm, more preferably 30 to 150 µm.

[001919] As woven fabric or knitted fabric, monofilaments, multifilaments, or yarns thereof, a slit yarn, or the like, and various types of weaving methods, such as single weft, leno weft, knitted weft, weft, can be used cord and sirsaca, can be used.

[001920] The weft and arrangement of the reinforcement core materials in the membrane body are not particularly limited, and the preferred arrangement can be suitably provided considering the size and shape of the ion exchange membrane, desired physical properties for the membrane of ion exchange, the environment of use and the like.

[001921] For example, the reinforcement core materials can be arranged along a predetermined direction of the membrane body, but from the point of view of dimensional stability, it is preferable that the reinforcement core materials are arranged over a predetermined first direction, and other reinforcement core materials along a second direction substantially perpendicular to the first direction. By arranging the plurality of reinforcement core materials substantially orthogonally within the membrane body, it is possible to provide better dimensional stability and mechanical strength in several directions. For example, the arrangement in which reinforcement core materials arranged along the longitudinal direction (warp yarns) and reinforcement core materials arranged along the transverse direction (weft threads) are woven.

507/803 of the reinforcement core is not particularly limited, but is preferably 20 to 300 deniers, more preferably 50 to 250 deniers. The weave density (tissue count per unit length) is preferably 5 to 50 / inch. The shape of the reinforcement core materials is not particularly limited, for example, a woven fabric, a non-woven fabric and a knitted fabric are used, but it is preferably in the form of a woven fabric. The thickness of the woven fabric to be used is preferably 30 to 250 µm, more preferably 30 to 150 µm.

[001919] As woven fabric or knitted fabric, monofilaments, multifilaments, or yarns thereof, a slit yarn, or the like, and various types of weaving methods, such as single weft, leno weft, knitted weft, weft, can be used cord and sirsaca, can be used.

[001920] The weft and arrangement of the reinforcement core materials in the membrane body are not particularly limited, and the preferred arrangement can be suitably provided considering the size and shape of the ion exchange membrane, desired physical properties for the membrane of ion exchange, the environment of use and the like.

[001921] For example, the reinforcement core materials can be arranged along a predetermined direction of the membrane body, but from the point of view of dimensional stability, it is preferable that the reinforcement core materials are arranged over a predetermined first direction, and other reinforcement core materials along a second direction substantially perpendicular to the first direction. By arranging the plurality of reinforcement core materials substantially orthogonally within the membrane body, it is possible to provide better dimensional stability and mechanical strength in several directions. For example, the arrangement in which reinforcement core materials arranged along the longitudinal direction (warp yarns) and reinforcement core materials arranged along the transverse direction (weft threads) are woven.

508/803 on the surface side of the membrane body is preferred. The arrangement is most preferably in the form of driven flat weft and woven fabric allowing the warps and wefts to alternately move between themselves and underneath each other, smooth weft in which two warps are woven into wefts while twisted, weft in a driven and woven basket by insertion in two or more warps arranged in parallel, wefts of the same or similar number, from the point of view of dimensional stability, mechanical resistance and ease of production.

[001922] It is preferred that, in particular, the reinforcement core materials are arranged along both directions, the MD (Machine Direction) and TD (Transversal Direction) of the ion exchange membrane. In other words, the reinforcement core materials are preferably single woven in MD and TD. Here, MD refers to the direction in which the membrane body and various core materials (for example, the reinforcement core materials, reinforcement wires and sacrificial wires described below) are transported in a production step of ion exchange membrane described later (flow direction) and TD refers to the direction substantially perpendicular to the MD. The threads woven along the MD are called MD threads, and the threads woven along the TD are called TD threads. Typically, the ion exchange membrane used for electrolysis is rectangular, and in many cases, the longitudinal direction is the MD, and the width direction is the TD. By weaving the reinforcement core materials that are MD yarns and the reinforcement core materials that are TD yarns, it is possible to provide better dimensional stability and mechanical strength in many directions.

[001923] The range of arrangement of the reinforcement core materials is not particularly limited, and the preferred arrangement can be adequately provided considering the desired physical properties for the ion exchange membrane, the environment of use and the like.

[001924] The orifice ratio for reinforcement core materials is not

508/803 on the surface side of the membrane body is preferred. The arrangement is most preferably in the form of driven flat weft and woven fabric allowing the warps and wefts to alternately move between themselves and underneath each other, smooth weft in which two warps are woven into wefts while twisted, weft in a driven and woven basket by insertion in two or more warps arranged in parallel, wefts of the same or similar number, from the point of view of dimensional stability, mechanical resistance and ease of production.

[001922] It is preferred that, in particular, the reinforcement core materials are arranged along both directions, the MD (Machine Direction) and TD (Transversal Direction) of the ion exchange membrane. In other words, the reinforcement core materials are preferably single woven in MD and TD. Here, MD refers to the direction in which the membrane body and various core materials (for example, the reinforcement core materials, reinforcement wires and sacrificial wires described below) are transported in a production step of ion exchange membrane described later (flow direction) and TD refers to the direction substantially perpendicular to the MD. The threads woven along the MD are called MD threads, and the threads woven along the TD are called TD threads. Typically, the ion exchange membrane used for electrolysis is rectangular, and in many cases, the longitudinal direction is the MD, and the width direction is the TD. By weaving the reinforcement core materials that are MD yarns and the reinforcement core materials that are TD yarns, it is possible to provide better dimensional stability and mechanical strength in many directions.

[001923] The range of arrangement of the reinforcement core materials is not particularly limited, and the preferred arrangement can be adequately provided considering the desired physical properties for the ion exchange membrane, the environment of use and the like.

[001924] The orifice ratio for reinforcement core materials is not

509/803 is particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The orifice ratio is preferably 30% or more from the point of view of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the point of view of the mechanical strength of the ion exchange membrane.

[001925] The orifice ratio for the reinforcement core materials refers to a ratio of a total area of a surface through which substances such as fons (an electrolyte solution and cations contained in it (for example, sodium fons)) they can pass (B) to the area of one of the surfaces of the membrane body (A) (B / A). The total surface area through which substances such as fons can pass (B) can refer to the total areas of regions in which the ion exchange membrane, cations, an electrolyte solution and the like are not blocked by the reinforcement core materials and similar substances contained in the ion exchange membrane.

[001926] Figure 121 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane. Figure 121, in which a portion of the ion exchange membrane is enlarged, shows only the arrangement of the reinforcement core materials 21 and 22 in the regions, omitting the illustration of the other members.

[001927] By subtracting the total area of the reinforcement core materials (C) from the area of the region surrounded by the reinforcement core materials 21 arranged along the longitudinal direction and the reinforcement core materials 22 arranged along the transverse direction, the region including the area of the reinforcement core materials (A), the total area of regions through which substances such as phons can pass (B) in the area of the region described above (A) can be obtained. That is, the orifice ratio can be determined by the following formula (1): Orifice ratio = (B) / (A) = ((A) - (O0)) / (A) ... (D

509/803 is particularly limited, but is preferably 30% or more, more preferably 50% or more and 90% or less. The orifice ratio is preferably 30% or more from the point of view of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the point of view of the mechanical strength of the ion exchange membrane.

[001925] The orifice ratio for the reinforcement core materials refers to a ratio of a total area of a surface through which substances such as fons (an electrolyte solution and cations contained in it (for example, sodium fons)) they can pass (B) to the area of one of the surfaces of the membrane body (A) (B / A). The total surface area through which substances such as fons can pass (B) can refer to the total areas of regions in which the ion exchange membrane, cations, an electrolyte solution and the like are not blocked by the reinforcement core materials and similar substances contained in the ion exchange membrane.

[001926] Figure 121 illustrates a schematic view to explain the orifice ratio of the reinforcement core materials that make up the ion exchange membrane. Figure 121, in which a portion of the ion exchange membrane is enlarged, shows only the arrangement of the reinforcement core materials 21 and 22 in the regions, omitting the illustration of the other members.

[001927] By subtracting the total area of the reinforcement core materials (C) from the area of the region surrounded by the reinforcement core materials 21 arranged along the longitudinal direction and the reinforcement core materials 22 arranged along the transverse direction, the region including the area of the reinforcement core materials (A), the total area of regions through which substances such as phons can pass (B) in the area of the region described above (A) can be obtained. That is, the orifice ratio can be determined by the following formula (1): Orifice ratio = (B) / (A) = ((A) - (O0)) / (A) ... (D

510/803

[001928] Among the materials of the reinforcement core, a particularly preferred form are highly oriented tape yarns or monofilaments comprising PTFE from the point of view of chemical resistance and heat resistance. Specifically, reinforcement core materials forming a single web in which 50 to 300 denier ribbon yarns obtained by cutting a high strength porous sheet comprising PTFE into a ribbon form, or highly oriented 50 to 300 denier monofilaments are used comprising PTFE and having a weave density of 10 to 50 threads or monofilaments / inch and having a thickness in the range of 50 to 100 µm are more preferred. The orifice ratio of an ion exchange membrane comprising such reinforcement core materials is still preferably 60% or more.

[001929] Examples of the shape of the reinforcement threads include round threads and ribbon threads. (Continuous holes)

[001930] The ion exchange membrane preferably has continuous holes inside the body of the membrane.

[001931] Continuous holes refer to holes that can be flow paths for fons generated in electrolysis and an electrolyte solution. The continuous holes, which are tubular holes formed inside the membrane body, are formed by dissolving the sacrificial core materials (or sacrificial threads) described below. The shape, diameter or the like of the continuous holes can be controlled by selecting the shape or diameter of the sacrificial core materials (sacrificial threads).

[001932] Forming the continuous holes inside the ion exchange membrane can guarantee the mobility of an electrolyte solution in electrolysis. The shape of the continuous holes is not particularly limited, but it may be the shape of the sacrificial core materials to be used for forming the continuous holes according to the production method described below.

510/803

[001928] Among the materials of the reinforcement core, a particularly preferred form are highly oriented tape yarns or monofilaments comprising PTFE from the point of view of chemical resistance and heat resistance. Specifically, reinforcement core materials forming a single web in which 50 to 300 denier ribbon yarns obtained by cutting a high strength porous sheet comprising PTFE into a ribbon form, or highly oriented 50 to 300 denier monofilaments are used comprising PTFE and having a weave density of 10 to 50 threads or monofilaments / inch and having a thickness in the range of 50 to 100 µm are more preferred. The orifice ratio of an ion exchange membrane comprising such reinforcement core materials is still preferably 60% or more.

[001929] Examples of the shape of the reinforcement threads include round threads and ribbon threads. (Continuous holes)

[001930] The ion exchange membrane preferably has continuous holes inside the body of the membrane.

[001931] Continuous holes refer to holes that can be flow paths for fons generated in electrolysis and an electrolyte solution. The continuous holes, which are tubular holes formed inside the membrane body, are formed by dissolving the sacrificial core materials (or sacrificial threads) described below. The shape, diameter or the like of the continuous holes can be controlled by selecting the shape or diameter of the sacrificial core materials (sacrificial threads).

[001932] Forming the continuous holes inside the ion exchange membrane can guarantee the mobility of an electrolyte solution in electrolysis. The shape of the continuous holes is not particularly limited, but it may be the shape of the sacrificial core materials to be used for forming the continuous holes according to the production method described below.

[001933] The continuous holes are preferably formed so as to pass alternately through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcement core materials. With this structure, in a portion in which continuous holes are formed on the cathode side of the reinforcement core materials, ions (eg sodium fons) carried by the electrolyte solution with which the continuous holes are filled can also flow on the side of the cathode of the reinforcement core materials. As a result, the flow of cations is not interrupted and, therefore, it is possible to further reduce the electrical resistance of the ion exchange membrane.

[001934] Continuous holes can be formed along only a predetermined direction of the membrane body that constitutes the ion exchange membrane, but are preferably formed both in the longitudinal and in the transverse direction of the membrane body from the point of view of presenting a more stable electrolytic performance. [Production method]

[001935] A suitable example of a method for producing an ion exchange membrane includes a method including the following steps (1) to (6): Step (1): the step of producing a fluorine-containing polymer with an exchange group ionic or an ion exchange group precursor capable of forming an ion exchange group by hydrolysis, Step (2): the step of weaving at least a plurality of reinforcement core materials, as required, and sacrificial yarns with a proprietary dissolving in an acid or an alkali, and forming continuous holes to obtain a reinforcement material in which the sacrifice wires are arranged between the reinforcement core materials adjacent to each other, Step (3): the formation step in a fluorine-containing polymer film above with an ion exchange group or a precursor to the group

[001933] The continuous holes are preferably formed so as to pass alternately through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcement core materials. With this structure, in a portion in which continuous holes are formed on the cathode side of the reinforcement core materials, ions (eg sodium fons) carried by the electrolyte solution with which the continuous holes are filled can also flow on the side of the cathode of the reinforcement core materials. As a result, the flow of cations is not interrupted and, therefore, it is possible to further reduce the electrical resistance of the ion exchange membrane.

[001934] Continuous holes can be formed along only a predetermined direction of the membrane body that constitutes the ion exchange membrane, but are preferably formed both in the longitudinal and in the transverse direction of the membrane body from the point of view of presenting a more stable electrolytic performance. [Production method]

[001935] A suitable example of a method for producing an ion exchange membrane includes a method including the following steps (1) to (6): Step (1): the step of producing a fluorine-containing polymer with an exchange group ionic or an ion exchange group precursor capable of forming an ion exchange group by hydrolysis, Step (2): the step of weaving at least a plurality of reinforcement core materials, as required, and sacrificial yarns with a proprietary dissolving in an acid or an alkali, and forming continuous holes to obtain a reinforcement material in which the sacrifice wires are arranged between the reinforcement core materials adjacent to each other, Step (3): the formation step in a fluorine-containing polymer film above with an ion exchange group or a precursor to the ion exchange group capable of forming an ion exchange group by hydrolysis, Step (4): the step of embedding the reinforcement materials above, as required, in the film above a to obtain a membrane body within which the reinforcement materials are arranged, Step (5): the hydrolysis step of the membrane body obtained in step (4) (hydrolysis step), and Step (6): a step of providing a coating layer on the membrane body obtained in step (5) (application step).

[001936] Next, each of the steps will be described in detail.

Step (1): Fluorine-containing polymer production step

[001937] In step (1), the raw material monomers described in the first group for the third group above are used to produce a fluorine-containing polymer. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the raw material monomers must be adjusted in the production of the fluorine-containing polymer that forms the layers.

Step (2): Reinforcement materials production step

[001938] The reinforcement material is a woven fabric obtained by weaving reinforcement threads or the like. The reinforcement material is embedded in the membrane to form reinforcement core materials. When an ion exchange membrane with continuous holes is formed, the sacrificial threads are additionally woven into the reinforcement material. The amount of the sacrificial yarns contained in that case is preferably 10 to 80% by weight, more preferably 30 to 70% by weight based on the entire reinforcement material. Weaving the sacrificial yarns can also prevent the yarn from slipping the reinforcement core materials.

[001939] As sacrificial threads, which have solubility in the membrane production stage or under an electrolysis environment, rayon, polyethylene terephthalate (PET), cellulose, polyamide and the like are used. They are also ion exchange capable of forming an ion exchange group by hydrolysis, Step (4): the step of embedding the reinforcement materials above, as required, in the film above to obtain a membrane body inside which the materials of reinforcement are arranged, Step (5): the hydrolysis step of the membrane body obtained in step (4) (hydrolysis step), and Step (6): the step of providing a coating layer on the membrane body obtained in step (5) (application step).

[001936] Next, each of the steps will be described in detail.

Step (1): Fluorine-containing polymer production step

[001937] In step (1), the raw material monomers described in the first group for the third group above are used to produce a fluorine-containing polymer. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of the raw material monomers must be adjusted in the production of the fluorine-containing polymer that forms the layers.

Step (2): Reinforcement materials production step

[001938] The reinforcement material is a woven fabric obtained by weaving reinforcement threads or the like. The reinforcement material is embedded in the membrane to form reinforcement core materials. When an ion exchange membrane with continuous holes is formed, the sacrificial threads are additionally woven into the reinforcement material. The amount of the sacrificial yarns contained in that case is preferably 10 to 80% by weight, more preferably 30 to 70% by weight based on the entire reinforcement material. Weaving the sacrificial yarns can also prevent the yarn from slipping the reinforcement core materials.

[001939] As sacrificial threads, which have solubility in the membrane production stage or under an electrolysis environment, rayon, polyethylene terephthalate (PET), cellulose, polyamide and the like are used. They are also

513/803 preferred monofilaments or multifilaments with a thickness of 20 to 50 deniers and comprising polyvinyl alcohol and the like.

[001940] In step (2), the orifice ratio, the arrangement of continuous and similar holes can be controlled by adjusting the arrangement of the reinforcement core materials and the sacrifice wires. Step (3): Film forming step

[001941] In step (3), the fluorine-containing polymer obtained in step (1) is formed into a film using an extruder. The film can be a single layer configuration, a two layer configuration of a sulfonic acid layer and a layer of carboxylic acid, as mentioned above, or a multilayer configuration of three layers or more.

[001942] Examples of the film-forming method include the following: a method in which a fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are formed separately in films; and a method in which the fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are coextruded into a composite film.

[001943] The number of each film can be more than one. Coextrusion of different films is preferred because of their contribution to an increase in adhesive strength at the interface. Stage (4): Stage of obtaining the membrane body

[001944] In step (4), the reinforcement material obtained in step (2) is embedded in the film obtained in step (3) to provide a membrane body including the reinforcement material in it.

[001945] Preferable examples of the method for forming a membrane body include (1) a method in which a fluorine-containing polymer with

513/803 preferred monofilaments or multifilaments with a thickness of 20 to 50 deniers and comprising polyvinyl alcohol and the like.

[001940] In step (2), the orifice ratio, the arrangement of continuous and similar holes can be controlled by adjusting the arrangement of the reinforcement core materials and the sacrifice wires. Step (3): Film forming step

[001941] In step (3), the fluorine-containing polymer obtained in step (1) is formed into a film using an extruder. The film can be a single layer configuration, a two layer configuration of a sulfonic acid layer and a layer of carboxylic acid, as mentioned above, or a multilayer configuration of three layers or more.

[001942] Examples of the film-forming method include the following: a method in which a fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are formed separately in films; and a method in which the fluorine-containing polymer with a carboxylic acid group and a fluorine-containing polymer with a sulfonic acid group are coextruded into a composite film.

[001943] The number of each film can be more than one. Coextrusion of different films is preferred because of their contribution to an increase in adhesive strength at the interface. Stage (4): Stage of obtaining the membrane body

[001944] In step (4), the reinforcement material obtained in step (2) is embedded in the film obtained in step (3) to provide a membrane body including the reinforcement material in it.

[001945] Preferable examples of the method for forming a membrane body include (1) a method in which a fluorine-containing polymer with

514/803 a carboxylic acid group precursor (for example, carboxylate functional group) (hereinafter, a layer comprising the same is called the first layer) located on the cathode side and a fluorine-containing polymer with a sulfonic acid group precursor (for example, sulfonyl fluoride functional group) (hereinafter, a layer comprising the same is called a second layer) are formed in a film by a coextrusion method and, using a heat source and a vacuum source as If necessary, a reinforcement material and the second layer / first layer composite film are laminated in that order on heat-resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer is exposed. it melts while the air between each layer is evacuated under reduced pressure; and (11) a method in which, in addition to the composite film of the second layer / first layer, a fluorine-containing polymer with a precursor to the sulfonic acid group is formed separately in a film (the third layer) in advance and, using a heat source and a vacuum source as needed, the third layer film, the reinforcement core materials and the composite film comprising the second layer / first layer are laminated in that order on heat resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated under reduced pressure.

[001946] The coextrusion of the first layer and the second layer contributes to an increase in the adhesive strength at the interface.

[001947] The method including integration under reduced pressure is characterized by making the third layer in the reinforcement material thicker than that of the pressure method of applying pressure. In addition, since the reinforcement material is attached to the internal surface of the

514/803 a carboxylic acid group precursor (for example, carboxylate functional group) (hereinafter, a layer comprising the same is called the first layer) located on the cathode side and a fluorine-containing polymer with a sulfonic acid group precursor (for example, sulfonyl fluoride functional group) (hereinafter, a layer comprising the same is called a second layer) are formed in a film by a coextrusion method and, using a heat source and a vacuum source as If necessary, a reinforcement material and the second layer / first layer composite film are laminated in that order on heat-resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer is exposed. it melts while the air between each layer is evacuated under reduced pressure; and (11) a method in which, in addition to the composite film of the second layer / first layer, a fluorine-containing polymer with a precursor to the sulfonic acid group is formed separately in a film (the third layer) in advance and, using a heat source and a vacuum source as needed, the third layer film, the reinforcement core materials and the composite film comprising the second layer / first layer are laminated in that order on heat resistant breathable release paper on a flat plate or drum with many pores on its surface and integrated at a temperature at which each polymer melts while the air between each layer is evacuated under reduced pressure.

[001946] The coextrusion of the first layer and the second layer contributes to an increase in the adhesive strength at the interface.

[001947] The method including integration under reduced pressure is characterized by making the third layer in the reinforcement material thicker than that of the pressure method of applying pressure. In addition, since the reinforcement material is attached to the internal surface of the

515/803 membrane, the method has a property of sufficiently retaining the mechanical resistance of the ion exchange membrane.

[001948] The lamination variations described here are exemplary, and coextrusion can be performed after a preferred lamination pattern (for example, the combination of layers) is appropriately selected considering the desired layer configuration of the membrane body and physical properties, and the like.

[001949] In order to further improve the electrical properties of the ion exchange membrane, it is also possible to additionally interpose a fourth layer comprising a fluorine-containing polymer with a precursor of the carboxylic acid group and a precursor of the sulfonic acid group between the first layer and the second layer or using a fourth layer comprising a fluorine-containing polymer with a carboxylic acid group precursor and a sulfonic acid group precursor instead of the second layer.

[001950] The method for forming the fourth layer can be a method in which a fluorine-containing polymer with a carboxylic acid group precursor and a fluorine-containing polymer with a sulfonic acid group precursor are separately produced and then mixed or can be a method wherein a monomer with a precursor to the carboxylic acid group and a monomer with a precursor to the sulfonic acid group are copolymerized.

[001951] When the fourth layer is used as a component of the ion exchange membrane, a coextruded film of the first layer and the fourth layer is formed, in addition, the third layer and the second layer are formed separately in films, and the lamination can be performed by the method mentioned above. Alternatively, the three layers of the first layer / fourth layer / second layer can be simultaneously formed into a film by coextrusion.

515/803 membrane, the method has a property of sufficiently retaining the mechanical resistance of the ion exchange membrane.

[001948] The lamination variations described here are exemplary, and coextrusion can be performed after a preferred lamination pattern (for example, the combination of layers) is appropriately selected considering the desired layer configuration of the membrane body and physical properties, and the like.

[001949] In order to further improve the electrical properties of the ion exchange membrane, it is also possible to additionally interpose a fourth layer comprising a fluorine-containing polymer with a precursor of the carboxylic acid group and a precursor of the sulfonic acid group between the first layer and the second layer or using a fourth layer comprising a fluorine-containing polymer with a carboxylic acid group precursor and a sulfonic acid group precursor instead of the second layer.

[001950] The method for forming the fourth layer can be a method in which a fluorine-containing polymer with a carboxylic acid group precursor and a fluorine-containing polymer with a sulfonic acid group precursor are separately produced and then mixed or can be a method wherein a monomer with a precursor to the carboxylic acid group and a monomer with a precursor to the sulfonic acid group are copolymerized.

[001951] When the fourth layer is used as a component of the ion exchange membrane, a coextruded film of the first layer and the fourth layer is formed, in addition, the third layer and the second layer are formed separately in films, and the lamination can be performed by the method mentioned above. Alternatively, the three layers of the first layer / fourth layer / second layer can be simultaneously formed into a film by coextrusion.

516/803

[001952] In this case, the direction in which the extruded film flows is the MD. As mentioned above, it is possible to form a membrane body containing a fluorine-containing polymer with an ion exchange group in a reinforcement material.

[001953] Additionally, the ion exchange membrane preferably has protruding portions composed of the fluorine-containing polymer with a sulfonic acid group, that is, projections, on the surface side composed of the sulfonic acid layer. As a method for forming such projections, which is not particularly limited, one can also use a known method including forming projections on a resin surface. A specific example of the method is a method of embossing the surface of the membrane body. For example, the above projections can be formed using release paper embossed in advance when the composite film mentioned above, reinforcement material and the like are integrated. In the case where the projections are formed by embossing, the height and density of arrangement of the projections can be controlled by controlling the form of embossing to be transferred (shape of the release paper). (5) Hydrolysis step

[001954] In step (5), a hydrolysis step of the membrane body obtained in step (4) is carried out to convert the precursor of the ion exchange group into an ion exchange group (hydrolysis step).

[001955] In step (5), it is also possible to form dissolution holes in the membrane body by dissolving and removing the sacrifice wires included in the membrane body with acid or alkali. The sacrifice wires can remain in the continuous holes without being completely dissolved and removed. The sacrifice wires that remain in the continuous holes can be dissolved and removed by the electrolyte solution when the ion exchange membrane is subjected to electrolysis.

516/803

[001952] In this case, the direction in which the extruded film flows is the MD. As mentioned above, it is possible to form a membrane body containing a fluorine-containing polymer with an ion exchange group in a reinforcement material.

[001953] Additionally, the ion exchange membrane preferably has protruding portions composed of the fluorine-containing polymer with a sulfonic acid group, that is, projections, on the surface side composed of the sulfonic acid layer. As a method for forming such projections, which is not particularly limited, one can also use a known method including forming projections on a resin surface. A specific example of the method is a method of embossing the surface of the membrane body. For example, the above projections can be formed using release paper embossed in advance when the composite film mentioned above, reinforcement material and the like are integrated. In the case where the projections are formed by embossing, the height and density of arrangement of the projections can be controlled by controlling the form of embossing to be transferred (shape of the release paper). (5) Hydrolysis step

[001954] In step (5), a hydrolysis step of the membrane body obtained in step (4) is carried out to convert the precursor of the ion exchange group into an ion exchange group (hydrolysis step).

[001955] In step (5), it is also possible to form dissolution holes in the membrane body by dissolving and removing the sacrifice wires included in the membrane body with acid or alkali. The sacrifice wires can remain in the continuous holes without being completely dissolved and removed. The sacrifice wires that remain in the continuous holes can be dissolved and removed by the electrolyte solution when the ion exchange membrane is subjected to electrolysis.

517/803

[001956] The sacrifice wire has solubility in acid or alkali in the production stage of an ion exchange membrane or under an electrolysis environment. The sacrifice wires are eluted to form continuous holes at the corresponding locations.

[001957] Step (5) can be carried out by immersing the membrane body obtained in step (4) in a hydrolysis solution containing acid or alkali. An example of the hydrolysis solution that can be used is a mixed solution containing KOH and dimethyl sulfoxide (DMSO).

[001958] The mixed solution preferably contains 2.5 to 4.0 N KOH and 25 to 35% by weight DMSO.

[001959] The temperature for hydrolysis is preferably 70 to 100 ° C. The higher the temperature, the greater the apparent thickness. The temperature is more preferably 75 to 100 ° C.

[001960] The time for hydrolysis is preferably 10 to 120 minutes. The longer the time, the greater the apparent thickness. The time is most preferably 20 to 120 minutes.

[001961] The step of forming continuous holes eluting the sacrificial wire will now be described in more detail. Figures 122 (a) and (b) are schematic views to explain a method for forming the continuous holes in the ion exchange membrane.

[001962] Figures 122 (a) and (b) show the reinforcement wires 52, the sacrifice wires 504a and the continuous holes 504 formed only by the sacrifice wires 504a, omitting the illustration of the other members, such as a body of membrane.

[001963] Firstly, the reinforcement wires 52 which constitute reinforcement core materials in the ion exchange membrane and the sacrifice wires 504a to form the continuous holes 504 in the ion exchange membrane are used as interlaced reinforcement materials. Then, in step (5), the sacrifice threads 504a are eluted to form continuous holes 504.

517/803

[001956] The sacrifice wire has solubility in acid or alkali in the production stage of an ion exchange membrane or under an electrolysis environment. The sacrifice wires are eluted to form continuous holes at the corresponding locations.

[001957] Step (5) can be carried out by immersing the membrane body obtained in step (4) in a hydrolysis solution containing acid or alkali. An example of the hydrolysis solution that can be used is a mixed solution containing KOH and dimethyl sulfoxide (DMSO).

[001958] The mixed solution preferably contains 2.5 to 4.0 N KOH and 25 to 35% by weight DMSO.

[001959] The temperature for hydrolysis is preferably 70 to 100 ° C. The higher the temperature, the greater the apparent thickness. The temperature is more preferably 75 to 100 ° C.

[001960] The time for hydrolysis is preferably 10 to 120 minutes. The longer the time, the greater the apparent thickness. The time is most preferably 20 to 120 minutes.

[001961] The step of forming continuous holes eluting the sacrificial wire will now be described in more detail. Figures 122 (a) and (b) are schematic views to explain a method for forming the continuous holes in the ion exchange membrane.

[001962] Figures 122 (a) and (b) show the reinforcement wires 52, the sacrifice wires 504a and the continuous holes 504 formed only by the sacrifice wires 504a, omitting the illustration of the other members, such as a body of membrane.

[001963] Firstly, the reinforcement wires 52 which constitute reinforcement core materials in the ion exchange membrane and the sacrifice wires 504a to form the continuous holes 504 in the ion exchange membrane are used as interlaced reinforcement materials. Then, in step (5), the sacrifice threads 504a are eluted to form continuous holes 504.

518/803

[001964] The above method is simple because the method for interlacing the reinforcement wires 52 and the sacrifice wires 504a can be adjusted depending on the arrangement of the reinforcement core materials and the continuous holes in the membrane body of the ion exchange membrane.

[001965] Figure 122 (a) exemplifies the simple fabric reinforcement material in which reinforcement threads 52 and sacrifice threads 504a are interwoven along the longitudinal and lateral direction on the paper, and the arrangement of the reinforcement 52 and the sacrifice wires 504a in the reinforcement material may vary as required. (6) Application stage

[001966] In step (6), a coating layer can be formed by preparing a coating liquid containing particles of inorganic material obtained by grinding raw ore or melting raw ore and a binder, applying the coating liquid on the surface of the ion exchange membrane obtained in step (5), and drying of the coating liquid.

[001967] A preferred binder is a binder obtained by hydrolysis of a fluorine-containing polymer with an ion exchange group precursor with an aqueous solution containing dimethylsulfoxide (DMSO) and potassium hydroxide (KOH) and then immersion of the polymer in hydrochloric acid to replace the counter-ion of the ion exchange group with H + (for example, a fluorine-containing polymer with a carboxyl group or a sulfo group). Thus, the polymer is more likely to dissolve in water or ethanol mentioned below, which is preferable.

[001968] This binder is dissolved in a mixed solution of water and ethanol. The volume ratio between water and ethanol is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 2: 1 to 1: 2. The particles of inorganic material are dispersed with a ball mill in the dissolution liquid thus obtained to provide a liquid of

518/803

[001964] The above method is simple because the method for interlacing the reinforcement wires 52 and the sacrifice wires 504a can be adjusted depending on the arrangement of the reinforcement core materials and the continuous holes in the membrane body of the ion exchange membrane.

[001965] Figure 122 (a) exemplifies the simple fabric reinforcement material in which reinforcement threads 52 and sacrifice threads 504a are interwoven along the longitudinal and lateral direction on the paper, and the arrangement of the reinforcement 52 and the sacrifice wires 504a in the reinforcement material may vary as required. (6) Application stage

[001966] In step (6), a coating layer can be formed by preparing a coating liquid containing particles of inorganic material obtained by grinding raw ore or melting raw ore and a binder, applying the coating liquid on the surface of the ion exchange membrane obtained in step (5), and drying of the coating liquid.

[001967] A preferred binder is a binder obtained by hydrolysis of a fluorine-containing polymer with an ion exchange group precursor with an aqueous solution containing dimethylsulfoxide (DMSO) and potassium hydroxide (KOH) and then immersion of the polymer in hydrochloric acid to replace the counter-ion of the ion exchange group with H + (for example, a fluorine-containing polymer with a carboxyl group or a sulfo group). Thus, the polymer is more likely to dissolve in water or ethanol mentioned below, which is preferable.

[001968] This binder is dissolved in a mixed solution of water and ethanol. The volume ratio between water and ethanol is preferably 10: 1 to 1:10, more preferably 5: 1 to 1: 5, even more preferably 2: 1 to 1: 2. The particles of inorganic material are dispersed with a ball mill in the dissolution liquid thus obtained to provide a liquid of

519/803 coating. In this case, it is also possible to adjust the average particle size and the like of the particles by adjusting the time and speed of rotation during dispersion. The preferable amount of the particles of inorganic material and the binder to be mixed is as mentioned above.

[001969] The concentration of the particles of inorganic material and the binder in the coating liquid is not particularly limited, but a thin-coated liquid is preferable. This allows uniform application to the surface of the ion exchange membrane.

[001970] Additionally, a surfactant can be added to the dispersion when the particles of inorganic material are dispersed. Like the surfactant, nonionic surfactants are preferable and examples of them include HS-210, NS-210, P-210 and E-212 manufactured by NOF CORPORATION.

[001971] The coating liquid obtained is applied on the surface of the ion exchange membrane by spray application or roller coating, thus providing an ion exchange membrane. [Microporous membrane]

[001972] The microporous membrane of the present modality is not particularly limited as long as the membrane can be formed in a laminate with the electrolysis electrode, as mentioned above. Several microporous membranes can be used.

[001973] The porosity of the microporous membrane of the present embodiment is not particularly limited, but it can be from 20 to 90, for example, and is preferably from 30 to 85. The porosity above can be calculated by the following formula: Porosity = (1 - (the weight of the membrane in a dry state) / (the weight calculated from the volume calculated from the thickness, width and length of the membrane and the density of the membrane material)) x 100

[001974] The average pore size of the microporous membrane of the

519/803 coating. In this case, it is also possible to adjust the average particle size and the like of the particles by adjusting the time and speed of rotation during dispersion. The preferable amount of the particles of inorganic material and the binder to be mixed is as mentioned above.

[001969] The concentration of the particles of inorganic material and the binder in the coating liquid is not particularly limited, but a thin-coated liquid is preferable. This allows uniform application to the surface of the ion exchange membrane.

[001970] Additionally, a surfactant can be added to the dispersion when the particles of inorganic material are dispersed. Like the surfactant, nonionic surfactants are preferable and examples of them include HS-210, NS-210, P-210 and E-212 manufactured by NOF CORPORATION.

[001971] The coating liquid obtained is applied on the surface of the ion exchange membrane by spray application or roller coating, thus providing an ion exchange membrane. [Microporous membrane]

[001972] The microporous membrane of the present modality is not particularly limited as long as the membrane can be formed in a laminate with the electrolysis electrode, as mentioned above. Several microporous membranes can be used.

[001973] The porosity of the microporous membrane of the present embodiment is not particularly limited, but it can be from 20 to 90, for example, and is preferably from 30 to 85. The porosity above can be calculated by the following formula: Porosity = (1 - (the weight of the membrane in a dry state) / (the weight calculated from the volume calculated from the thickness, width and length of the membrane and the density of the membrane material)) x 100

[001974] The average pore size of the microporous membrane of the

520/803 the present embodiment is not particularly limited, and may be 0.01 µm to 1 µm, for example, preferably 0.05 µm to 5 µm. Regarding the average pore size, for example, the membrane is cut vertically in the direction of thickness, and the section is observed with an FE-SEM. The average pore size can be obtained by measuring the diameter of about 100 observed pores and averaging the measurements.

[001975] The thickness of the microporous membrane of the present embodiment is not particularly limited, and can be from 10 µm to 1000 µm, for example, preferably 50 µm to 600 µm. The above thickness can be measured using a micrometer (manufactured by Mitutoyo Corporation) or similar, for example.

[001976] Specific examples of the microporous membrane as mentioned above include Zirfon Perl UTP 500 manufactured by Agfa and those described in International Publication No. WO 2013-183584 and International Publication No. WO 2016-203701.

[001977] In the method of producing an electrolyzer according to the present embodiment, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with an EW (ion exchange capacity) different from that of the first ion exchange resin layer. In addition, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different functional group than that of the first layer of ion exchange resin. The ion exchange capacity can be adjusted by the functional group to be introduced, and functional groups that can be introduced are as mentioned above. (Water electrolysis)

[001978] The electrolyzer in the present modality, as an electrolyzer in the case of water electrolysis, has a configuration in which the ion exchange membrane in an electrolyzer for use in the case of common salt electrolysis

520/803 the present embodiment is not particularly limited, and may be 0.01 µm to 1 µm, for example, preferably 0.05 µm to 5 µm. Regarding the average pore size, for example, the membrane is cut vertically in the direction of thickness, and the section is observed with an FE-SEM. The average pore size can be obtained by measuring the diameter of about 100 observed pores and averaging the measurements.

[001975] The thickness of the microporous membrane of the present embodiment is not particularly limited, and can be from 10 µm to 1000 µm, for example, preferably 50 µm to 600 µm. The above thickness can be measured using a micrometer (manufactured by Mitutoyo Corporation) or similar, for example.

[001976] Specific examples of the microporous membrane as mentioned above include Zirfon Perl UTP 500 manufactured by Agfa and those described in International Publication No. WO 2013-183584 and International Publication No. WO 2016-203701.

[001977] In the method of producing an electrolyzer according to the present embodiment, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with an EW (ion exchange capacity) different from that of the first ion exchange resin layer. In addition, the membrane preferably comprises a first layer of ion exchange resin and a second layer of ion exchange resin with a different functional group than that of the first layer of ion exchange resin. The ion exchange capacity can be adjusted by the functional group to be introduced, and functional groups that can be introduced are as mentioned above. (Water electrolysis)

[001978] The electrolyzer in the present modality, as an electrolyzer in the case of water electrolysis, has a configuration in which the ion exchange membrane in an electrolyzer for use in the case of common salt electrolysis

521/803 mentioned above is replaced by a microporous membrane. The raw material to be supplied, which is water, is different from that for the electrolyser in the case of electrolysis of the common salt mentioned above. As for the other components, components similar to those of the electrolyser in the case of electrolysis of common salt can also be used in the electrolyser in the case of water electrolysis. Since chlorine gas is generated in the anodic chamber in the case of common salt electrolysis, titanium is used as the material in the anodic chamber, but in the case of water electrolysis, only oxygen gas is generated in the anodic chamber. Thus, a material identical to that of the cathodic chamber can be used. An example of this is nickel. For the anode coating, the catalyst coating for oxygen generation is suitable. Examples of the catalyst coating include metals, oxides and hydroxides of the metals of the platinum group and metals of the transition metal group. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used. Examples

[001979] The present invention will be described in more detail with reference to the Examples and Comparative Examples below, but the present invention is not limited to the Examples below in any way. <Verification of the first modality>

[001980] As will be described below, Experimental Examples were provided according to the first modality (in the <Verification of the first modality> section below, simply called “Examples”) and Experimental Examples not according to the first modality (in the section <Verification of the first modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 10 to 21, as appropriate. [Evaluation method]

521/803 mentioned above is replaced by a microporous membrane. The raw material to be supplied, which is water, is different from that for the electrolyser in the case of electrolysis of the common salt mentioned above. As for the other components, components similar to those of the electrolyser in the case of electrolysis of common salt can also be used in the electrolyser in the case of water electrolysis. Since chlorine gas is generated in the anodic chamber in the case of common salt electrolysis, titanium is used as the material in the anodic chamber, but in the case of water electrolysis, only oxygen gas is generated in the anodic chamber. Thus, a material identical to that of the cathodic chamber can be used. An example of this is nickel. For the anode coating, the catalyst coating for oxygen generation is suitable. Examples of the catalyst coating include metals, oxides and hydroxides of the metals of the platinum group and metals of the transition metal group. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt and iron can be used. Examples

[001979] The present invention will be described in more detail with reference to the Examples and Comparative Examples below, but the present invention is not limited to the Examples below in any way. <Verification of the first modality>

[001980] As will be described below, Experimental Examples were provided according to the first modality (in the <Verification of the first modality> section below, simply called “Examples”) and Experimental Examples not according to the first modality (in the section <Verification of the first modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 10 to 21, as appropriate. [Evaluation method]

522/803 (1) Opening ratio

[001981] An electrode was cut to a size of 130 mm x 100 mm. A digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale of 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the electrode thickness (gauge thickness) to calculate the volume. Subsequently, an electronic scale was used to measure the mass. From the specific gravity of each metal (specific gravity of nickel = 8.908 glem ?, specific gravity of titanium = 4.506 g / emi), the opening ratio or vacuum ratio was calculated. Opening ratio (Vacuum ratio) (%) = (1 - (electrode mass) / (electrode volume x specific gravity of the nickel)) x 100 (2) Mass per unit area (mg / cm?)

[001982] An electrode was cut to a size of 130 mm x 100 mm, and the mass was measured by an electronic scale. The value was divided by the area (130 mm x 100 mm) to calculate the mass per unit area. (3) Force applied per unit mass-unit area (1) (adhesive force) (N / mg: cm?)) [Method (i)]

[001983] A tensile and compression test machine was used for measurement (Imada-SS Corporation, main testing machine: SDT-S2NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[001984] A 200 mm square nickel plate with a thickness of 1.2 mm was subjected to pickling processing with 320 grain size alumina. The arithmetic mean roughness of the surface (Ra) of the nickel plate after treatment by pickling was 0.7 µm. To measure the surface roughness, an instrument for measuring surface roughness of the SJ-310 type probe (Mitutoyo Corporation) was used.

522/803 (1) Opening ratio

[001981] An electrode was cut to a size of 130 mm x 100 mm. A digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale of 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the electrode thickness (gauge thickness) to calculate the volume. Subsequently, an electronic scale was used to measure the mass. From the specific gravity of each metal (specific gravity of nickel = 8.908 glem ?, specific gravity of titanium = 4.506 g / emi), the opening ratio or vacuum ratio was calculated. Opening ratio (Vacuum ratio) (%) = (1 - (electrode mass) / (electrode volume x specific gravity of the nickel)) x 100 (2) Mass per unit area (mg / cm?)

[001982] An electrode was cut to a size of 130 mm x 100 mm, and the mass was measured by an electronic scale. The value was divided by the area (130 mm x 100 mm) to calculate the mass per unit area. (3) Force applied per unit mass-unit area (1) (adhesive force) (N / mg: cm?)) [Method (i)]

[001983] A tensile and compression test machine was used for measurement (Imada-SS Corporation, main testing machine: SDT-S2NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[001984] A 200 mm square nickel plate with a thickness of 1.2 mm was subjected to pickling processing with 320 grain size alumina. The arithmetic mean roughness of the surface (Ra) of the nickel plate after treatment by pickling was 0.7 µm. To measure the surface roughness, an instrument for measuring surface roughness of the SJ-310 type probe (Mitutoyo Corporation) was used.

523/803 A measurement sample was placed on the surface plate parallel to the soil surface to measure the arithmetic mean roughness Ra under measurement conditions as described below. The measurement was repeated 6 times and the average value was listed.

<Probe shape> conical tapering angle = 60º, tip radius = 2 um, static measuring force = 0.75 mN <Roughness pattern> JIS2001 <Evaluation curve> R <Filter> GAUSS <Ac cut value> 0.8 mm <As cut value> 2.5 um <Number of sections> 5 <Pre-run, post-run> available

[001985] This nickel plate was fixed vertically to the lower shim of the tensile and compression testing machine.

[001986] As the membrane, an ion exchange membrane À below was used.

[001987] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarn) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[001988] Next, a dry resin A which was a copolymer of CF; = CF, and

523/803 A measurement sample was placed on the surface plate parallel to the soil surface to measure the arithmetic mean roughness Ra under measurement conditions as described below. The measurement was repeated 6 times and the average value was listed.

<Probe shape> conical tapering angle = 60º, tip radius = 2 um, static measuring force = 0.75 mN <Roughness pattern> JIS2001 <Evaluation curve> R <Filter> GAUSS <Ac cut value> 0.8 mm <As cut value> 2.5 um <Number of sections> 5 <Pre-run, post-run> available

[001985] This nickel plate was fixed vertically to the lower shim of the tensile and compression testing machine.

[001986] As the membrane, an ion exchange membrane À below was used.

[001987] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarn) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[001988] Next, a dry resin A which was a copolymer of CF; = CF, and

524/803 CF; = CFOCF; CF (CF3) OCF; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a B resin of a dry resin that was a copolymer of CF; = CF ,; and CF. = CFOCF; CF (CF3) OCF; CF3SO, xF and had an ion exchange capacity of 1.03 mg equivalent / g.

[001989] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[001990] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[001991] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[001992] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of acid type B resin and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the surfaces of the

524/803 CF; = CFOCF; CF (CF3) OCF; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a B resin of a dry resin that was a copolymer of CF; = CF ,; and CF. = CFOCF; CF (CF3) OCF; CF3SO, xF and had an ion exchange capacity of 1.03 mg equivalent / g.

[001989] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[001990] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[001991] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[001992] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of acid type B resin and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the surfaces of the

525/803 composite membrane to obtain an ion exchange membrane A. The zirconium oxide coating density measured by X-ray fluorescence measurement was 0.5 mg / em ?. The average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[001993] The ion exchange membrane (membrane) obtained above was immersed in pure water for 12 hours or more and then used for the test. The membrane was placed in contact with the nickel plate above sufficiently moistened with pure water and allowed to adhere to the plate by the water tension. At that time, the nickel plate and the ion exchange membrane were placed in order to align their upper ends.

[001994] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The ion exchange membrane A was cut into a 170 mm square. One side of the electrode was sandwiched by two stainless steel plates (thickness: 1 mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[001995] The upper shim of the tensile and compression testing machine was lowered, and the electrode sample for electrolysis was allowed to adhere to the

525/803 composite membrane to obtain an ion exchange membrane A. The zirconium oxide coating density measured by X-ray fluorescence measurement was 0.5 mg / em ?. The average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[001993] The ion exchange membrane (membrane) obtained above was immersed in pure water for 12 hours or more and then used for the test. The membrane was placed in contact with the nickel plate above sufficiently moistened with pure water and allowed to adhere to the plate by the water tension. At that time, the nickel plate and the ion exchange membrane were placed in order to align their upper ends.

[001994] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The ion exchange membrane A was cut into a 170 mm square. One side of the electrode was sandwiched by two stainless steel plates (thickness: 1 mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[001995] The upper shim of the tensile and compression testing machine was lowered, and the electrode sample for electrolysis was allowed to adhere to the

526/803 surface of the ion exchange membrane by the surface tension of pure water. The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and ion exchange membrane entirely in order to sufficiently moisten the membrane and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess pure water. The roll was laminated only once.

[001996] The electrode was raised at a rate of 10 mm / minute to start the measurement of charge, and the charge when the size of the overlapped portion of the electrode and the membrane reached 130 mm in width and 100 mm in length was recorded. This measurement was repeated three times and the average value was calculated.

[001997] This average value was divided by the area of the overlapping portion of the electrode and the ion exchange membrane and the mass of the electrode of the portion overlapping the ion exchange membrane to calculate the force applied per unit mass-unit area (1) . The electrode mass of the portion superimposed on the ion exchange membrane was determined through proportional calculation from the value obtained in (2) Mass per unit area (mg / cm?) Described above.

[001998] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[001999] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to the ion exchange membrane that adhered to a nickel plate fixed vertically through the surface tension.

[002000] A schematic view of a method for assessing strength

526/803 surface of the ion exchange membrane by the surface tension of pure water. The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and ion exchange membrane entirely in order to sufficiently moisten the membrane and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess pure water. The roll was laminated only once.

[001996] The electrode was raised at a rate of 10 mm / minute to start the measurement of charge, and the charge when the size of the overlapped portion of the electrode and the membrane reached 130 mm in width and 100 mm in length was recorded. This measurement was repeated three times and the average value was calculated.

[001997] This average value was divided by the area of the overlapping portion of the electrode and the ion exchange membrane and the mass of the electrode of the portion overlapping the ion exchange membrane to calculate the force applied per unit mass-unit area (1) . The electrode mass of the portion superimposed on the ion exchange membrane was determined through proportional calculation from the value obtained in (2) Mass per unit area (mg / cm?) Described above.

[001998] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[001999] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to the ion exchange membrane that adhered to a nickel plate fixed vertically through the surface tension.

[002000] A schematic view of a method for assessing strength

527/803 applied (1) is shown in Figure 10.

[002001] The lower limit of measurement of the tensile testing machine was 0.01 (N). (4) Force applied per unit mass-unit area (2) (adhesive force) (N / mg: cm?)) [Method (ii)]

[002002] A tensile and compression test machine was used for measurement (Imada-SS Corporation, main testing machine: SDT-S2NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[002003] A nickel plate identical to that of Method (1) was fixed vertically to the lower shim of the tensile and compression testing machine.

[002004] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The ion exchange membrane A was cut into a 170 mm square. One side of the electrode was sandwiched by two stainless steel plates (thickness: 1 mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[002005] The upper shim of the tensile and compression testing machine

527/803 applied (1) is shown in Figure 10.

[002001] The lower limit of measurement of the tensile testing machine was 0.01 (N). (4) Force applied per unit mass-unit area (2) (adhesive force) (N / mg: cm?)) [Method (ii)]

[002002] A tensile and compression test machine was used for measurement (Imada-SS Corporation, main testing machine: SDT-S2NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[002003] A nickel plate identical to that of Method (1) was fixed vertically to the lower shim of the tensile and compression testing machine.

[002004] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The ion exchange membrane A was cut into a 170 mm square. One side of the electrode was sandwiched by two stainless steel plates (thickness: 1 mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[002005] The upper shim of the tensile and compression testing machine

528/803 was lowered, and the electrolysis electrode sample was allowed to adhere to the nickel plate surface through the surface tension of a solution. The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and the nickel plate entirely in order to sufficiently moisten the nickel plate and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess solution. The roll was laminated only once.

[002006] The electrode was raised at a rate of 10 mm / minute to start the charge measurement, and the charge when the size of the overlapping portion of the electrode and the nickel plate in the longitudinal direction reached 100 mm was recorded. This measurement was repeated three times and the average value was calculated.

[002007] This average value was divided by the area of the overlapping portion of the electrode and the nickel plate and the mass of the electrode of the portion overlapping the nickel plate to calculate the force applied per unit mass-unit area (2). The electrode mass of the portion superimposed on the membrane was determined through proportional calculation from the value obtained in (2) mass per unit area (mg / cm?) Described above.

[002008] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[002009] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to a nickel plate fixed vertically through the surface tension.

[002010] The lower limit of measurement of the tensile testing machine was 0.01 (N).

528/803 was lowered, and the electrolysis electrode sample was allowed to adhere to the nickel plate surface through the surface tension of a solution. The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and the nickel plate entirely in order to sufficiently moisten the nickel plate and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess solution. The roll was laminated only once.

[002006] The electrode was raised at a rate of 10 mm / minute to start the charge measurement, and the charge when the size of the overlapping portion of the electrode and the nickel plate in the longitudinal direction reached 100 mm was recorded. This measurement was repeated three times and the average value was calculated.

[002007] This average value was divided by the area of the overlapping portion of the electrode and the nickel plate and the mass of the electrode of the portion overlapping the nickel plate to calculate the force applied per unit mass-unit area (2). The electrode mass of the portion superimposed on the membrane was determined through proportional calculation from the value obtained in (2) mass per unit area (mg / cm?) Described above.

[002008] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[002009] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to a nickel plate fixed vertically through the surface tension.

[002010] The lower limit of measurement of the tensile testing machine was 0.01 (N).

529/803 (5) Method for evaluating the winding around the 280 mm diameter column (1) (%) (Membrane and column)

[002011] The evaluation method (1) was conducted by the following procedure.

[002012] The ion exchange membrane A (membrane) produced in [Method (1)] was cut into a 170 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In Comparative Examples 10 and 11, the electrode was integrated with the ion exchange membrane by thermal pressing, and thus an integrated part of an ion exchange membrane and an electrode (130 mm square electrode) was provided. After the ion exchange membrane was sufficiently immersed in pure water, the membrane was placed on the curved surface of a plastic (polyethylene) tube with an outer diameter of 280 mm. Subsequently, the excess solution was removed with a roller formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (external diameter: 38 mm). The roll was laminated over the ion exchange membrane from left to right from the schematic view shown in Figure 11. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the plastic tube electrode with an external diameter of 280 mm was measured. (6) Method for evaluating the winding around the 280 mm diameter column (2) (%) (Membrane and electrode)

[002013] The evaluation method (2) was conducted by the following procedure.

[002014] The ion exchange membrane A (membrane) produced in the

529/803 (5) Method for evaluating the winding around the 280 mm diameter column (1) (%) (Membrane and column)

[002011] The evaluation method (1) was conducted by the following procedure.

[002012] The ion exchange membrane A (membrane) produced in [Method (1)] was cut into a 170 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In Comparative Examples 10 and 11, the electrode was integrated with the ion exchange membrane by thermal pressing, and thus an integrated part of an ion exchange membrane and an electrode (130 mm square electrode) was provided. After the ion exchange membrane was sufficiently immersed in pure water, the membrane was placed on the curved surface of a plastic (polyethylene) tube with an outer diameter of 280 mm. Subsequently, the excess solution was removed with a roller formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (external diameter: 38 mm). The roll was laminated over the ion exchange membrane from left to right from the schematic view shown in Figure 11. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the plastic tube electrode with an external diameter of 280 mm was measured. (6) Method for evaluating the winding around the 280 mm diameter column (2) (%) (Membrane and electrode)

[002013] The evaluation method (2) was conducted by the following procedure.

[002014] The ion exchange membrane A (membrane) produced in the

530/803 [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 280 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was laminated from left to right in the schematic view shown in Figure 12 with light pressure on the electrode to remove excess solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured. (7) Method for assessing the winding around the 145 mm diameter column (3) (%) (Membrane and electrode)

[002015] The evaluation method (3) was conducted by the following procedure.

[002016] The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 145 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a tube of vinyl chloride (diameter

530/803 [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 280 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was laminated from left to right in the schematic view shown in Figure 12 with light pressure on the electrode to remove excess solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured. (7) Method for assessing the winding around the 145 mm diameter column (3) (%) (Membrane and electrode)

[002015] The evaluation method (3) was conducted by the following procedure.

[002016] The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 145 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a tube of vinyl chloride (diameter

531/803 external: 38 mm) was laminated from left to right from the schematic view shown in Figure 13 with light pressure on the electrode to remove excess solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured. (8) Handling property (response assessment)

[002017] (A) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: aqueous sodium bicarbonate solution, aqueous 0.1 N NaOH solution and pure water, then laminated and placed immobile on a Teflon plate. The interval between the anodic cell and the cathodic cell used in the electrolytic evaluation was established at about 3 cm. The laminate placed immobile was lifted and an insertion and retention operation of the laminate was carried out between them. This operation was performed while the electrode was checked for displacement and fall.

[002018] (B) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: an aqueous solution of sodium bicarbonate, an aqueous solution of NaOH 0.1 N and pure water, then laminated and placed immobile on a Teflon plate . The two adjacent corners of the membrane portion of the laminate were held by hands to lift the laminate so that it was vertical. The two corners held by the hands were moved from this state to be close to each other, so that the

531/803 external: 38 mm) was laminated from left to right from the schematic view shown in Figure 13 with light pressure on the electrode to remove excess solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured. (8) Handling property (response assessment)

[002017] (A) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: aqueous sodium bicarbonate solution, aqueous 0.1 N NaOH solution and pure water, then laminated and placed immobile on a Teflon plate. The interval between the anodic cell and the cathodic cell used in the electrolytic evaluation was established at about 3 cm. The laminate placed immobile was lifted and an insertion and retention operation of the laminate was carried out between them. This operation was performed while the electrode was checked for displacement and fall.

[002018] (B) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: an aqueous solution of sodium bicarbonate, an aqueous solution of NaOH 0.1 N and pure water, then laminated and placed immobile on a Teflon plate . The two adjacent corners of the membrane portion of the laminate were held by hands to lift the laminate so that it was vertical. The two corners held by the hands were moved from this state to be close to each other, so that the

532/803 membrane was designed or embedded. This movement was repeated again to check the conformability of the electrode to the membrane. The results were evaluated on a four-level scale from 1 to 4, based on the following indices: 1: good manipulation property 2: able to be manipulated 3: difficult to manipulate 4: substantially unable to be manipulated

[002019] Here, the sample from Comparative Example 5, provided in a size equivalent to that of a large electrolytic cell including an electrode in a size of 1.3 mx 2.5 m and an ion exchange membrane in a size of 1.5 mx 2.8 m, was subjected to manipulation. The result of the evaluation of Comparative Example 5 (“3” as described below) was used as an Index to assess the difference between the evaluation of (A) and (B) above and the largest. That is, in the case where the result of the evaluation of a small laminate was "1" or "2", it was considered that there was no problem in the handling property even if the laminate was provided in a larger size. (9) Electrolytic evaluation (voltage (V), current efficiency (%), common saline concentration in caustic soda (ppm, on the basis of 50%))

[002020] Electrolytic performance was assessed by the following electrolytic experiment.

[002021] A titanium anode cell with an anodic chamber in which an anode (anode terminal cell) was provided and a cathode cell with a nickel cathode chamber in which a cathode (cathode terminal cell) was provided were arranged opposite. A pair of gaskets were arranged between the cells, and a laminate (an I-exchange membrane laminate and an electrolysis electrode) was sandwiched between the gaskets. So, the anodic cell, the gasket, the laminate, the gasket and the cathode

532/803 membrane was designed or embedded. This movement was repeated again to check the conformability of the electrode to the membrane. The results were evaluated on a four-level scale from 1 to 4, based on the following indices: 1: good manipulation property 2: able to be manipulated 3: difficult to manipulate 4: substantially unable to be manipulated

[002019] Here, the sample from Comparative Example 5, provided in a size equivalent to that of a large electrolytic cell including an electrode in a size of 1.3 mx 2.5 m and an ion exchange membrane in a size of 1.5 mx 2.8 m, was subjected to manipulation. The result of the evaluation of Comparative Example 5 (“3” as described below) was used as an Index to assess the difference between the evaluation of (A) and (B) above and the largest. That is, in the case where the result of the evaluation of a small laminate was "1" or "2", it was considered that there was no problem in the handling property even if the laminate was provided in a larger size. (9) Electrolytic evaluation (voltage (V), current efficiency (%), common saline concentration in caustic soda (ppm, on the basis of 50%))

[002020] Electrolytic performance was assessed by the following electrolytic experiment.

[002021] A titanium anode cell with an anodic chamber in which an anode (anode terminal cell) was provided and a cathode cell with a nickel cathode chamber in which a cathode (cathode terminal cell) was provided were arranged opposite. A pair of gaskets were arranged between the cells, and a laminate (an I-exchange membrane laminate and an electrolysis electrode) was sandwiched between the gaskets. So, the anodic cell, the gasket, the laminate, the gasket and the cathode

533/803 were placed in close contact to obtain an electrolytic cell, and an electrolyzer including the cell was provided.

[002022] The anode was produced by applying a mixed solution of ruthenium chloride, iridium chloride and titanium tetrachloride on a titanium substrate subjected to pickling and acid attack treatment as a pretreatment, followed by drying and cooking. The anode was fixed to the anode chamber by welding. As a cathode, one described in each of the Examples and Comparative Examples was used. As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. Nickel mesh formed by simple weaving nickel wire with a diameter of 150 µm in a size 40 mesh was placed on top and a rope made of Teflon (R) was used to fix the four corners of the Ni mesh to the collector. This Ni mesh was used as a supply conductor. This electrolytic cell has a zero interstice structure using the repulsive force of the mattress like the elastic metal body. Like gaskets, ethylene-propylene-diene rubber (EPDM) gaskets were used. As a membrane, the ion exchange membrane A (160 square mm) produced in [Method (i)] was used.

[002023] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and in the cathodic chamber was adjusted to allow the temperature in each electrolytic cell to reach 90ºC. Was common salt electrolysis performed at a current density of 6 kA / m? to measure voltage, current density and concentration of common salt in caustic soda. The current efficiency here is the proportion of the amount of soda

533/803 were placed in close contact to obtain an electrolytic cell, and an electrolyzer including the cell was provided.

[002022] The anode was produced by applying a mixed solution of ruthenium chloride, iridium chloride and titanium tetrachloride on a titanium substrate subjected to pickling and acid attack treatment as a pretreatment, followed by drying and cooking. The anode was fixed to the anode chamber by welding. As a cathode, one described in each of the Examples and Comparative Examples was used. As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. Nickel mesh formed by simple weaving nickel wire with a diameter of 150 µm in a size 40 mesh was placed on top and a rope made of Teflon (R) was used to fix the four corners of the Ni mesh to the collector. This Ni mesh was used as a supply conductor. This electrolytic cell has a zero interstice structure using the repulsive force of the mattress like the elastic metal body. Like gaskets, ethylene-propylene-diene rubber (EPDM) gaskets were used. As a membrane, the ion exchange membrane A (160 mm square) produced in [Method (i)] was used.

[002023] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and in the cathodic chamber was adjusted to allow the temperature in each electrolytic cell to reach 90ºC. Was common salt electrolysis performed at a current density of 6 kA / m? to measure voltage, current density and concentration of common salt in caustic soda. The current efficiency here is the proportion of the amount of soda

534/803 caustic produced for the passed current, and when impurity fons and hydroxide fons instead of sodium ions move through the ion exchange membrane due to the passed current, the current efficiency decreases. The current efficiency was obtained by dividing the number of moles of caustic soda produced for a certain time by the number of moles of electrons in the current that passed during that time. The number of moles of caustic soda was obtained by recovering the caustic soda produced by electrolysis in a plastic container and measuring its mass. As the concentration of common salt in caustic soda, a value obtained by converting the concentration of caustic soda to the base of 50% was shown.

[002024] The specification of the electrode and the supply conductor used in each of the Examples and Comparative Examples is shown in Table 1. (11) Measurement of the catalytic layer thickness, electrode substrate for electrolysis and electrode thickness

[002025] For the thickness of the electrode substrate for electrolysis, a digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the substrate thickness for the electrolysis electrode (gauge thickness). For the electrode thickness, a digital thickness gauge was used to calculate an average value of 10 points obtained by measuring uniformly in the plane, in the same way as for the electrode substrate. The value was used as the electrode thickness (gauge thickness). The thickness of the catalytic layer was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness. (12) Test of elastic deformation of the electrode

[002026] The ion exchange membrane A (membrane) and the electrode produced in [Method (i)] were cut, each, in a square of 110

534/803 caustic produced for the passed current, and when impurity fons and hydroxide fons instead of sodium ions move through the ion exchange membrane due to the passed current, the current efficiency decreases. The current efficiency was obtained by dividing the number of moles of caustic soda produced for a certain time by the number of moles of electrons in the current that passed during that time. The number of moles of caustic soda was obtained by recovering the caustic soda produced by electrolysis in a plastic container and measuring its mass. As the concentration of common salt in caustic soda, a value obtained by converting the concentration of caustic soda to the base of 50% was shown.

[002024] The specification of the electrode and the supply conductor used in each of the Examples and Comparative Examples is shown in Table 1. (11) Measurement of the catalytic layer thickness, electrode substrate for electrolysis and electrode thickness

[002025] For the thickness of the electrode substrate for electrolysis, a digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the substrate thickness for the electrolysis electrode (gauge thickness). For the electrode thickness, a digital thickness gauge was used to calculate an average value of 10 points obtained by measuring uniformly in the plane, in the same way as for the electrode substrate. The value was used as the electrode thickness (gauge thickness). The thickness of the catalytic layer was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness. (12) Test of elastic deformation of the electrode

[002026] The ion exchange membrane A (membrane) and the electrode produced in [Method (i)] were cut, each, in a square of 110

535/803 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. After the ion exchange membrane and the electrode were laminated to produce a laminate under conditions of a temperature: 23 + 2ºC and a relative humidity: 30 + 5%, the laminate was wrapped around a PVC tube with an outside diameter of 632 mm and a length of 20 cm without any interstice, as shown in Figure 14. The laminate was fixed using a polyethylene clamp so that the laminated coil did not come out of the PVC tube or come loose. The laminate was retained in this state for 6 hours. Subsequently, the cable tie was removed and the laminate was unrolled from the PVC tube. Only the electrode was placed on a surface plate, and the heights L, and L7 of a raised portion of the surface plate were measured to determine an average value. This value was used as the electrode strain index. In other words, a lower value means that the laminate is unlikely to deform.

[002027] When an expanded metal is used, there are two winding directions: the SW direction and the LW direction. In this test, the laminate was rolled in the SW direction.

[002028] The deformed electrodes (electrodes that did not return to their original flat state) were evaluated for smoothness after plastic deformation according to a method shown in Figure 15. That is, a deformed electrode was placed in a membrane sufficiently immersed in water. pure. One end of the electrode was attached, and the other raised end was pressed into the membrane to release a force, and an assessment was made as to whether the deformed electrode matched the membrane. (13) Assessment of membrane damage

[002029] Like the membrane, an ion exchange membrane B below was used.

[002030] As reinforcement core materials, those obtained were used

535/803 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. After the ion exchange membrane and the electrode were laminated to produce a laminate under conditions of a temperature: 23 + 2ºC and a relative humidity: 30 + 5%, the laminate was wrapped around a PVC tube with an outside diameter of 632 mm and a length of 20 cm without any interstice, as shown in Figure 14. The laminate was fixed using a polyethylene clamp so that the laminated coil did not come out of the PVC tube or come loose. The laminate was retained in this state for 6 hours. Subsequently, the cable tie was removed and the laminate was unrolled from the PVC tube. Only the electrode was placed on a surface plate, and the heights L, and L7 of a raised portion of the surface plate were measured to determine an average value. This value was used as the electrode strain index. In other words, a lower value means that the laminate is unlikely to deform.

[002027] When an expanded metal is used, there are two winding directions: the SW direction and the LW direction. In this test, the laminate was rolled in the SW direction.

[002028] The deformed electrodes (electrodes that did not return to their original flat state) were evaluated for smoothness after plastic deformation according to a method shown in Figure 15. That is, a deformed electrode was placed in a membrane sufficiently immersed in water. pure. One end of the electrode was attached, and the other raised end was pressed into the membrane to release a force, and an assessment was made as to whether the deformed electrode matched the membrane. (13) Assessment of membrane damage

[002029] Like the membrane, an ion exchange membrane B below was used.

[002030] As reinforcement core materials, those obtained were used

536/803 by twisting strands of 100 denier polytetrafluoroethylene (PTFE) tape 900 times / m in a thread form (hereinafter called PTFE wires). As warp sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. As weft sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m were used. First, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric with a thickness of 100 µm.

[002031] Next, a polymer (Al) of a dry resin which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF; COOCH; and had an ion exchange capacity of 0.92 mg equivalent / g, and a polymer (B1) of a dry resin that was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF; SO, F and had an ion exchange capacity of 1.10 mg equivalent / g. Using these polymers (Al) and (B1), a two-layer film X in which the thickness of a polymer layer (Al) was 25 µm and the thickness of a polymer layer (B1) was 89 µm was obtained by a coextrusion matrix method T. As the ion exchange capacity of each polymer, the ion exchange capacity was shown in the case of hydrolysis of the precursors of the ion exchange group of each polymer for conversion into ion exchange groups.

[002032] Separately, a polymer (B2) of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF3SO, F and had an ion exchange capacity of 1 , 10 mg equivalent / g. This polymer was extruded in a single layer to obtain a Y film with a thickness of 20 µm.

[002033] Subsequently, the release paper, film Y, a

536/803 by twisting strands of 100 denier polytetrafluoroethylene (PTFE) tape 900 times / m in a thread form (hereinafter called PTFE wires). As warp sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. As weft sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m were used. First, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric with a thickness of 100 µm.

[002031] Next, a polymer (Al) of a dry resin which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF; COOCH; and had an ion exchange capacity of 0.92 mg equivalent / g, and a polymer (B1) of a dry resin that was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF; SO, F and had an ion exchange capacity of 1.10 mg equivalent / g. Using these polymers (Al) and (B1), a two-layer film X in which the thickness of a polymer layer (Al) was 25 µm and the thickness of a polymer layer (B1) was 89 µm was obtained by a coextrusion matrix method T. As the ion exchange capacity of each polymer, the ion exchange capacity was shown in the case of hydrolysis of the precursors of the ion exchange group of each polymer for conversion into ion exchange groups.

[002032] Separately, a polymer (B2) of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF3SO, F and had an ion exchange capacity of 1 , 10 mg equivalent / g. This polymer was extruded in a single layer to obtain a Y film with a thickness of 20 µm.

[002033] Subsequently, the release paper, film Y, a

537/803 reinforcement material and film X were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate temperature of 225ºC and a reduced pressure degree of 0.022 MPa for two minutes, and then the release paper was removed to obtain a composite membrane. The resulting composite membrane was immersed in an aqueous solution comprising dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) for one hour for saponification. Then, the membrane was immersed in 0.5N NaOH for one hour to replace the fons attached to the ion exchange groups with Na and then washed with water. In addition, the membrane was dried at 60ºC.

[002034] Additionally, a polymer (B3) of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, xF and had an ion exchange capacity of 1.05 mg equivalent / g was hydrolyzed and then transformed into an acid type with hydrochloric acid. Zirconium oxide particles with an average particle size of primary particles of 0.02 µm were added to a mixed solution of water and ethanol 50/50 (mass ratio) in which the polymer (B3 ') of this acid type was dissolved in a proportion of 5% by mass so that the mass ratio of the polymer (B3 ') to the zirconium oxide particles was 20/80. Subsequently, the polymer (B3 ') was dispersed in a suspension of the zirconium oxide particles with a ball mill to obtain a suspension.

[002035] This suspension was applied by a spray method on both surfaces of the dry and ion exchange membrane to obtain an ion exchange membrane B with a coating layer containing the polymer (B3 ') and the oxide particles of zirconium. The coating density of zirconium oxide measured by X-ray fluorescence measurement was 0.35 mg / em ?.

[002036] The anode used was the same as for (9) Electrolytic evaluation.

537/803 reinforcement material and film X were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate temperature of 225ºC and a reduced pressure degree of 0.022 MPa for two minutes, and then the release paper was removed to obtain a composite membrane. The resulting composite membrane was immersed in an aqueous solution comprising dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) for one hour for saponification. Then, the membrane was immersed in 0.5N NaOH for one hour to replace the fons attached to the ion exchange groups with Na and then washed with water. In addition, the membrane was dried at 60ºC.

[002034] Additionally, a polymer (B3) of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, xF and had an ion exchange capacity of 1.05 mg equivalent / g was hydrolyzed and then transformed into an acid type with hydrochloric acid. Zirconium oxide particles with an average particle size of primary particles of 0.02 µm were added to a mixed solution of water and ethanol 50/50 (mass ratio) in which the polymer (B3 ') of this acid type was dissolved in a proportion of 5% by mass so that the mass ratio of the polymer (B3 ') to the zirconium oxide particles was 20/80. Subsequently, the polymer (B3 ') was dispersed in a suspension of the zirconium oxide particles with a ball mill to obtain a suspension.

[002035] This suspension was applied by a spray method on both surfaces of the dry and ion exchange membrane to obtain an ion exchange membrane B with a coating layer containing the polymer (B3 ') and the oxide particles of zirconium. The coating density of zirconium oxide measured by X-ray fluorescence measurement was 0.35 mg / em ?.

[002036] The anode used was the same as for (9) Electrolytic evaluation.

538/803

[002037] The cathode used was one described in each of the Examples and Comparative Examples. The collector, mattress and feeding conductor of the cathodic chamber used were the same as in (9) Electrolytic evaluation. That is, a zero interstice structure was provided by the use of Ni mesh as the feed conductor and the repulsive force of the mattress as the elastic metal body. The gaskets used were the same as for (9) Electrolytic evaluation. As a membrane, ion exchange membrane B produced by the method mentioned above was used. That is, an electrolyzer equivalent to that of (9) was provided, except that the laminate of the ion exchange membrane B and the electrolysis electrode were sandwiched between a pair of gaskets.

[002038] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and the cathodic chamber was adjusted so that the temperature in each electrolytic cell reached 70ºC. Common salt electrolysis was carried out at a current density of 8 kKA / m ?. Electrolysis was interrupted 12 hours after the start of electrolysis, and the ion exchange membrane B was removed and observed for its damage condition.

[002039] "0" means no damage. "1 to 3" means that the damage was present and a higher number means a greater degree of damage. (14) Electrode ventilation resistance

[002040] The ventilation resistance of the electrode was measured using a KES-F8 air permeability tester (trade name, KATO TECH CO., LTD.). The unit for the ventilation resistance value is kKPa-s / m. The measurement was repeated 5 times and the average value was listed in Table 2. The measurement was conducted following two conditions. The temperature of the measuring chamber was 24ºC and the relative humidity was 32%.

538/803

[002037] The cathode used was one described in each of the Examples and Comparative Examples. The collector, mattress and feeding conductor of the cathodic chamber used were the same as in (9) Electrolytic evaluation. That is, a zero interstice structure was provided by the use of Ni mesh as the feed conductor and the repulsive force of the mattress as the elastic metal body. The gaskets used were the same as for (9) Electrolytic evaluation. As a membrane, ion exchange membrane B produced by the method mentioned above was used. That is, an electrolyzer equivalent to that of (9) was provided, except that the laminate of the ion exchange membrane B and the electrolysis electrode were sandwiched between a pair of gaskets.

[002038] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and the cathodic chamber was adjusted so that the temperature in each electrolytic cell reached 70ºC. Common salt electrolysis was carried out at a current density of 8 kKA / m ?. Electrolysis was interrupted 12 hours after the start of electrolysis, and the ion exchange membrane B was removed and observed for its damage condition.

[002039] "0" means no damage. "1 to 3" means that the damage was present and a higher number means a greater degree of damage. (14) Electrode ventilation resistance

[002040] The ventilation resistance of the electrode was measured using a KES-F8 air permeability tester (trade name, KATO TECH CO., LTD.). The unit for the ventilation resistance value is kKPa-s / m. The measurement was repeated 5 times and the average value was listed in Table 2. The measurement was conducted following two conditions. The temperature of the measuring chamber was 24ºC and the relative humidity was 32%.

539/803 “Measuring condition 1 (ventilation resistance 1) Piston speed: 0.2 cm / s Ventilation volume: 0.4 cc / in? / S Measuring range: SENSE L (low) Sample size: 50 mm x 50 mm “Measuring condition 2 (ventilation resistance 2) Piston speed: 2 cm / s Ventilation volume: 4 cc / in? / S Measuring range: SENSE M (high) or H (high) Size sample size: 50 mm x 50 mm [Example 1]

[002041] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 16 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002042] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 49%.

[002043] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002044] A vat containing the above coating liquid was

539/803 “Measuring condition 1 (ventilation resistance 1) Piston speed: 0.2 cm / s Ventilation volume: 0.4 cc / in? / S Measuring range: SENSE L (low) Sample size: 50 mm x 50 mm “Measuring condition 2 (ventilation resistance 2) Piston speed: 2 cm / s Ventilation volume: 4 cc / in? / S Measuring range: SENSE M (high) or H (high) Size sample size: 50 mm x 50 mm [Example 1]

[002041] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 16 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002042] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 49%.

[002043] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002044] A vat containing the above coating liquid was

540/803 placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced in Example 1 was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface. The thickness was the total thickness of ruthenium oxide and cerium oxide.

[002045] The results of measuring the adhesive force of the electrode produced by the method above are shown in Table 2. A sufficient adhesive force was observed.

[002046] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002047] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

540/803 placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced in Example 1 was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface. The thickness was the total thickness of ruthenium oxide and cerium oxide.

[002045] The results of measuring the adhesive force of the electrode produced by the method above are shown in Table 2. A sufficient adhesive force was observed.

[002046] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002047] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

541/803

[002048] The electrode produced by the above method was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was placed opposite in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane À (size: 160 mm x 160 mm), produced in [Method (1)] and balanced with a aqueous solution of 0.1 N NaOH and allowed to adhere to it through the surface tension of the aqueous solution.

[002049] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002050] The electrode integrated into the membrane above was sandwiched between the anode cell and the cathode cell in such a way that the surface on which the electrode was affixed was left facing the side of the cathode chamber. In the sectional structure, the collector, mattress, nickel mesh feed conductor, electrode, membrane and anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure.

[002051] The resulting electrode was subjected to electrolytic evaluation. The results are shown in Table 2.

[002052] The electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "o".

[002053] When the amount of coating after electrolysis has been

541/803

[002048] The electrode produced by the above method was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was placed opposite in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane À (size: 160 mm x 160 mm), produced in [Method (1)] and balanced with a aqueous solution of 0.1 N NaOH and allowed to adhere to it through the surface tension of the aqueous solution.

[002049] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002050] The electrode integrated into the membrane above was sandwiched between the anode cell and the cathode cell in such a way that the surface on which the electrode was affixed was left facing the side of the cathode chamber. In the sectional structure, the collector, mattress, nickel mesh feed conductor, electrode, membrane and anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure.

[002051] The resulting electrode was subjected to electrolytic evaluation. The results are shown in Table 2.

[002052] The electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "o".

[002053] When the amount of coating after electrolysis has been

542/803 measured by X-ray fluorescence analysis (XRF), substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 2]

[002054] In Example 2, an electrolytic nickel blade with a gauge thickness of 22 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 0.96 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002055] The thickness of the electrode was 29 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[002056] Sufficient adhesive strength has been observed.

[002057] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002058] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0033 (kPa-s / m) in the condition of measurement 2.

542/803 measured by X-ray fluorescence analysis (XRF), substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 2]

[002054] In Example 2, an electrolytic nickel blade with a gauge thickness of 22 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 0.96 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002055] The thickness of the electrode was 29 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[002056] Sufficient adhesive strength has been observed.

[002057] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002058] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0033 (kPa-s / m) in the condition of measurement 2.

543/803

[002059] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". The damage to the membrane was also rated as good: "0".

[002060] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 3]

[002061] In Example 3, an electrolytic nickel blade with a gauge thickness of 30 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 1.38 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002062] The thickness of the electrode was 38 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface.

[002063] Sufficient adhesive strength has been observed.

[002064] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. The electrode was found to have a

543/803

[002059] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". The damage to the membrane was also rated as good: "0".

[002060] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 3]

[002061] In Example 3, an electrolytic nickel blade with a gauge thickness of 30 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 1.38 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002062] The thickness of the electrode was 38 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface.

[002063] Sufficient adhesive strength has been observed.

[002064] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. The electrode was found to have a

544/803 wide region of elastic deformation.

[002065] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002066] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002067] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4]

[002068] In Example 4, an electrolytic nickel blade with a gauge thickness of 16 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 75%. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002069] The thickness of the electrode was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

544/803 wide region of elastic deformation.

[002065] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002066] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002067] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4]

[002068] In Example 4, an electrolytic nickel blade with a gauge thickness of 16 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 75%. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002069] The thickness of the electrode was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

545/803

[002070] Sufficient adhesive strength has been observed.

[002071] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002072] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002073] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002074] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 5]

[002075] In Example 5, an electrolytic nickel blade with a thickness of 20 µm was provided as a substrate for the electrode for cathode electrolysis. Both surfaces of this nickel blade were subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.96 µm. Both surfaces had the same roughness. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 49%. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results

545/803

[002070] Sufficient adhesive strength has been observed.

[002071] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002072] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002073] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002074] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 5]

[002075] In Example 5, an electrolytic nickel blade with a thickness of 20 µm was provided as a substrate for the electrode for cathode electrolysis. Both surfaces of this nickel blade were subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.96 µm. Both surfaces had the same roughness. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 49%. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results

546/803 are shown in Table 2.

[002076] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm. The coating was also formed on the non-roughened surface.

[002077] Sufficient adhesive strength has been observed.

[002078] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002079] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002080] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002081] Additionally, when the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on both surfaces. In consideration of the comparison with Examples 1 to 4, this indicates that the other surface not opposed to the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 6]

[002082] In Example 6, the evaluation was carried out in the same way as in Example 1, except that the coating of the substrate for the electrode for cathode electrolysis was carried out by ion plating, and the results are shown in Table 2. In ion plating , the film formation was carried out using Ru metal target at a heating temperature of 200ºC and under an argon / oxygen atmosphere at a pressure of formation of

546/803 are shown in Table 2.

[002076] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm. The coating was also formed on the non-roughened surface.

[002077] Sufficient adhesive strength has been observed.

[002078] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002079] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002080] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002081] Additionally, when the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on both surfaces. In consideration of the comparison with Examples 1 to 4, this indicates that the other surface not opposed to the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 6]

[002082] In Example 6, the evaluation was carried out in the same way as in Example 1, except that the coating of the substrate for the electrode for cathode electrolysis was carried out by ion plating, and the results are shown in Table 2. In ion plating , the film formation was carried out using Ru metal target at a heating temperature of 200ºC and under an argon / oxygen atmosphere at a pressure of formation of

547/803 7 x 10? Pa. The coating formed was ruthenium oxide.

[002083] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002084] Sufficient adhesive strength has been observed.

[002085] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002086] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

[002087] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 7]

[002088] In Example 7, the electrode substrate for cathode electrolysis was produced by an electroforming method. The photomask had a shape formed by a vertical and horizontal arrangement of 0.485 mm x 0.485 mm square in a range of 0.15 mm. Exposure, development and electroplating were performed sequentially to obtain a porous nickel film with a gauge thickness of 20 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002089] The thickness of the electrode was 37 µm. The layer thickness

547/803 7 x 10? Pa. The coating formed was ruthenium oxide.

[002083] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002084] Sufficient adhesive strength has been observed.

[002085] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002086] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

[002087] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 7]

[002088] In Example 7, the electrode substrate for cathode electrolysis was produced by an electroforming method. The photomask had a shape formed by a vertical and horizontal arrangement of 0.485 mm x 0.485 mm square in a range of 0.15 mm. Exposure, development and electroplating were performed sequentially to obtain a porous nickel film with a gauge thickness of 20 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002089] The thickness of the electrode was 37 µm. The layer thickness

548/803 catalytic, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 17 µm.

[002090] Sufficient adhesive strength has been observed.

[002091] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002092] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002093] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 8]

[002094] In Example 8, the electrode substrate for cathode electrolysis was produced by an electroforming method. The substrate had a gauge thickness of 50 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.73 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002095] The thickness of the electrode was 60 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002096] Sufficient adhesive strength has been observed.

[002097] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

548/803 catalytic, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 17 µm.

[002090] Sufficient adhesive strength has been observed.

[002091] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002092] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002093] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 8]

[002094] In Example 8, the electrode substrate for cathode electrolysis was produced by an electroforming method. The substrate had a gauge thickness of 50 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.73 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002095] The thickness of the electrode was 60 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002096] Sufficient adhesive strength has been observed.

[002097] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

549/803

[002098] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002099] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 9]

[002100] In Example 9, a nickel nonwoven fabric with a gauge thickness of 150 µm and a void ratio of 76% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrode for cathode electrolysis. The nonwoven fabric had a nickel fiber diameter of about 40 µm and a base weight of 300 g / m2. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002101] The thickness of the electrode was 165 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 15 µm.

[002102] Sufficient adhesive strength has been observed.

[002103] When an electrode deformation test was performed, the average value of L, and L, was 29 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002104] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0612 (kPa-s / m) in the condition of measurement 2.

549/803

[002098] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002099] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 9]

[002100] In Example 9, a nickel nonwoven fabric with a gauge thickness of 150 µm and a void ratio of 76% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrode for cathode electrolysis. The nonwoven fabric had a nickel fiber diameter of about 40 µm and a base weight of 300 g / m2. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002101] The thickness of the electrode was 165 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 15 µm.

[002102] Sufficient adhesive strength has been observed.

[002103] When an electrode deformation test was performed, the average value of L, and L, was 29 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002104] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0612 (kPa-s / m) in the condition of measurement 2.

550/803

[002105] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 10]

[002106] In Example 10, a nickel nonwoven fabric with a gauge thickness of 200 µm and a void ratio of 72% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrode for cathode electrolysis. The non-woven fabric had a nickel fiber diameter of about 40 µm and a base weight of 500 g / m2. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002107] The thickness of the electrode was 215 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 15 µm.

[002108] Sufficient adhesive strength has been observed.

[002109] When an electrode deformation test was performed, the average value of L, and L, was 40 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002110] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0164 (kPa-s / m) in the condition of measurement 2.

[002111] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode

550/803

[002105] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 10]

[002106] In Example 10, a nickel nonwoven fabric with a gauge thickness of 200 µm and a void ratio of 72% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrode for cathode electrolysis. The non-woven fabric had a nickel fiber diameter of about 40 µm and a base weight of 500 g / m2. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002107] The thickness of the electrode was 215 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 15 µm.

[002108] Sufficient adhesive strength has been observed.

[002109] When an electrode deformation test was performed, the average value of L, and L, was 40 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002110] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0164 (kPa-s / m) in the condition of measurement 2.

[002111] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode

551/803 had a “2” handling property and was determined to be manipulable as a large laminate. The damage to the membrane was rated as good: "0". [Example 11]

[002112] In Example 11, a foamy nickel with a gauge thickness of 200 µm and a void ratio of 72% (manufactured by Mitsubishi Materials Corporation) was used as a substrate for the electrode for cathode electrolysis. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002113] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm. [0021 14] Sufficient adhesive strength has been observed.

[002115] When an electrode deformation test was performed, the average value of L, and L, was 17 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002116] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0402 (kPa: s / m) in the condition of measurement 2.

[002117] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 12]

551/803 had a “2” handling property and was determined to be manipulable as a large laminate. The damage to the membrane was rated as good: "0". [Example 11]

[002112] In Example 11, a foamy nickel with a gauge thickness of 200 µm and a void ratio of 72% (manufactured by Mitsubishi Materials Corporation) was used as a substrate for the electrode for cathode electrolysis. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002113] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm. [0021 14] Sufficient adhesive strength has been observed.

[002115] When an electrode deformation test was performed, the average value of L, and L, was 17 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002116] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0402 (kPa: s / m) in the condition of measurement 2.

[002117] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 12]

552/803

[002118] In Example 12, a 200 mesh nickel mesh with a line diameter of 50 µm, a gauge thickness of 100 µm and an opening ratio of 37% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 12, a nickel plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of a piece of wire of the wire mesh was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002119] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002120] Sufficient adhesive strength has been observed.

[002121] When an electrode deformation test was performed, the average value of L, and L, was 0.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002122] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0154 (kPa-s / m) in the condition of measurement 2.

[002123] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". The damage to the membrane was rated as good: "0".

552/803

[002118] In Example 12, a 200 mesh nickel mesh with a line diameter of 50 µm, a gauge thickness of 100 µm and an opening ratio of 37% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 12, a nickel plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of a piece of wire of the wire mesh was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002119] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002120] Sufficient adhesive strength has been observed.

[002121] When an electrode deformation test was performed, the average value of L, and L, was 0.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002122] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0154 (kPa-s / m) in the condition of measurement 2.

[002123] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". The damage to the membrane was rated as good: "0".

553/803 [Example 13]

[002124] In Example 13, a 150 mesh nickel mesh with a line diameter of 65 µm, a gauge thickness of 130 µm and an opening ratio of 38% was used as substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 13, a nickel plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.66 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except for what was described above, the above assessment was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002125] The thickness of the electrode was 133 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 3 µm.

[002126] Sufficient adhesive strength has been observed.

[002127] When an electrode deformation test was performed, the average value of L, and L, was 6.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002128] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0124 (kPa-s / m) in the condition of measurement 2.

[002129] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be

553/803 [Example 13]

[002124] In Example 13, a 150 mesh nickel mesh with a line diameter of 65 µm, a gauge thickness of 130 µm and an opening ratio of 38% was used as substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 13, a nickel plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.66 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except for what was described above, the above assessment was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002125] The thickness of the electrode was 133 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 3 µm.

[002126] Sufficient adhesive strength has been observed.

[002127] When an electrode deformation test was performed, the average value of L, and L, was 6.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002128] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0124 (kPa-s / m) in the condition of measurement 2.

[002129] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be

554/803 manipulable as a large laminate. The damage to the membrane was also rated as good: "0". [Example 14]

[002130] In Example 14, a substrate identical to that of Example 3 (gauge thickness of 30 µm and an opening ratio of 44%) was used as the substrate for the electrode for cathode electrolysis. The electrolytic evaluation was carried out with a structure identical to that of Example 1, except that no nickel mesh feed conductor was included. That is, in the sectional structure of the cell, the collector, the mattress, the electrode integrated into the membrane and the anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the mattress serves as the conductor feed. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002131] Sufficient adhesive strength has been observed.

[002132] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002133] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002134] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 15]

[002135] In Example 15, a substrate identical to that of Example 3 (gauge thickness of 30 µm and an opening ratio of 44%) was used as the substrate for the electrode for cathode electrolysis. The cathode used in the

554/803 manipulable as a large laminate. The damage to the membrane was also rated as good: "0". [Example 14]

[002130] In Example 14, a substrate identical to that of Example 3 (gauge thickness of 30 µm and an opening ratio of 44%) was used as the substrate for the electrode for cathode electrolysis. The electrolytic evaluation was carried out with a structure identical to that of Example 1, except that no nickel mesh feed conductor was included. That is, in the sectional structure of the cell, the collector, the mattress, the electrode integrated into the membrane and the anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the mattress serves as the conductor feed. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002131] Sufficient adhesive strength has been observed.

[002132] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002133] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002134] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 15]

[002135] In Example 15, a substrate identical to that of Example 3 (gauge thickness of 30 µm and an opening ratio of 44%) was used as the substrate for the electrode for cathode electrolysis. The cathode used in the

555/803 Reference Example 1, which was degraded and had an intensified electrolytic voltage, was placed instead of the nickel mesh feed conductor. With the exception of the one described above, the electrolytic evaluation was carried out with a structure identical to that of Example 1. That is, in the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage (serves as conductor the electrode for electrolysis (cathode), the membrane and the anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstitial structure, and the cathode which is degraded and has an intensified electrolytic voltage serves as a supply conductor. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002136] Sufficient adhesive strength has been observed.

[002137] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002138] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002139] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 16]

[002140] A titanium blade with a thickness of 20 µm was provided as a substrate for the electrode for electrolysis of the anode. Both surfaces of the titanium sheet were subjected to a roughness treatment. A porous sheet was formed by drilling this titanium sheet with circular holes by drilling. The hole diameter was 1

555/803 Reference Example 1, which was degraded and had an intensified electrolytic voltage, was placed instead of the nickel mesh feed conductor. With the exception of the one described above, the electrolytic evaluation was carried out with a structure identical to that of Example 1. That is, in the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage (serves as conductor the electrode for electrolysis (cathode), the membrane and the anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstitial structure, and the cathode which is degraded and has an intensified electrolytic voltage serves as a supply conductor. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002136] Sufficient adhesive strength has been observed.

[002137] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002138] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002139] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 16]

[002140] A titanium blade with a thickness of 20 µm was provided as a substrate for the electrode for electrolysis of the anode. Both surfaces of the titanium sheet were subjected to a roughness treatment. A porous sheet was formed by drilling this titanium sheet with circular holes by drilling. The hole diameter was 1

556/803 mm, and the opening ratio was 14%. The arithmetic mean roughness Ra of the surface was 0.37 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002141] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anodic coating liquid.

[002142] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, preliminary cooking and cooking operations were carried out repeatedly, and then

556/803 mm, and the opening ratio was 14%. The arithmetic mean roughness Ra of the surface was 0.37 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002141] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anodic coating liquid.

[002142] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, preliminary cooking and cooking operations were carried out repeatedly, and then

557/803 520ºC was performed for one hour.

[002143] The electrode produced by the method above was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The cut electrode was allowed to adhere through the surface tension of the aqueous solution to a substantial central position on the side of the sulfonic acid layer of the ion exchange membrane A (size: 160 mm x 160 mm) produced in [Method (1)] and balanced with a 0.1 N aqueous solution of NaOH.

[002144] The cathode was prepared in the following procedure. First, a 40 mesh nickel wire mesh with a line diameter of 150 µm was provided as a substrate. After stripping with alumina as a pretreatment, the wire mesh was immersed in 6 N hydrochloric acid for 5 minutes, washed sufficiently with pure, dry water.

[002145] Then a solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and cerium chloride (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the ruthenium element and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002146] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the

557/803 520ºC was performed for one hour.

[002143] The electrode produced by the method above was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The cut electrode was allowed to adhere through the surface tension of the aqueous solution to a substantial central position on the side of the sulfonic acid layer of the ion exchange membrane A (size: 160 mm x 160 mm) produced in [Method (1)] and balanced with a 0.1 N aqueous solution of NaOH.

[002144] The cathode was prepared in the following procedure. First, a 40 mesh nickel wire mesh with a line diameter of 150 µm was provided as a substrate. After stripping with alumina as a pretreatment, the wire mesh was immersed in 6 N hydrochloric acid for 5 minutes, washed sufficiently with pure, dry water.

[002145] Then a solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and cerium chloride (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the ruthenium element and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002146] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the

558/803 electrode substrate passed between the second coating roll and the PVC roll at the top (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was performed at 300ºC for 3 minutes and cooking at 550ºC for 10 minutes. Then, cooking was carried out at 550ºC for one hour. A series of these coating, drying, preliminary cooking and cooking operations were repeated.

[002147] As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. The cathode produced by the above method was placed on it, and a rope made of Teflon (R) was used to fix the four corners of the mesh to the collector.

[002148] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the anodes, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002149] The anode used in Reference Example 3, which was degraded and had an intensified electrolytic voltage, was attached to the anode cell by welding, and the electrode integrated into the above membrane was placed between the anode cell and the cathode cell so that the surface on which the electrode was attached was left facing the side of the anodic chamber. That is, in the sectional structure of the cell, the collector, the mattress, the cathode, the membrane, the electrolysis electrode (porous titanium sheet anode) and the anode that was degraded and had an intensified electrolytic voltage were

558/803 electrode substrate passed between the second coating roll and the PVC roll at the top (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was performed at 300ºC for 3 minutes and cooking at 550ºC for 10 minutes. Then, cooking was carried out at 550ºC for one hour. A series of these coating, drying, preliminary cooking and cooking operations were repeated.

[002147] As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. The cathode produced by the above method was placed on it, and a rope made of Teflon (R) was used to fix the four corners of the mesh to the collector.

[002148] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the anodes, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002149] The anode used in Reference Example 3, which was degraded and had an intensified electrolytic voltage, was attached to the anode cell by welding, and the electrode integrated into the above membrane was placed between the anode cell and the cathode cell so that the surface on which the electrode was attached was left facing the side of the anodic chamber. That is, in the sectional structure of the cell, the collector, the mattress, the cathode, the membrane, the electrolysis electrode (porous titanium sheet anode) and the anode that was degraded and had an intensified electrolytic voltage were

559/803 arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure. The anode that was degraded and had an intensified electrolytic voltage served as the supply conductor. The porous titanium blade anode and the anode that was degraded and had an intensified electrolytic voltage were only in physical contact with each other and were not fixed to each other by welding.

[002150] The evaluation in this structure was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002151] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 6 µm.

[002152] Sufficient adhesive strength has been observed.

[002153] When an electrode deformation test was performed, the average value of L, and L, was 4 mm. It was found that the electrode had a wide region of elastic deformation.

[002154] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0060 (kPa-s / m) in the condition of measurement 2.

[002155] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 17]

[002156] In Example 17, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 30% was used as a substrate for the electrode for anode electrolysis. At the average arithmetic roughness Ra of the surface was 0.37 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

559/803 arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure. The anode that was degraded and had an intensified electrolytic voltage served as the supply conductor. The porous titanium blade anode and the anode that was degraded and had an intensified electrolytic voltage were only in physical contact with each other and were not fixed to each other by welding.

[002150] The evaluation in this structure was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002151] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 6 µm.

[002152] Sufficient adhesive strength has been observed.

[002153] When an electrode deformation test was performed, the average value of L, and L, was 4 mm. It was found that the electrode had a wide region of elastic deformation.

[002154] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0060 (kPa-s / m) in the condition of measurement 2.

[002155] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 17]

[002156] In Example 17, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 30% was used as a substrate for the electrode for anode electrolysis. At the average arithmetic roughness Ra of the surface was 0.37 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

560/803 Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002157] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002158] Sufficient adhesive strength has been observed.

[002159] When an electrode deformation test was performed, the average value of L, and L, was 5 mm. It was found that the electrode had a wide region of elastic deformation.

[002160] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2.

[002161] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 18]

[002162] In Example 18, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 42% was used as a substrate for the electrode for anode electrolysis. The average arithmetic roughness Ra of the surface was 0.38 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002163] The thickness of the electrode was 32 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 12 µm.

[002164] Sufficient adhesive strength has been observed.

560/803 Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002157] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002158] Sufficient adhesive strength has been observed.

[002159] When an electrode deformation test was performed, the average value of L, and L, was 5 mm. It was found that the electrode had a wide region of elastic deformation.

[002160] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2.

[002161] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 18]

[002162] In Example 18, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 42% was used as a substrate for the electrode for anode electrolysis. The average arithmetic roughness Ra of the surface was 0.38 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002163] The thickness of the electrode was 32 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 12 µm.

[002164] Sufficient adhesive strength has been observed.

561/803

[002165] When an electrode deformation test was performed, the average value of L, and L, was 2.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002166] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0022 (kPa: s / m) in the condition of measurement 2.

[002167] Additionally, the electrode showed low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 19]

[002168] In Example 19, a titanium blade with a caliber thickness of 50 µm and an opening ratio of 47% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.40 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002169] The thickness of the electrode was 69 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 19 µm.

[002170] Sufficient adhesive strength has been observed.

[002171] When an electrode deformation test was performed, the average value of L, and L, was 8 mm. It was found that the electrode had a wide region of elastic deformation.

[002172] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0024 (kPa: s / m) in the condition of measurement 2.

561/803

[002165] When an electrode deformation test was performed, the average value of L, and L, was 2.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002166] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0022 (kPa: s / m) in the condition of measurement 2.

[002167] Additionally, the electrode showed low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 19]

[002168] In Example 19, a titanium blade with a caliber thickness of 50 µm and an opening ratio of 47% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.40 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002169] The thickness of the electrode was 69 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 19 µm.

[002170] Sufficient adhesive strength has been observed.

[002171] When an electrode deformation test was performed, the average value of L, and L, was 8 mm. It was found that the electrode had a wide region of elastic deformation.

[002172] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0024 (kPa: s / m) in the condition of measurement 2.

562/803

[002173] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 20]

[002174] In Example 20, a titanium nonwoven fabric with a gauge thickness of 100 µm, a titanium fiber diameter of 20 µm, a base weight of 100 g / m? Was used, and an opening ratio of 78% as substrate for the electrode for electrolysis of the anode. Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002175] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002176] Sufficient adhesive strength has been observed.

[002177] When an electrode deformation test was performed, the average value of L, and L, was 2 mm. It was found that the electrode had a wide region of elastic deformation.

[002178] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0228 (kPa-s / m) in the condition of measurement 2.

[002179] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 21]

[002180] In Example 21, a 150 mesh titanium wire mesh with a gauge thickness of 120 µm and a titanium fiber diameter of about 60 µm was used as a substrate for the electrode for the electrolysis of the

562/803

[002173] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 20]

[002174] In Example 20, a titanium nonwoven fabric with a gauge thickness of 100 µm, a titanium fiber diameter of 20 µm, a base weight of 100 g / m? Was used, and an opening ratio of 78% as substrate for the electrode for electrolysis of the anode. Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002175] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002176] Sufficient adhesive strength has been observed.

[002177] When an electrode deformation test was performed, the average value of L, and L, was 2 mm. It was found that the electrode had a wide region of elastic deformation.

[002178] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0228 (kPa-s / m) in the condition of measurement 2.

[002179] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 21]

[002180] In Example 21, a 150 mesh titanium wire mesh with a gauge thickness of 120 µm and a titanium fiber diameter of about 60 µm was used as a substrate for the electrode for the electrolysis of the

563/803 anode. The opening ratio was 42%. A pickling treatment was carried out with grain size alumina number 320. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 21, a titanium plate with a thickness of 1 mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002181] The thickness of the electrode was 140 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 20 µm.

[002182] Sufficient adhesive strength has been observed.

[002183] When an electrode deformation test was performed, the average value of L, and L, was 10 mm. It was found that the electrode had a wide region of elastic deformation.

[002184] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0132 (kPa-s / m) in the condition of measurement 2.

[002185] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 22]

[002186] In Example 22, an anode was used which was degraded and had an intensified electrolytic voltage in the same way as in Example 16

563/803 anode. The opening ratio was 42%. A pickling treatment was carried out with grain size alumina number 320. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 21, a titanium plate with a thickness of 1 mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002181] The thickness of the electrode was 140 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 20 µm.

[002182] Sufficient adhesive strength has been observed.

[002183] When an electrode deformation test was performed, the average value of L, and L, was 10 mm. It was found that the electrode had a wide region of elastic deformation.

[002184] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0132 (kPa-s / m) in the condition of measurement 2.

[002185] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 22]

[002186] In Example 22, an anode was used which was degraded and had an intensified electrolytic voltage in the same way as in Example 16

564/803 than the anode feed conductor, and a titanium non-woven fabric identical to that of Example 20 as an anode. A cathode that was degraded and had an intensified electrolytic voltage was used in the same way as in Example 15 as the cathode supply conductor, and a nickel blade electrode identical to that of Example 3 was used as the cathode. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified tension, the cathode of the porous nickel blade, the membrane, the anode of the titanium non-woven fabric, and the anode that was degraded and had an intensified electrolytic voltage are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the cathode and anode which is degraded and has an intensified electrolytic voltage serve as the supply conductor. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002187] The thickness of the electrode (anode) was 114 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode (anode) thickness, was 14 µm. The thickness of the electrode (cathode) was 38 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the substrate for the electrode from the electrode thickness (cathode), was 8 µm.

[002188] Sufficient adhesive force was observed both on the anode and on the cathode.

[002189] When a deformation test of the electrode (anode) was performed, the average value of L, and L7 was 2 mm. When an electrode deformation test (cathode) was performed, the average value of L, and L, was 0 mm.

[002190] When the ventilation resistance of the electrode (anode) was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in

564/803 than the anode feed conductor, and a titanium non-woven fabric identical to that of Example 20 as an anode. A cathode that was degraded and had an intensified electrolytic voltage was used in the same way as in Example 15 as the cathode supply conductor, and a nickel blade electrode identical to that of Example 3 was used as the cathode. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified tension, the cathode of the porous nickel blade, the membrane, the anode of the titanium non-woven fabric, and the anode that was degraded and had an intensified electrolytic voltage are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the cathode and anode which is degraded and has an intensified electrolytic voltage serve as the supply conductor. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002187] The thickness of the electrode (anode) was 114 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode (anode) thickness, was 14 µm. The thickness of the electrode (cathode) was 38 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the substrate for the electrode from the electrode thickness (cathode), was 8 µm.

[002188] Sufficient adhesive force was observed both on the anode and on the cathode.

[002189] When a deformation test of the electrode (anode) was performed, the average value of L, and L7 was 2 mm. When an electrode deformation test (cathode) was performed, the average value of L, and L, was 0 mm.

[002190] When the ventilation resistance of the electrode (anode) was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in

565/803 measuring condition 1 and 0.0228 (kPa-s / m) in measuring condition 2. When the ventilation resistance of the electrode (cathode) was measured, the ventilation resistance was 0.07 (kPa-s / m) or less in measurement condition 1 and 0.0027 (kKPa-s / m) in measurement condition 2.

[002191] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: “0” at both the anode and the cathode. In Example 22, the cathode and anodes were combined by affixing the cathode to one surface of the membrane and the anode to the other surface and subjecting them to membrane damage assessment. [Example 23]

[002192] In Example 23, a microporous membrane "Zirfon Perl UTP 500" manufactured by Agfa was used.

[002193] The Zirfon membrane was immersed in pure water for 12 hours or more and used for the test. Except for what was described above, the above assessment was carried out in the same way as in Example 3, and the results are shown in Table 2.

[002194] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002195] Similar to the case where an ion exchange membrane was used as a membrane, sufficient adhesive strength was observed. The microporous membrane was placed in close contact with the electrode through surface tension, and the manipulation property was good: “1”. [Example 24]

[002196] A carbon cloth obtained by weaving a carbon fiber with a thickness of 566 µm caliber was provided as a substrate for the electrode for cathode electrolysis. A coating liquid for use

565/803 measuring condition 1 and 0.0228 (kPa-s / m) in measuring condition 2. When the ventilation resistance of the electrode (cathode) was measured, the ventilation resistance was 0.07 (kPa-s / m) or less in measurement condition 1 and 0.0027 (kKPa-s / m) in measurement condition 2.

[002191] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: “0” at both the anode and the cathode. In Example 22, the cathode and anodes were combined by affixing the cathode to one surface of the membrane and the anode to the other surface and subjecting them to membrane damage assessment. [Example 23]

[002192] In Example 23, a microporous membrane "Zirfon Perl UTP 500" manufactured by Agfa was used.

[002193] The Zirfon membrane was immersed in pure water for 12 hours or more and used for the test. Except for what was described above, the above assessment was carried out in the same way as in Example 3, and the results are shown in Table 2.

[002194] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002195] Similar to the case where an ion exchange membrane was used as a membrane, sufficient adhesive strength was observed. The microporous membrane was placed in close contact with the electrode through surface tension, and the manipulation property was good: “1”. [Example 24]

[002196] A carbon cloth obtained by weaving a carbon fiber with a thickness of 566 µm caliber was provided as a substrate for the electrode for cathode electrolysis. A coating liquid for use

566/803 in the formation of an electrode catalyst on this carbon cloth was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002197] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088 (trade name), thickness 10 mm) in around a polyvinyl chloride (PVC) cylinder was always in contact with the above coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the produced electrode was 570 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 4 µm. The thickness of the catalytic layer was the total thickness of ruthenium oxide and cerium oxide.

[002198] The resulting electrode was subjected to electrolytic evaluation. The

566/803 in the formation of an electrode catalyst on this carbon cloth was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002197] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088 (trade name), thickness 10 mm) in around a polyvinyl chloride (PVC) cylinder was always in contact with the above coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the produced electrode was 570 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 4 µm. The thickness of the catalytic layer was the total thickness of ruthenium oxide and cerium oxide.

[002198] The resulting electrode was subjected to electrolytic evaluation. The

567/803 results are shown in Table 2.

[002199] When an electrode deformation test was performed, the average value of L, and L, was O mm.

[002200] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.19 (kPa: -s / m) in the measurement condition | and 0.176 (kPa-s / m) in measurement condition 2.

[002201] The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate.

[002202] The voltage was high, the damage to the membrane was rated "1" and the damage to the membrane was observed. It was conceived that this is due to the fact that the NaOH that was generated in the electrode accumulated at the interface between the electrode and the membrane to increase its concentration, due to the high ventilation resistance of the electrode of Example 24. [Reference example 1 ]

[002203] In Reference Example 1, a cathode was used as a cathode in a large electrolyzer for eight years, degraded and with an intensified electrolytic voltage. The above cathode was placed instead of the nickel mesh feed conductor on the cathode chamber mattress, and the ion exchange membrane A produced in [Method (1)] was sandwiched between them. Then, electrolytic evaluation was performed. In Reference Example 1, no electrodes integrated into the membrane were used. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage, the ion exchange membrane A and the anodes were arranged in the order mentioned from the side of the cathode chamber to form a structure of zero interstice.

[002204] As a result of the electrolytic evaluation with this structure, the voltage was 3.04 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) 20 ppm. Consequently, due to the cathode degradation, the voltage was high.

567/803 results are shown in Table 2.

[002199] When an electrode deformation test was performed, the average value of L, and L, was O mm.

[002200] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.19 (kPa: -s / m) in the measurement condition | and 0.176 (kPa-s / m) in measurement condition 2.

[002201] The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate.

[002202] The voltage was high, the damage to the membrane was rated "1" and the damage to the membrane was observed. It was conceived that this is due to the fact that the NaOH that was generated in the electrode accumulated at the interface between the electrode and the membrane to increase its concentration, due to the high ventilation resistance of the electrode of Example 24. [Reference example 1 ]

[002203] In Reference Example 1, a cathode was used as a cathode in a large electrolyzer for eight years, degraded and with an intensified electrolytic voltage. The above cathode was placed instead of the nickel mesh feed conductor on the cathode chamber mattress, and the ion exchange membrane A produced in [Method (1)] was sandwiched between them. Then, electrolytic evaluation was performed. In Reference Example 1, no electrodes integrated into the membrane were used. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage, the ion exchange membrane A and the anodes were arranged in the order mentioned from the side of the cathode chamber to form a structure of zero interstice.

[002204] As a result of the electrolytic evaluation with this structure, the voltage was 3.04 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) 20 ppm. Consequently, due to the cathode degradation, the voltage was high.

568/803 [Reference example 2]

[002205] In Reference Example 2, a nickel mesh feed conductor was used as the cathode. In other words, electrolysis was performed on a nickel mesh without a catalyst coating.

[002206] The nickel mesh cathode was placed on the mattress of the cathodic chamber, and the ion exchange membrane A produced in [Method (i)] was sandwiched between them. Then, electrolytic evaluation was performed. In the sectional structure of the electrical cell of Reference Example 2, the collector, mattress, nickel mesh, ion exchange membrane A and anodes were arranged in the order mentioned from the side of the cathode chamber to form an interstitial structure zero.

[002207] As a result of the electrolytic evaluation with this structure, the voltage was 3.38 V, the current efficiency was 97.7%, the concentration of common salt in the caustic soda (value converted into the base of 50%) 24 ppm. Consequently, the tension was high because the cathode catalyst was uncoated. [Reference example 3]

[002208] In Reference Example 3, an anode was used as an anode in a large electrolyzer for about eight years, degraded and with an intensified electrolytic voltage.

[002209] In the sectional structure of the electrolytic cell of Reference Example 3, the collector, mattress, cathode, ion exchange membrane À produced in [Method (1i)], and the anode that was degraded and had an electrolytic voltage intensified were arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure.

[002210] As a result of the electrolytic evaluation with this structure, the voltage was 3.18 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) of 22 ppm. Consequently, due to degradation of the anode, the voltage was high.

568/803 [Reference example 2]

[002205] In Reference Example 2, a nickel mesh feed conductor was used as the cathode. In other words, electrolysis was performed on a nickel mesh without a catalyst coating.

[002206] The nickel mesh cathode was placed on the mattress of the cathodic chamber, and the ion exchange membrane A produced in [Method (i)] was sandwiched between them. Then, electrolytic evaluation was performed. In the sectional structure of the electrical cell of Reference Example 2, the collector, mattress, nickel mesh, ion exchange membrane A and anodes were arranged in the order mentioned from the side of the cathode chamber to form an interstitial structure zero.

[002207] As a result of the electrolytic evaluation with this structure, the voltage was 3.38 V, the current efficiency was 97.7%, the concentration of common salt in the caustic soda (value converted into the base of 50%) 24 ppm. Consequently, the tension was high because the cathode catalyst was uncoated. [Reference example 3]

[002208] In Reference Example 3, an anode was used as an anode in a large electrolyzer for about eight years, degraded and with an intensified electrolytic voltage.

[002209] In the sectional structure of the electrolytic cell of Reference Example 3, the collector, mattress, cathode, ion exchange membrane À produced in [Method (1i)], and the anode that was degraded and had an electrolytic voltage intensified were arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure.

[002210] As a result of the electrolytic evaluation with this structure, the voltage was 3.18 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) of 22 ppm. Consequently, due to degradation of the anode, the voltage was high.

569/803 [Comparative Example 1]

[002211] In Comparative Example 1, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 33% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 1, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.68 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002212] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002213] The mass per unit area was 67.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.05 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 64%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 22%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The damage to

569/803 [Comparative Example 1]

[002211] In Comparative Example 1, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 33% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 1, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.68 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002212] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002213] The mass per unit area was 67.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.05 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 64%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 22%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The damage to

570/803 membrane was rated “0”.

[002214] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002215] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Comparative Example 2]

[002216] In Comparative Example 2, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 16% was used as substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 2, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002217] The thickness of the electrode was 107 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm.

[002218] The mass per unit area was 78.1 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.04 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 37%, and the result of the

570/803 membrane was rated “0”.

[002214] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002215] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Comparative Example 2]

[002216] In Comparative Example 2, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 16% was used as substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 2, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002217] The thickness of the electrode was 107 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm.

[002218] The mass per unit area was 78.1 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.04 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 37%, and the result of the

571/803 evaluation of the winding around the 145 mm diameter column (3) was 25%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002219] When an electrode deformation test was performed, the average value of L, and L> was 18.5 mm.

[002220] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0176 (kPa-s / m) in the condition of measurement 2. [Comparative Example 3]

[002221] In Comparative Example 3, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 40% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 3, a nickel plate with a thickness of 1 mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.70 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002222] The substrate coating for the electrolysis electrode was carried out by ion galvanizing in the same way as in Example 6.

571/803 evaluation of the winding around the 145 mm diameter column (3) was 25%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002219] When an electrode deformation test was performed, the average value of L, and L> was 18.5 mm.

[002220] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0176 (kPa-s / m) in the condition of measurement 2. [Comparative Example 3]

[002221] In Comparative Example 3, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 40% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 3, a nickel plate with a thickness of 1 mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.70 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002222] The substrate coating for the electrolysis electrode was carried out by ion galvanizing in the same way as in Example 6.

572/803 Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002223] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002224] The force applied per unit mass-unit area (1) was a small value like 0.07 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was 80%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was 32%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "3", which was also problematic. The membrane damage was rated “0”.

[002225] When an electrode deformation test was performed, the average value of L, and L> was 11 mm.

[002226] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2. [Comparative Example 4]

[002227] In Comparative Example 4, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 58% was used as substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 4, a nickel plate with a thickness of 1 mm was submitted simultaneously to the treatment

572/803 Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002223] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002224] The force applied per unit mass-unit area (1) was a small value like 0.07 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was 80%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was 32%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "3", which was also problematic. The membrane damage was rated “0”.

[002225] When an electrode deformation test was performed, the average value of L, and L> was 11 mm.

[002226] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2. [Comparative Example 4]

[002227] In Comparative Example 4, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 58% was used as substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 4, a nickel plate with a thickness of 1 mm was submitted simultaneously to the treatment

573/803 by pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002228] The thickness of the electrode was 109 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 9 µm.

[002229] The force applied per unit mass-unit area (1) was a small value such as 0.06 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was 69%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was 39%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "3", which was also problematic. The membrane damage was rated “0”.

[002230] When an electrode deformation test was performed, the average value of L, and L> was 11.5 mm.

[002231] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2. [Comparative Example 5]

[002232] In Comparative Example 5, a nickel wire mesh with a gauge thickness of 300 µm and an opening ratio of 56% was used as a substrate for the electrode for cathode electrolysis. It is difficult to measure

573/803 by pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002228] The thickness of the electrode was 109 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 9 µm.

[002229] The force applied per unit mass-unit area (1) was a small value such as 0.06 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was 69%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was 39%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "3", which was also problematic. The membrane damage was rated “0”.

[002230] When an electrode deformation test was performed, the average value of L, and L> was 11.5 mm.

[002231] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2. [Comparative Example 5]

[002232] In Comparative Example 5, a nickel wire mesh with a gauge thickness of 300 µm and an opening ratio of 56% was used as a substrate for the electrode for cathode electrolysis. It is difficult to measure

574/803 the roughness of the wire mesh surface. Thus, in Comparative Example 5, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. The arithmetic mean roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002233] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002234] The mass per unit area was 49.2 (mg / cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 88%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 42%. The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. When the large size electrode was actually operated, it was possible to evaluate the handling property as “3”. The membrane damage was rated “0”.

[002235] When an electrode deformation test was performed, the average value of L, and L> was 23 mm.

[002236] When the ventilation resistance of the electrode was measured, the

574/803 the roughness of the wire mesh surface. Thus, in Comparative Example 5, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. The arithmetic mean roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 1, and the results are shown in Table 2.

[002233] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002234] The mass per unit area was 49.2 (mg / cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 88%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 42%. The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. When the large size electrode was actually operated, it was possible to evaluate the handling property as “3”. The membrane damage was rated “0”.

[002235] When an electrode deformation test was performed, the average value of L, and L> was 23 mm.

[002236] When the ventilation resistance of the electrode was measured, the

575/803 ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in measurement condition 2. [Comparative Example 6]

[002237] In Comparative Example 6, a nickel wire mesh with a gauge thickness of 200 µm and an opening ratio of 37% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the wire mesh. Thus, in Comparative Example 6, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.65 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. With the exception of the one described above, the assessment of electrode electrolysis, the results of the measurement of the adhesive force and the adhesiveness were performed in the same way as in Example 1. The results are shown in Table 2.

[002238] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002239] The mass per unit area was 56.45 mg / in ?. Thus, the result of the method of assessing the winding around the 145 mm diameter column (3) was 63%, and the adhesion between the electrode and the membrane was poor. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. The damage to

575/803 ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in measurement condition 2. [Comparative Example 6]

[002237] In Comparative Example 6, a nickel wire mesh with a gauge thickness of 200 µm and an opening ratio of 37% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the wire mesh. Thus, in Comparative Example 6, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.65 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. With the exception of the one described above, the assessment of electrode electrolysis, the results of the measurement of the adhesive force and the adhesiveness were performed in the same way as in Example 1. The results are shown in Table 2.

[002238] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002239] The mass per unit area was 56.45 mg / in ?. Thus, the result of the method of assessing the winding around the 145 mm diameter column (3) was 63%, and the adhesion between the electrode and the membrane was poor. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. The damage to

576/803 membrane was rated “0”.

[002240] When an electrode deformation test was performed, the average value of L, and L> was 19 mm.

[002241] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0096 (kPa-s / m) in the condition of measurement 2. [Comparative Example 7]

[002242] In Comparative Example 7, a fully laminated expanded titanium metal with a gauge thickness of 500 µm and an opening ratio of 17% was used as a substrate for the electrode for the anode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 7, a titanium plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002243] The thickness of the electrode was 508 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002244] The mass per unit area was 152.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the winding assessment around the 280 mm diameter column (2) was less than 5%, and the result

576/803 membrane was rated “0”.

[002240] When an electrode deformation test was performed, the average value of L, and L> was 19 mm.

[002241] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0096 (kPa-s / m) in the condition of measurement 2. [Comparative Example 7]

[002242] In Comparative Example 7, a fully laminated expanded titanium metal with a gauge thickness of 500 µm and an opening ratio of 17% was used as a substrate for the electrode for the anode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 7, a titanium plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 16, and the results are shown in Table 2.

[002243] The thickness of the electrode was 508 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002244] The mass per unit area was 152.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002245] When an electrode deformation test was carried out, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002246] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0072 (kPa-s / m) in the condition of measurement 2. [Comparative Example 8]

[002247] In Comparative Example 8, a fully rolled titanium expanded metal with a caliber thickness of 800 µm and an opening ratio of 8% was used as a substrate for the electrode for anode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 8, a titanium plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.61 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except for what was described above, the above evaluation was carried out in the same way as in Example 16, and the results are shown in the Table for the evaluation of the winding around the 145 mm diameter column (3) was less than 5%. The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002245] When an electrode deformation test was carried out, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002246] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0072 (kPa-s / m) in the condition of measurement 2. [Comparative Example 8]

[002247] In Comparative Example 8, a fully rolled titanium expanded metal with a caliber thickness of 800 µm and an opening ratio of 8% was used as a substrate for the electrode for anode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 8, a titanium plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.61 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the above assessment was performed in the same way as in Example 16, and the results are shown in Table

578/803

2.

[002248] The thickness of the electrode was 808 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002249] The mass per unit area was 251.3 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002250] When a deformation test of the electrode was performed, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002251] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0172 (kPa-s / m) in the condition of measurement 2. [Comparative Example 9]

[002252] In Comparative Example 9, a fully laminated titanium expanded metal with a caliber thickness of 1000 µm and an opening ratio of 46% was used as a substrate for the electrode for the anode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 9, a titanium plate

578/803

2.

[002248] The thickness of the electrode was 808 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002249] The mass per unit area was 251.3 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002250] When a deformation test of the electrode was performed, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002251] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0172 (kPa-s / m) in the condition of measurement 2. [Comparative Example 9]

[002252] In Comparative Example 9, a fully laminated titanium expanded metal with a caliber thickness of 1000 µm and an opening ratio of 46% was used as a substrate for the electrode for the anode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Comparative Example 9, a titanium plate

579/803 with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.59 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the above assessment was performed in the same way as in Example 16, and the results are shown in Table

2.

[002253] The thickness of the electrode was 1011 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 11 µm.

[002254] The mass per unit area was 245.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002255] When a deformation test of the electrode was performed, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002256] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

579/803 with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.59 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the above assessment was performed in the same way as in Example 16, and the results are shown in Table

2.

[002253] The thickness of the electrode was 1011 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 11 µm.

[002254] The mass per unit area was 245.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002255] When a deformation test of the electrode was performed, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002256] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

580/803 [Comparative Example 10]

[002257] In Comparative Example 10, a set of membrane electrodes was produced by thermal compression of an electrode on a membrane with reference to a prior art document (Examples of Japanese Patent Open to the Public No. 58-48686).

[002258] A fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 33% was used as a substrate for the electrode for electrolyzing the cathode to perform electrode coating in the same manner as in Example 1. Subsequently, an electrode surface was subjected to an inactivation treatment in the following procedure. Polyimide adhesive tape (Chukoh Chemical Industries, Ltd.) was affixed to an electrode surface. A dispersion of PTFE (Dupont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was applied to the other surface and dried in a muffle at 120ºC for 10 minutes. The polyimide tape was peeled and a sintering treatment was carried out in a muffle at 380ºC for 10 minutes. This operation was repeated twice to inactivate the electrode surface.

[002259] A membrane formed by two layers of a perfluorocarbon polymer whose terminal functional group is "-COOCH; 3" (polymer C) and a perfluorocarbon polymer whose terminal group is "- SO3F" (polymer S) was produced. The thickness of polymer layer C was 3 mils and the thickness of polymer layer S was 4 mils. This two-layer membrane was subjected to a saponification treatment to introduce ion exchange groups at the polymer terminals by hydrolysis. The polymer C terminals were hydrolyzed in carboxylic acid groups and the polymer S terminals in sulfo groups. The ion exchange capacity, like the sulfonic acid group, was 1.0 meq / g, and the ion exchange capacity, like the carboxylic acid group, was 0.9 meq / g.

[002260] The surface of the inactivated electrode was arranged in the opposite way

580/803 [Comparative Example 10]

[002257] In Comparative Example 10, a set of membrane electrodes was produced by thermal compression of an electrode on a membrane with reference to a prior art document (Examples of Japanese Patent Open to the Public No. 58-48686).

[002258] A fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 33% was used as a substrate for the electrode for electrolyzing the cathode to perform electrode coating in the same manner as in Example 1. Subsequently, an electrode surface was subjected to an inactivation treatment in the following procedure. Polyimide adhesive tape (Chukoh Chemical Industries, Ltd.) was affixed to an electrode surface. A dispersion of PTFE (Dupont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was applied to the other surface and dried in a muffle at 120ºC for 10 minutes. The polyimide tape was peeled and a sintering treatment was carried out in a muffle at 380ºC for 10 minutes. This operation was repeated twice to inactivate the electrode surface.

[002259] A membrane formed by two layers of a perfluorocarbon polymer whose terminal functional group is "-COOCH; 3" (polymer C) and a perfluorocarbon polymer whose terminal group is "- SO3F" (polymer S) was produced. The thickness of polymer layer C was 3 mils and the thickness of polymer layer S was 4 mils. This two-layer membrane was subjected to a saponification treatment to introduce ion exchange groups at the polymer terminals by hydrolysis. The polymer C terminals were hydrolyzed in carboxylic acid groups and the polymer S terminals in sulfo groups. The ion exchange capacity, like the sulfonic acid group, was 1.0 meq / g, and the ion exchange capacity, like the carboxylic acid group, was 0.9 meq / g.

[002260] The surface of the inactivated electrode was arranged in the opposite way

581/803 and thermally pressed on the surface with carboxylic acid groups such as ion exchange groups to integrate the ion exchange membrane and the electrode. The electrode surface was exposed even after thermal compression, and the electrode passed through no portion of the membrane.

[002261] Subsequently, in order to suppress the display of bubbles to be generated during electrolysis to the membrane, a mixture of zirconium oxide and a perfluorocarbon polymer in which sulfo groups were introduced was applied on both surfaces. Thus, the set of membrane electrodes of Comparative Example 10 was produced.

[002262] When the force applied per unit mass-unit area (1) was measured using this membrane electrode assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression . Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.50 (N / mg: ecm?) Was applied, a portion of the membrane was broken. The membrane electrode set of Comparative Example 10 had a force applied per unit mass-unit area (1) of at least 1.50 (N / mg: cm?) And was strongly bonded.

[002263] When the winding was evaluated around the 280 mm diameter column (1), the area in contact with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and the membrane were 100% connected to each other, but the membrane was not wound around the column in the first place. The result of the assessment of the winding around the 145 mm diameter column (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The manipulation property was “3”, which was

581/803 and thermally pressed on the surface with carboxylic acid groups such as ion exchange groups to integrate the ion exchange membrane and the electrode. The electrode surface was exposed even after thermal compression, and the electrode passed through no portion of the membrane.

[002261] Subsequently, in order to suppress the display of bubbles to be generated during electrolysis to the membrane, a mixture of zirconium oxide and a perfluorocarbon polymer in which sulfo groups were introduced was applied on both surfaces. Thus, the set of membrane electrodes of Comparative Example 10 was produced.

[002262] When the force applied per unit mass-unit area (1) was measured using this membrane electrode assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression . Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.50 (N / mg: ecm?) Was applied, a portion of the membrane was broken. The membrane electrode set of Comparative Example 10 had a force applied per unit mass-unit area (1) of at least 1.50 (N / mg: cm?) And was strongly bonded.

[002263] When the winding was evaluated around the 280 mm diameter column (1), the area in contact with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and the membrane were 100% connected to each other, but the membrane was not wound around the column in the first place. The result of the assessment of the winding around the 145 mm diameter column (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The manipulation property was “3”, which was

582/803 problematic. The membrane damage was rated “0”. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda (value converted to the base of 50%) was increased and the electrolytic performance deteriorated.

[002264] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002265] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002266] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Comparative Example 11]

[002267] In Comparative Example 11, a 40 mesh nickel mesh with a line diameter of 150 µm, a gauge thickness of 300 µm and an opening ratio of 58% was used as substrate for the electrode for cathode electrolysis . Except for the above, a set of membrane electrodes was produced in the same way as in Comparative Example 10.

[002268] When the force applied per unit mass-unit area (1) was measured using this membrane electrode assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression . Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.60 (N / mg: in?) Was applied, a portion of the membrane was broken. The membrane electrode set of Comparative Example 11 had a force applied per unit mass-unit area (1) of at least 1.60

582/803 problematic. The membrane damage was rated “0”. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda (value converted to the base of 50%) was increased and the electrolytic performance deteriorated.

[002264] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002265] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002266] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Comparative Example 11]

[002267] In Comparative Example 11, a 40 mesh nickel mesh with a line diameter of 150 µm, a gauge thickness of 300 µm and an opening ratio of 58% was used as substrate for the electrode for cathode electrolysis . Except for the above, a set of membrane electrodes was produced in the same way as in Comparative Example 10.

[002268] When the force applied per unit mass-unit area (1) was measured using this membrane electrode assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression . Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.60 (N / mg: in?) Was applied, a portion of the membrane was broken. The membrane electrode set of Comparative Example 11 had a force applied per unit mass-unit area (1) of at least 1.60

583/803 (N / mg: cm?) And was tightly bound.

[002269] When the winding was evaluated around the 280 mm diameter column (1) using this membrane electrode set, the contact area with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and the membrane were 100% connected to each other, but the membrane was not wound around the column in the first place. The result of the evaluation of the winding around the column of 145 mm in diameter (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The handling property was "3", which was problematic. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda was increased and the electrolytic performance deteriorated.

[002270] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002271] When an electrode deformation test was performed, the average value of L, and L> was 23 mm.

[002272] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in the condition of measurement 2. [Comparative Example 12] (Preparation of the catalyst)

[002273] An aqueous metal salt solution was produced by adding 0.728 g of silver nitrate (Wako Pure Chemical Industries, Ltd.) and 1.86 g of cerium nitrate hexahydrate (Wako Pure Chemical Industries, Ltd .) to 150 ml of pure water. An alkaline solution was produced by adding 240 g

583/803 (N / mg: cm?) And was tightly bound.

[002269] When the winding was evaluated around the 280 mm diameter column (1) using this membrane electrode set, the contact area with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and the membrane were 100% connected to each other, but the membrane was not wound around the column in the first place. The result of the evaluation of the winding around the column of 145 mm in diameter (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The handling property was "3", which was problematic. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda was increased and the electrolytic performance deteriorated.

[002270] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002271] When an electrode deformation test was performed, the average value of L, and L> was 23 mm.

[002272] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in the condition of measurement 2. [Comparative Example 12] (Preparation of the catalyst)

[002273] An aqueous metal salt solution was produced by adding 0.728 g of silver nitrate (Wako Pure Chemical Industries, Ltd.) and 1.86 g of cerium nitrate hexahydrate (Wako Pure Chemical Industries, Ltd .) to 150 ml of pure water. An alkaline solution was produced by adding 240 g

584/803 of pure water to 100 g of a 15% aqueous solution of tetramethylammonium hydroxide (Wako Pure Chemical Industries, Ltd.). While the alkaline solution was stirred using a magnetic stirrer, the aqueous metal salt solution was added dropwise at 5 ml / minute using a burette. A suspension containing the resulting metal hydroxide particles was filtered with suction and then washed with water to remove the alkali content. Then, the residue was transferred to 200 ml of 2-propanol (KISHIDA CHEMICAL Co. Ltd.) and redispersed by an ultrasonic dispersion apparatus (US-600T, NISSEI Corporation) for 10 minutes to obtain a uniform suspension.

[002274] A carbon black suspension was obtained by dispersing 0.36 g of hydrophobic carbon black (DENKA BLACK (R) AB-7 (trade name), Denka Company Limited) and 0.84 g of black hydrophilic smoke (Ketjenblack (R) EC-600JD (trade name), Mitsubishi Chemical Corporation) in 100 ml of 2-propanol and dispersion of the mixture by the ultrasonic dispersion apparatus for 10 minutes. The suspension of the metal hydroxide precursor and the carbon black suspension were mixed and dispersed by the ultrasonic dispersion apparatus for 10 minutes. This suspension was suction filtered and dried at room temperature for half a day to obtain carbon black containing the dispersed and fixed metal hydroxide precursor. Subsequently, an inert gas cooking oven (type VMFI65, YAMADA DENKI CO ,, LTD.) Was used to cook in an atmosphere of nitrogen at 400ºC for one hour to obtain carbon black A containing a fixed and dispersed electrode catalyst. (Powder production for reaction layer)

[002275] To 1.6 g of carbon black AÀ containing a dispersed and fixed electrode catalyst, 0.84 ml of a Triton (R) X-100 surfactant (trade name, ICN Biomedicals) was added diluted to 20% by weight with pure water and 15 ml of pure water, and the mixture was dispersed by a

584/803 of pure water to 100 g of a 15% aqueous solution of tetramethylammonium hydroxide (Wako Pure Chemical Industries, Ltd.). While the alkaline solution was stirred using a magnetic stirrer, the aqueous metal salt solution was added dropwise at 5 ml / minute using a burette. A suspension containing the resulting metal hydroxide particles was filtered with suction and then washed with water to remove the alkali content. Then, the residue was transferred to 200 ml of 2-propanol (KISHIDA CHEMICAL Co. Ltd.) and redispersed by an ultrasonic dispersion apparatus (US-600T, NISSEI Corporation) for 10 minutes to obtain a uniform suspension.

[002274] A carbon black suspension was obtained by dispersing 0.36 g of hydrophobic carbon black (DENKA BLACK (R) AB-7 (trade name), Denka Company Limited) and 0.84 g of black hydrophilic smoke (Ketjenblack (R) EC-600JD (trade name), Mitsubishi Chemical Corporation) in 100 ml of 2-propanol and dispersion of the mixture by the ultrasonic dispersion apparatus for 10 minutes. The suspension of the metal hydroxide precursor and the carbon black suspension were mixed and dispersed by the ultrasonic dispersion apparatus for 10 minutes. This suspension was suction filtered and dried at room temperature for half a day to obtain carbon black containing the dispersed and fixed metal hydroxide precursor. Subsequently, an inert gas cooking oven (type VMFI65, YAMADA DENKI CO ,, LTD.) Was used to cook in an atmosphere of nitrogen at 400ºC for one hour to obtain carbon black A containing a fixed and dispersed electrode catalyst. (Powder production for reaction layer)

[002275] To 1.6 g of carbon black AÀ containing a dispersed and fixed electrode catalyst, 0.84 ml of a Triton (R) X-100 surfactant (trade name, ICN Biomedicals) was added diluted to 20% by weight with pure water and 15 ml of pure water, and the mixture was dispersed by a

585/803 ultrasonic dispersion for 10 minutes. To that dispersion, 0.664 g of a polytetrafluoroethylene (PTFE) dispersion (PTFE30J (tradename), Dupont-Mitsui Fluorochemicals Co., Ltd.) was added. After the mixture had been stirred for five minutes, suction filtration was performed. In addition, the residue was dried in a dryer at 80ºC for one hour and the spraying was carried out by a mill to obtain a powder for reaction layer A. (Powder production for gas diffusion layer)

[002276] 20 g of hydrophobic carbon black (DENKA BLACK (R) AB-7 (trade name)), 50 ml of a Triton (R) X-100 (trade name) surfactant diluted to 20% by weight with pure water and 360 ml of pure water by an ultrasonic dispersion device for 10 minutes. To the resulting dispersion, 22.32 g of the PTFE dispersion was added. The mixture was stirred for 5 minutes, and then filtration was carried out. In addition, the residue was dried in a dryer at 80ºC for one hour and the spraying was carried out by a mill to obtain a powder for the gas diffusion layer A. (Production of the gas diffusion electrode)

[002277] To 4 g of the powder for the gas diffusion layer A, 8.7 ml of ethanol were added and the mixture was kneaded into a paste. This powder for the gas diffusion layer in the form of paste was formed into a sheet form by a roll former. Silver mesh (SW = 1, LW = 2 and thickness = 0.3 mm) as the collector was embedded in the sheet and finally formed into a sheet shape with a thickness of 1.8 mm. To 1 g of the powder for reaction layer A, 2.2 ml of ethanol was added and the mixture was kneaded into a paste. This powder for the paste reaction layer was formed into a sheet form with a thickness of 0.2 mm. In addition, the two sheets, that is, the sheet obtained using the powder for the A-gas diffusion layer produced and the sheet obtained using the powder for the À-reaction layer were

585/803 ultrasonic dispersion for 10 minutes. To that dispersion, 0.664 g of a polytetrafluoroethylene (PTFE) dispersion (PTFE30J (tradename), Dupont-Mitsui Fluorochemicals Co., Ltd.) was added. After the mixture had been stirred for five minutes, suction filtration was performed. In addition, the residue was dried in a dryer at 80ºC for one hour and the spraying was carried out by a mill to obtain a powder for reaction layer A. (Powder production for gas diffusion layer)

[002276] 20 g of hydrophobic carbon black (DENKA BLACK (R) AB-7 (trade name)), 50 ml of a Triton (R) X-100 (trade name) surfactant diluted to 20% by weight with pure water and 360 ml of pure water by an ultrasonic dispersion device for 10 minutes. To the resulting dispersion, 22.32 g of the PTFE dispersion was added. The mixture was stirred for 5 minutes, and then filtration was carried out. In addition, the residue was dried in a dryer at 80ºC for one hour and the spraying was carried out by a mill to obtain a powder for the gas diffusion layer A. (Production of the gas diffusion electrode)

[002277] To 4 g of the powder for the gas diffusion layer A, 8.7 ml of ethanol were added and the mixture was kneaded into a paste. This powder for the gas diffusion layer in the form of paste was formed into a sheet form by a roll former. Silver mesh (SW = 1, LW = 2 and thickness = 0.3 mm) as the collector was embedded in the sheet and finally formed into a sheet shape with a thickness of 1.8 mm. To 1 g of the powder for reaction layer A, 2.2 ml of ethanol was added and the mixture was kneaded into a paste. This powder for the paste reaction layer was formed into a sheet form with a thickness of 0.2 mm. In addition, the two sheets, that is, the sheet obtained using the powder for the A-gas diffusion layer produced and the sheet obtained using the powder for the À-reaction layer were

586/803 laminated and formed into a sheet shape with a thickness of 1.8 mm by a roll former. This laminated sheet was dried at room temperature for one day and overnight to remove ethanol. In addition, in order to remove the remaining surfactant, the leaf was subjected to an air pyrolysis treatment at 300ºC for one hour. The sheet was wrapped in aluminum foil and subjected to hot pressing by a hot pressing machine (SA303 (trade name), TESTER SANGYO CO ,. LTD) at 360ºC and 50 kgf / cm? for 1 minute to obtain a gas diffusion electrode. The thickness of the gas diffusion electrode was 412 µm.

[002278] The resulting electrode was used to perform electrolytic evaluation. In the sectional structure of the electrolytic cell, the collector, mattress, nickel mesh feed conductor, electrode, membrane and anode are arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure. The results are shown in Table 2.

[002279] When an electrode deformation test was performed, the average value of L, and L> was 19 mm.

[002280] When the ventilation resistance of the electrode was measured, the ventilation resistance was 25.88 (kPa-s / m) in measurement condition 1.

[002281] The handling property was "3", which was problematic. In addition, when the electrolytic evaluation was carried out, the current efficiency was low, the concentration of common salt in the caustic soda was increased and the electrolytic performance deteriorated remarkably. The membrane damage, which was rated "3", also had a problem.

[002282] These results revealed that the gas diffusion electrode obtained in Comparative Example 12 had a remarkably weak electrolytic performance. In addition, damage was observed to the substantially entire surface of the ion exchange membrane. It was conceived that this

586/803 laminated and formed into a sheet shape with a thickness of 1.8 mm by a roll former. This laminated sheet was dried at room temperature for one day and overnight to remove ethanol. In addition, in order to remove the remaining surfactant, the leaf was subjected to an air pyrolysis treatment at 300ºC for one hour. The sheet was wrapped in aluminum foil and subjected to hot pressing by a hot pressing machine (SA303 (trade name), TESTER SANGYO CO ,. LTD) at 360ºC and 50 kgf / cm? for 1 minute to obtain a gas diffusion electrode. The thickness of the gas diffusion electrode was 412 µm.

[002278] The resulting electrode was used to perform electrolytic evaluation. In the sectional structure of the electrolytic cell, the collector, mattress, nickel mesh feed conductor, electrode, membrane and anode are arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure. The results are shown in Table 2.

[002279] When an electrode deformation test was performed, the average value of L, and L> was 19 mm.

[002280] When the ventilation resistance of the electrode was measured, the ventilation resistance was 25.88 (kPa-s / m) in measurement condition 1.

[002281] The handling property was "3", which was problematic. In addition, when the electrolytic evaluation was carried out, the current efficiency was low, the concentration of common salt in the caustic soda was increased and the electrolytic performance deteriorated remarkably. The membrane damage, which was rated "3", also had a problem.

[002282] These results revealed that the gas diffusion electrode obtained in Comparative Example 12 had a remarkably weak electrolytic performance. In addition, damage was observed to the substantially entire surface of the ion exchange membrane. It was conceived that this

587/803 is due to the fact that the NaOH that was generated in the electrode accumulated at the interface between the electrode and the membrane to increase its concentration, due to the remarkably high ventilation resistance of the gas diffusion electrode of Comparative Example 12. [Comparative Example 13]

[002283] A nickel line with a gauge thickness of 150 µm was provided as a substrate for the electrode for electrolysis of the cathode. A roughness treatment by this nickel line was carried out. It is difficult to measure the surface roughness of the nickel line. Thus, in Comparative Example 13, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the nickel line. A pickling treatment was carried out with grain size alumina number 320. The arithmetic mean roughness Ra was 0.64 µm.

[002284] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002285] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088 (trade name), thickness 10 mm) in around a polyvinyl chloride (PVC) cylinder was always in contact with the coating liquid

587/803 is due to the fact that the NaOH that was generated in the electrode accumulated at the interface between the electrode and the membrane to increase its concentration, due to the remarkably high ventilation resistance of the gas diffusion electrode of Comparative Example 12. [Comparative Example 13]

[002283] A nickel line with a gauge thickness of 150 µm was provided as a substrate for the electrode for electrolysis of the cathode. A roughness treatment by this nickel line was carried out. It is difficult to measure the surface roughness of the nickel line. Thus, in Comparative Example 13, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the nickel line. A pickling treatment was carried out with grain size alumina number 320. The arithmetic mean roughness Ra was 0.64 µm.

[002284] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002285] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088 (trade name), thickness 10 mm) in around a polyvinyl chloride (PVC) cylinder was always in contact with the coating liquid

588/803 above. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the nickel line produced in Comparative Example 13 was 158 µm.

[002286] The nickel line produced by the above method was cut to a length of 110 mm and a length of 95 mm. As shown in Figure 16, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and the results are shown in Table 2.

[002287] The portion of the electrode in which the nickel lines were superimposed was the largest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.7%.

[002288] The mass per unit area of the electrode was 0.5 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The manipulation property was “4”,

588/803 above. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the nickel line produced in Comparative Example 13 was 158 µm.

[002286] The nickel line produced by the above method was cut to a length of 110 mm and a length of 95 mm. As shown in Figure 16, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and the results are shown in Table 2.

[002287] The portion of the electrode in which the nickel lines were superimposed was the largest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.7%.

[002288] The mass per unit area of the electrode was 0.5 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The manipulation property was “4”,

589/803 which was also problematic. The membrane damage was rated “0”.

[002289] When an electrode deformation test was performed, the average value of L, and L> was 15 mm.

[002290] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance value was 0.0002 (kPa-s / m).

[002291] In addition, the structure shown in Figure 17 was used to position the electrode (cathode) in the Ni mesh feed conductor, and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.16 V. [Comparative Example 14]

[002292] In Comparative Example 14, the electrode produced in Comparative Example 13 was used. As shown in Figure 18, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and the results are shown in Table 2.

[002293] The portion of the electrode in which the nickel lines overlapped was the largest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.4%.

[002294] The mass per unit area of the electrode was 0.9 (mg / em?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode

589/803 which was also problematic. The membrane damage was rated “0”.

[002289] When an electrode deformation test was performed, the average value of L, and L> was 15 mm.

[002290] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance value was 0.0002 (kPa-s / m).

[002291] In addition, the structure shown in Figure 17 was used to position the electrode (cathode) in the Ni mesh feed conductor, and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.16 V. [Comparative Example 14]

[002292] In Comparative Example 14, the electrode produced in Comparative Example 13 was used. As shown in Figure 18, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and the results are shown in Table 2.

[002293] The portion of the electrode in which the nickel lines overlapped was the largest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.4%.

[002294] The mass per unit area of the electrode was 0.9 (mg / em?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode

590/803 detached from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002295] When an electrode deformation test was performed, the average value of L, and L> was 16 mm.

[002296] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0004 (kPa-s / m).

[002297] In addition, the structure shown in Figure 19 was used to position the electrode (cathode) in the Ni mesh feed conductor, and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Comparative Example 15]

[002298] In Comparative Example 15, the electrode produced in Comparative Example 13 was used. As shown in Figure 20, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and the results are shown in Table 2.

[002299] The portion of the electrode in which the nickel lines were superimposed was of the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 98.8%.

[002300] The mass per unit area of the electrode was 1.9 (mg / em?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the

590/803 detached from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002295] When an electrode deformation test was performed, the average value of L, and L> was 16 mm.

[002296] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0004 (kPa-s / m).

[002297] In addition, the structure shown in Figure 19 was used to position the electrode (cathode) in the Ni mesh feed conductor, and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Comparative Example 15]

[002298] In Comparative Example 15, the electrode produced in Comparative Example 13 was used. As shown in Figure 20, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and the results are shown in Table 2.

[002299] The portion of the electrode in which the nickel lines were superimposed was of the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 98.8%.

[002300] The mass per unit area of the electrode was 1.9 (mg / em?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the

591/803 280 mm in diameter (1) was less than 5%, and the portions in which the electrode came off the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002301] When an electrode deformation test was performed, the average value of L, and L, was 14 mm.

[002302] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0005 (kPa-s / m).

[002303] In addition, the structure shown in Figure 21 was used to position the electrode (cathode) on the Ni mesh feed conductor, and the electrolytic evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Table 1] Substrate |. Substrate shape method for:: z for coating Electrode feed conductor electrode Example 1st Ni Perfection - cc - MalhadeNi pyrolysis Example? - Ni Perfiraçção - cc - Pirolise MalhadeNi Example3 - Ni —CPerfiraçção - == Pirolise MalhadeNi Example4 - Ni Perfiração = Pyrolysis MalhadeNi Examples - Ni Perfiração - = Malhação de Ni already 10nNICAa lExample 14 Ni Drilling - Giant - aopinstise - Colch Sample 15 Ni Perforation (equal to 2 birolysis' with increase in: example 3) ensão ensao ensão ensão ensão

591/803 280 mm in diameter (1) was less than 5%, and the portions in which the electrode came off the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002301] When an electrode deformation test was performed, the average value of L, and L, was 14 mm.

[002302] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0005 (kPa-s / m).

[002303] In addition, the structure shown in Figure 21 was used to position the electrode (cathode) on the Ni mesh feed conductor, and the electrolytic evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Table 1] Substrate |. Substrate shape method for:: z for coating Electrode feed conductor electrode Example 1st Ni Perfection - cc - MalhadeNi pyrolysis Example? - Ni Perfiraçção - cc - Pirolise MalhadeNi Example3 - Ni —CPerfiraçção - == Pirolise MalhadeNi Example4 - Ni Perfiração = Pyrolysis MalhadeNi Examples - Ni Perfiração - = Malhação de Ni already 10nNICAa lExample 14 Ni Drilling - Giant - aopinstise - Colch Sample 15 Ni Perforation (equal to 2 birolysis' with increase in: example 3) ensão ensao ensão ensão ensão

592/803 Example 20 Non-woven fabric Pyrolysis - method with increase in tension Example 21 loops Pyrolysis - method with increase in tension lExample 22 NiTi 'ripening of Example 3 Chirolysis atodo and anode with increase) Example 20 ha tension Example 23 Ni - Drilling Próise E | [Example 24 woven acidic carbon Pyrolysis - Ni E mesh::. y xemplo Expanded Ni Pyrolysis - Ni mesh omparative 1 E::. y xample Ni Expanded Pyrolysis - Ni mesh omparative 2 E:: ã y xample Ni Expanded Galvanizag hn, of omparative Ni 3 x ionic ion ixpandido irolysis of Ni-omparative wire 4 [Example i Pyrolytic Mesh - omnative Ni mesh 5 xample Ni Irolysis mesh - Comparative Ni mesh 6 [Example Ti xpandido Pyrolysis A node with increase in omparative 7 tension [Example Ti xpandido Pyrolysis A node with increase in omparative 8 tension [Example Ti xpandido Pyrolysis A node with increase in omparative 9 so Exe as y ; xample Ni Expanded Pyrolysis - Ni mesh omparative 10 Exe as y; xemplo Ni alha Pyrolysis - Ni mesh omparative 11 Exe as y; xample arbono - powder Pyrolysis - Ni mesh 12 E:. y xemplo Ni alha Pyrolysis - Ni mesh omparative 13 E:. y xemplo Ni alha Pyrolysis - Ni mesh omparative 14 E:. y xemplo Ni alha Pirólise - Ni mesh omparativo 15

592/803 Example 20 Non-woven fabric Pyrolysis - method with increase in tension Example 21 loops Pyrolysis - method with increase in tension lExample 22 NiTi 'ripening of Example 3 Chirolysis atodo and anode with increase) Example 20 ha tension Example 23 Ni - Drilling Próise E | [Example 24 woven acidic carbon Pyrolysis - Ni E mesh::. y xemplo Expanded Ni Pyrolysis - Ni mesh omparative 1 E::. y xample Ni Expanded Pyrolysis - Ni mesh omparative 2 E:: ã y xample Ni Expanded Galvanizag hn, of omparative Ni 3 x ionic ion ixpandido irolysis of Ni-omparative wire 4 [Example i Pyrolytic Mesh - omnative Ni mesh 5 xample Ni Irolysis mesh - Comparative Ni mesh 6 [Example Ti xpandido Pyrolysis A node with increase in omparative 7 tension [Example Ti xpandido Pyrolysis A node with increase in omparative 8 tension [Example Ti xpandido Pyrolysis A node with increase in omparative 9 so Exe as y ; xample Ni Expanded Pyrolysis - Ni mesh omparative 10 Exe as y; xemplo Ni alha Pyrolysis - Ni mesh omparative 11 Exe as y; xample arbono - powder Pyrolysis - Ni mesh 12 E:. y xemplo Ni alha Pyrolysis - Ni mesh omparative 13 E:. y xemplo Ni alha Pyrolysis - Ni mesh omparative 14 E:. y xemplo Ni alha Pirólise - Ni mesh omparativo 15

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FS 23 Es 28 53 ê 3 2 dE sell elelel ze! slelelads 2LgêãE S & a e / 8/8 z | / 8 | S BIS E ala SE Ézã E as 2/4 and 4/8 | s 2a 2/8 | 82 | / & 4% and 328 82,

EE 2885zs 2 8858 283º ss 2 2 Be if = elelalz = / al she / he / els 52 ozZ Ss bp * only SEIT = aj = ZIZ + z "ER 2 393 ax É a = => oo & o = = SE Eo8 seia = bel * aj | = oo = o = = LSSÊ she le e Sl e = Xl IF GO E | = 2 | / Z 28 E eg GE 2 to 83 S 8 Are | EEE | TTE les E and ES E & ETZ dB EEB iv :: CIR IS | E | EE SR | RS | = | E | TX)

ET 2a EF8F ge ES à EêES 3882 els NE el. ã 2 2 3 à à EE slelelels Ss EEE sz ale lx / o e E E 8/8 E | Ss d8 2 to E to 8/8 E SÍ Ss 2 8 || = E 2 = E 8 and g 8 E 3 E $ is & $ E IS. It is 3 to Z5SESSTE i- to Lib to E «loyal. 8 & 8 8 E 8 8 be & E E = = & | E SE 8 & g = - FESSACEA ag a 2 & ã 2 8 e = o e z o a Ss m ale = | el lej = - | el a | [E = / 8 aj = | Z 7 if sl leaj / & / s / a | s / a s / a l / ea / sa | / sale s o | and E he and he and he and els E 8 CRISIS ININININININININ A, 2 Ss x | e) | | | 2 | 28) 2 | 2x | e | 2 | 2 | 2)> 8 E lss / wards S / S ls [S / S [8/8 / 8/4 Z - 2 3 Cs 3

Z 3 2 s & 8

| and Ss lax / elo & | ss ss Ss s E / S F / A / E | IS | S e] É E 8 s Z & 8 E Ss É SE S [/ S | S | S / S IF IT IS 2 / 8/8 | $ S / 3 | S8S | = 2 | / S | & * a S 8/8/8 / S | a / Sk SI a | 2 | 8, & 8 | 8 | 8 | / 8 | s2 | / 8 | s

É É TE É E É É É É É É É É É ENENCNENcCSCNENH 3 ê 3 ê 3 ê 8 ê 8 ê He le He Ie He He le É 8 8 8 8 8 8 8 8 8 8 8 = él á5 ls él í5 ls ls sil l5éE 5 E 5 Elvis sl sl 56535 SSIS ISSSTSCA ST SS 58/5/5358 SC / SE8 / 58/58/56

FL ESA sane: Ss sane and FS ÉESaa ““ E s2 tal "os e le 4 / Sl el. 23282 0 Ss alela = | + | e] = s | a = | x | 4 |« | 8 and jo = ejpejoe sn er oo <oo Ly ea a bl Ss es = || Sl = Ss = =] =] qm e = | <ESSES SR SEN ss Es Es E Es És smlals e la leila vs e | als = 2 = / Ss Ss?? 8a?? D?? D? D = ee 8 az & s ê ê ê se se se se se se se 3 se 8º 8 8º s / 8ls8 / | 8 | 8/8 / | 8 8 Bal 4H sl als 2 2 2 8 8 = g 8 8 if sl els are ES ES | 8% 8/8 8/8 8/88 => es | 8 2 2 2 Ss 8 ss / els / s / els / 3 / leils 2 s 2 s 2 sss 8 ss e / 8 e / j8 2/28/28 8/8 | / 8 | / 8 | / 8 | / 8 | 8 | / 8S | 8 2

S Ss uls se el Tx md de] x s | els S / S SIX 4 <so | E 8 | 2/2 ms & [2/2 and 3 | S |) 3 | / 8 | & S & | 8 & | & 2 Ss and selelz ala lvw | sl leBe da | ss her | = | = | = | = steel = o + * to s | s = S = = = | Ss | he aj ejlails |) e = |. The. - | 4 | 8 | is | bp = o = + = == rm o C o o o si o x r | the Sis * Z22Z2 8 E E E | & is | 4th / 4 | 8) &

It is x they le ls / T / s and | if e = ls s | = e | s = Z = e a] = z z / ss ex ds de la ss / eo e e | E) "slela / al = lg / slelelaz ls ses 8 / gg ses | sg s sl] Ss siela gi = | 3 je iS = | S&S | = / 8 | 8 $ | ss, / &% / & 8 | & 8 | = Z s Z ê FREEZERS sl s s 8 s 8 2 8 2 8 s = ss sc / 8 / & / S / 2 8 8/8 / 8/8 | / 8 | / | 8 | / 8 | 8 | / 8 | 8 o 218 gl Ss sig is E | E | &,) & sS | & 8 | & 8,) 8, & S | & 8É | EE = E are? E:? E É E z & SID RX / SC / 8 ls / S / S 3 ã & & ã & HÁ Z HÁ Z HÁ Z «S / s sl s / ae | 2/2/2988 83 [8E 28 828 88 88 983 88 | oã FS E) EEE / E / 2 | / E / E / AEE és ER 27 RF éR ER 27 és & E | / E / 5 | / E | / E8 / 5 | / E | / EF | SR RS 2 2 Sá 2ê [Pé Pê sé Rê sã 2 2 / 23/2/2/2 | / 2 | / 2 | 228 82 25 25 25 28 22 [28 22 85. 2 m ls ls s / d S / S 4 SÃSZ2ASQA SAS SA Sel Som Sel Without sSaãss ss 8 Cs 3

X 3% s & 2

| and Ss lax / elo & | ss ss Ss s E / S F / A / E | IS | S e] É E 8 s Z & 8 E Ss É SE S [/ S | S | S / S IF IT IS 2 / 8/8 | $ S / 3 | S8S | = 2 | / S | & * a S 8/8/8 / S | a / Sk SI a | 2 | 8, & 8 | 8 | 8 | / 8 | s2 | / 8 | s

É É TE É E É É É É É É É É É ENENCNENcCSCNENH 3 ê 3 ê 3 ê 8 ê 8 ê He le He Ie He He le É 8 8 8 8 8 8 8 8 8 8 8 = él á5 ls él í5 ls ls sil l5éE 5 E 5 Elvis sl sl 56535 SSIS ISSSTSCA ST SS 58/5/5358 SC / SE8 / 58/58/56

FL ESA sane: Ss sane and FS ÉESaa ““ E s2 tal "os e le 4 / Sl el. 23282 0 Ss alela = | + | e] = s | a = | x | 4 |« | 8 and jo = ejpejoe sn er oo <oo Ly ea a bl Ss es = || Sl = Ss = =] =] qm e = | <ESSES SR SEN ss Es Es E Es És smlals e la leila vs e | als = 2 = / Ss Ss?? 8a?? D?? D? D = ee 8 az & s ê ê ê se se se se se se se 3 se 8º 8 8º s / 8ls8 / | 8 | 8/8 / | 8 8 Bal 4H sl als 2 2 2 8 8 = g 8 8 if sl els are ES ES | 8% 8/8 8/8 8/88 => es | 8 2 2 2 Ss 8 ss / els / s / els / 3 / leils 2 s 2 s 2 sss 8 ss e / 8 e / j8 2/28/28 8/8 | / 8 | / 8 | / 8 | / 8 | 8 | / 8S | 8 2

S Ss uls se el Tx md de] x s | els S / S SIX 4 <so | E 8 | 2/2 ms & [2/2 and 3 | S |) 3 | / 8 | & S & | 8 & | & 2 Ss and selelz ala lvw | sl leBe da | ss her | = | = | = | = steel = o + * to s | s = S = = = | Ss | he aj ejlails |) e = |. The. - | 4 | 8 | is | bp = o = + = == rm o C o o o si o x r | the Sis * Z22Z2 8 E E E | & is | 4th / 4 | 8) &

It is x they le ls / T / s and | if e = ls s | = e | s = Z = e a] = z z / ss ex ds de la ss / eo e e | E) "slela / al = lg / slelelaz ls ses 8 / gg ses | sg s sl] Ss siela gi = | 3 je iS = | S&S | = / 8 | 8 $ | ss, / &% / & 8 | & 8 | = Z s Z ê FREEZERS sl s s 8 s 8 2 8 2 8 s = ss sc / 8 / & / S / 2 8 8/8 / 8/8 | / 8 | / | 8 | / 8 | 8 | / 8 | 8 o 218 gl Ss sig is E | E | &,) & sS | & 8 | & 8,) 8, & S | & 8É | EE = E are? E:? E É E z & SID RX / SC / 8 ls / S / S 3 ã & & ã & HÁ Z HÁ Z HÁ Z «S / s sl s / ae | 2/2/2988 83 [8E 28 828 88 88 983 88 | oã FS E) EEE / E / 2 | / E / E / AEE és ER 27 RF éR ER 27 és & E | / E / 5 | / E | / E8 / 5 | / E | / EF | SR RS 2 2 Sá 2ê [Pé Pê sé Rê sã 2 2 / 23/2/2/2 | / 2 | / 2 | 228 82 25 25 25 28 22 [28 22 85. 2 m ls ls s / d S / S 4 SÃSZ2ASQA SAS SA Sel Som Sel Without sSaãss ss 8 Cs 3

X 3% s & 2 s 4 Z 8 3 8 Ss 3 8 E Ss Ss Ss Ss

É É É é ê ê ê ê8 Es 8 g 8 = | 8 | 2ãâ |) se be = E = = E

INANN ns ls E | = a s EA o z o <<E <Za s s E 8 8 H 8 8 EPENRTPERS: PA E êu So Ze E Ze 2> 28 584 [288 Be FS 8 It is at at 2 z 2 2º 82º 82º. 8 HE 2 288 E 1 | 383 283 38 SS EoERE ETR E.ER

FERCITE CITE CI

TS EE SEE 2nd is [8th is [8th is FE FE 2a

ENSSCENERCENERE Em = = 2 ã 48 Ss o 4 2 234 9234 323 2 | E lg Es v iss ids 8 2 H3 E SF3233 <= | S | BRSsBDASADIASE a = o Ss and 2 a = z º z Z if ls Ss ss Ss ss 8 E 8 Ss & Ss Z & & =

Z ã

E s | 8 8 s Z g | 8 8 8 o & 3 & & & 2 e | E É and E Z Z Z Z Z «2E 88 288% 8% | 4% s Es | IS ER AND EL | 82 | 7% | E at 2 ESZEZ 28 | 284 | 2 3 mozãs dsST | / 4SZT RSS s 2 3 Cs be Zz be

R s & 8 s 4 Z 8 3 8 Ss 3 8 E Ss Ss Ss Ss

É É É é ê ê ê ê8 Es 8 g 8 = | 8 | 2ãâ |) se be = E = = E

INANN ns ls E | = a s EA o z o <<E <Za s s E 8 8 H 8 8 EPENRTPERS: PA E êu So Ze E Ze 2> 28 584 [288 Be FS 8 It is at at 2 z 2 2º 82º 82º. 8 HE 2 288 E 1 | 383 283 38 SS EoERE ETR E.ER

FERCITE CITE CI

TS EE SEE 2nd is [8th is [8th is FE FE 2a

ENSSCENERCENERE Em = = 2 ã 48 Ss o 4 2 234 9234 323 2 | E lg Es v iss ids 8 2 H3 E SF3233 <= | S | BRSsBDASADIASE a = o Ss and 2 a = z º z Z if ls Ss ss Ss ss 8 E 8 Ss & Ss Z & & =

Z ã

E s | 8 8 s Z g | 8 8 8 o & 3 & & & 2 e | E É and E Z Z Z Z Z «2E 88 288% 8% | 4% s Es | IS ER AND EL | 82 | 7% | E at 2 ESZEZ 28 | 284 | 2 3 mozãs dsST | / 4SZT RSS s 2 3 Cs be Zz be

R s & 8

596/803

[002304] In Table 2, all samples were able to remain alone due to surface tension before measuring “force applied per unit mass-unit area (1)” and “force applied per unit mass-unit area” (2) ”(that is, they did not slip).

[002305] In Comparative Examples 1, 2, 7 to 9, since the mass per unit area was large and the force applied per unit mass-unit area (1) was small, the adhesion to the membrane was weak. Thus, with a large size of electrolyzer (for example, 1.5 m long and 3 m wide), the membrane, which is a polymer membrane, can inevitably be loosened during handling. At that moment, the electrode comes loose and, thus, the samples do not resist practical use.

[002306] In Comparative Examples 3 and 4, since the force applied per unit mass-unit area (1) was small, the adhesion to the membrane was weak. Thus, with a large size of electrolyzer (for example, 1.5 m long and 3 m wide), the membrane, which is a polymer membrane, can inevitably be loosened during handling. At that moment, the electrode comes loose and, thus, the samples do not resist practical use.

[002307] In Comparative Examples 5 and 6, the mass per unit area was large, the adhesion to the membrane was weak. Thus, with a large size of electrolyzer (for example, 1.5 m long and 3 m wide), the membrane, which is a polymer membrane, can inevitably be loosened during handling. At that moment, the electrode comes loose and, thus, the samples do not resist practical use.

[002308] In Comparative Examples 10 and 11, since the membrane and electrode were strongly bonded by thermal pressure, the electrode did not come off the membrane during handling as in Comparative Examples 1, 2, 7 to 9. However, due to the strong connection to

596/803

[002304] In Table 2, all samples were able to remain alone due to surface tension before measuring “force applied per unit mass-unit area (1)” and “force applied per unit mass-unit area” (2) ”(that is, they did not slip).

[002305] In Comparative Examples 1, 2, 7 to 9, since the mass per unit area was large and the force applied per unit mass-unit area (1) was small, the adhesion to the membrane was weak. Thus, with a large size of electrolyzer (for example, 1.5 m long and 3 m wide), the membrane, which is a polymer membrane, can inevitably be loosened during handling. At that moment, the electrode comes loose and, thus, the samples do not resist practical use.

[002306] In Comparative Examples 3 and 4, since the force applied per unit mass-unit area (1) was small, the adhesion to the membrane was weak. Thus, with a large size of electrolyzer (for example, 1.5 m long and 3 m wide), the membrane, which is a polymer membrane, can inevitably be loosened during handling. At that moment, the electrode comes loose and, thus, the samples do not resist practical use.

[002307] In Comparative Examples 5 and 6, the mass per unit area was large, the adhesion to the membrane was weak. Thus, with a large size of electrolyzer (for example, 1.5 m long and 3 m wide), the membrane, which is a polymer membrane, can inevitably be loosened during handling. At that moment, the electrode comes loose and, thus, the samples do not resist practical use.

[002308] In Comparative Examples 10 and 11, since the membrane and electrode were strongly bonded by thermal pressure, the electrode did not come off the membrane during handling as in Comparative Examples 1, 2, 7 to 9. However, due to the strong connection to

597/803 electrode, the flexibility of the polymer membrane has been lost. Thus, it is difficult to place the samples on a roll and fold the samples. The samples have little handling properties and do not resist practical use.

[002309] In addition, in Comparative Examples 10 and 11, electrolytic performance has deteriorated significantly. Conceivably, the voltage increased notably because the flow of phonons was inhibited by the fact that the electrode was embedded in the ion exchange membrane. Regarding the reason for the decrease in current efficiency and the degradation of the concentration of common salt in caustic soda, possible factors included high current efficiency, occurrence of irregular thickness of the carboxylic acid layer due to the electrode being embedded in the carboxylic acid layer with an effect of presenting ion selectivity, and penetration of the embedded electrode in a portion of the carboxylic acid layer.

[002310] Additionally, in Comparative Examples 10 and 11, in the event that a problem occurred in the membrane or electrode and replacement was necessary, it was not possible to replace one of the membrane and electrode due to the strong connection, which led to a cost bigger.

[002311] In Comparative Example 12, the electrolytic performance deteriorated significantly. Conceivably, the voltage has increased markedly because a product has accumulated at the interface between the membrane and the electrode.

[002312] In Comparative Examples 13 to 15, both forces applied per unit mass-unit area (1) and (2) were small (equal to or less than the lower limit of measurement) and thus the adhesion to membrane was weak. Thus, with a large size of electrolyzer (for example, 1.5 m long and 3 m wide), the membrane, which is a polymer membrane, can inevitably be loosened during handling. At that moment, the electrode comes loose and, thus, the samples do not resist practical use.

597/803 electrode, the flexibility of the polymer membrane has been lost. Thus, it is difficult to place the samples on a roll and fold the samples. The samples have little handling properties and do not resist practical use.

[002309] In addition, in Comparative Examples 10 and 11, electrolytic performance has deteriorated significantly. Conceivably, the voltage increased notably because the flow of phonons was inhibited by the fact that the electrode was embedded in the ion exchange membrane. Regarding the reason for the decrease in current efficiency and the degradation of the concentration of common salt in caustic soda, possible factors included high current efficiency, occurrence of irregular thickness of the carboxylic acid layer due to the electrode being embedded in the carboxylic acid layer with an effect of presenting ion selectivity, and penetration of the embedded electrode in a portion of the carboxylic acid layer.

[002310] Additionally, in Comparative Examples 10 and 11, in the event that a problem occurred in the membrane or electrode and replacement was necessary, it was not possible to replace one of the membrane and electrode due to the strong connection, which led to a cost bigger.

[002311] In Comparative Example 12, the electrolytic performance deteriorated significantly. Conceivably, the voltage has increased markedly because a product has accumulated at the interface between the membrane and the electrode.

[002312] In Comparative Examples 13 to 15, both forces applied per unit mass-unit area (1) and (2) were small (equal to or less than the lower limit of measurement) and thus the adhesion to membrane was weak. Thus, with a large size of electrolyzer (for example, 1.5 m long and 3 m wide), the membrane, which is a polymer membrane, can inevitably be loosened during handling. At that moment, the electrode comes loose and, thus, the samples do not resist practical use.

598/803

[002313] In the present modality, the membrane and the electrode are in close contact with each other on each surface with a moderate force and, thus, there are no problems such as the electrode exit during manipulation. The flow of phonons in the membrane is not inhibited, and thus, a good electrolytic performance is presented. <Verification of the second modality>

[002314] As will be described below, Experimental Examples according to the second modality (in the section <Verification of the second modality> below, simply called “Examples”) and Experimental Examples not according to the second modality (in the section <Verification of the second modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 31 to 42, as appropriate. [Valuation method] (1) Opening reason

[002315] An electrode was cut to a size of 130 mm x 100 mm. A digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale of 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the electrode thickness (gauge thickness) to calculate the volume. Subsequently, an electronic scale was used to measure the mass. From the specific gravity of each metal (specific gravity of nickel = 8.908 glem ?, specific gravity of titanium = 4.506 g / emi), the opening ratio or vacuum ratio was calculated. Opening ratio (Vacuum ratio) (%) = (1 - (electrode mass) / (electrode volume x specific gravity of the nickel)) x 100 (2) Mass per unit area (mg / cm?)

[002316] An electrode was cut to a size of 130 mm x 100

598/803

[002313] In the present modality, the membrane and the electrode are in close contact with each other on each surface with a moderate force and, thus, there are no problems such as the electrode exit during manipulation. The flow of phonons in the membrane is not inhibited, and thus, a good electrolytic performance is presented. <Verification of the second modality>

[002314] As will be described below, Experimental Examples according to the second modality (in the section <Verification of the second modality> below, simply called “Examples”) and Experimental Examples not according to the second modality (in the section <Verification of the second modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 31 to 42, as appropriate. [Valuation method] (1) Opening reason

[002315] An electrode was cut to a size of 130 mm x 100 mm. A digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale of 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the electrode thickness (gauge thickness) to calculate the volume. Subsequently, an electronic scale was used to measure the mass. From the specific gravity of each metal (specific gravity of nickel = 8.908 glem ?, specific gravity of titanium = 4.506 g / emi), the opening ratio or vacuum ratio was calculated. Opening ratio (Vacuum ratio) (%) = (1 - (electrode mass) / (electrode volume x specific gravity of the nickel)) x 100 (2) Mass per unit area (mg / cm?)

[002316] An electrode was cut to a size of 130 mm x 100

599/803 mm, and the mass was measured by an electronic scale. The value was divided by the area (130 mm x 100 mm) to calculate the mass per unit area. (3) Force applied per unit mass-unit area (1) (adhesive force) (N / mg: cm?)) [Method (i)]

[002317] A tensile and compression test machine was used for measurement (Imada-SS Corporation, main test machine: SDT-52NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[002318] A 200 mm square nickel plate with a thickness of 1.2 mm was subjected to etching with grain size 320 alumina. The arithmetic mean roughness of the surface (Ra) of the nickel plate after treatment by pickling was 0.7 µm. To measure the surface roughness, an instrument for measuring surface roughness of the SJ-310 type probe (Mitutoyo Corporation) was used. A measurement sample was placed on the surface plate parallel to the soil surface to measure the average arithmetic roughness Ra under measurement conditions as described below. The measurement was repeated 6 times and the average value was listed.

<Probe shape> conical tapering angle = 60º, tip radius = 2 um, static measuring force = 0.75 mN <Roughness pattern> JIS2001 <Evaluation curve> R <Filter> GAUSS <Ac cut value> 0.8 mm <As cut value> 2.5 um <Number of sections> 5 <Pre-run, post-run> available

[002319] This nickel plate was fixed vertically on the bottom shim

599/803 mm, and the mass was measured by an electronic scale. The value was divided by the area (130 mm x 100 mm) to calculate the mass per unit area. (3) Force applied per unit mass-unit area (1) (adhesive force) (N / mg: cm?)) [Method (i)]

[002317] A tensile and compression test machine was used for measurement (Imada-SS Corporation, main test machine: SDT-52NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[002318] A 200 mm square nickel plate with a thickness of 1.2 mm was subjected to etching with grain size 320 alumina. The arithmetic mean roughness of the surface (Ra) of the nickel plate after treatment by pickling was 0.7 µm. To measure the surface roughness, an instrument for measuring surface roughness of the SJ-310 type probe (Mitutoyo Corporation) was used. A measurement sample was placed on the surface plate parallel to the soil surface to measure the average arithmetic roughness Ra under measurement conditions as described below. The measurement was repeated 6 times and the average value was listed.

<Probe shape> conical tapering angle = 60º, tip radius = 2 um, static measuring force = 0.75 mN <Roughness pattern> JIS2001 <Evaluation curve> R <Filter> GAUSS <Ac cut value> 0.8 mm <As cut value> 2.5 um <Number of sections> 5 <Pre-run, post-run> available

[002319] This nickel plate was fixed vertically on the bottom shim

600/803 of the tensile and compression testing machine.

[002320] Like the membrane, an ion exchange membrane À below was used.

[002321] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarns) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[002322] Next, a dry resin A which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a B resin of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.03 mg equivalent / g.

[002323] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[002324] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2

600/803 of the tensile and compression testing machine.

[002320] Like the membrane, an ion exchange membrane À below was used.

[002321] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarns) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[002322] Next, a dry resin A which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a B resin of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.03 mg equivalent / g.

[002323] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[002324] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2

601/803 minutes, and then the release paper was removed to obtain a composite membrane.

[002325] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[002326] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of the acid type B resin resin and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the composite membrane surfaces to obtain an ion exchange membrane A. At the zirconium oxide coating density measured by X-ray fluorescence measurement was 0.5 mg / in ?. The average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[002327] The ion exchange membrane (membrane) obtained above was immersed in pure water for 12 hours or more and then used for the test. The membrane was placed in contact with the nickel plate above sufficiently moistened with pure water and allowed to adhere to the plate by the water tension. At that time, the nickel plate and the ion exchange membrane were placed in order to align their upper ends.

[002328] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The ion exchange membrane A was cut into a 170 mm square. One side of the electrode was

601/803 minutes, and then the release paper was removed to obtain a composite membrane.

[002325] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[002326] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of the acid type B resin resin and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the composite membrane surfaces to obtain an ion exchange membrane A. At the zirconium oxide coating density measured by X-ray fluorescence measurement was 0.5 mg / in ?. The average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[002327] The ion exchange membrane (membrane) obtained above was immersed in pure water for 12 hours or more and then used for the test. The membrane was placed in contact with the nickel plate above sufficiently moistened with pure water and allowed to adhere to the plate by the water tension. At that time, the nickel plate and the ion exchange membrane were placed in order to align their upper ends.

[002328] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The ion exchange membrane A was cut into a 170 mm square. One side of the electrode was

602/803 sandwiched by two stainless steel plates (thickness: 1 mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[002329] The upper shim of the traction and compression testing machine was lowered, and the electrode sample for electrolysis was allowed to adhere to the surface of the ion exchange membrane by the surface tension of pure water. The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and ion exchange membrane entirely in order to sufficiently moisten the membrane and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess pure water. The roll was laminated only once.

[002330] The electrode was raised at a rate of 10 mm / minute to start the measurement of charge, and the charge when the size of the overlapped portion of the electrode and the membrane reached 130 mm in width and 100 mm in length was recorded. This measurement was repeated three times and the value

602/803 sandwiched by two stainless steel plates (thickness: 1 mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[002329] The upper shim of the traction and compression testing machine was lowered, and the electrode sample for electrolysis was allowed to adhere to the surface of the ion exchange membrane by the surface tension of pure water. The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and ion exchange membrane entirely in order to sufficiently moisten the membrane and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess pure water. The roll was laminated only once.

[002330] The electrode was raised at a rate of 10 mm / minute to start the measurement of charge, and the charge when the size of the overlapped portion of the electrode and the membrane reached 130 mm in width and 100 mm in length was recorded. This measurement was repeated three times and the value

Average 603/803 was calculated.

[002331] This average value was divided by the area of the overlapping portion of the electrode and the ion exchange membrane and the mass of the electrode of the portion overlapping the ion exchange membrane to calculate the force applied per unit mass-unit area (1) . The electrode mass of the portion superimposed on the ion exchange membrane was determined through proportional calculation from the value obtained in (2) Mass per unit area (mg / cm?) Described above.

[002332] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[002333] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to the ion exchange membrane that adhered to a nickel plate fixed vertically through the surface tension.

[002334] A schematic view of a method for evaluating the applied force (1) is shown in Figure 31.

[002335] The lower limit of measurement of the tensile testing machine was 0.01 (N). (4) Force applied per unit mass-unit area (2) (adhesive force) (N / mg: cm?)) [Method (ii)]

[002336] A tensile and compression test machine was used for measurement (Imada-SS Corporation, main testing machine: SDT-52NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[002337] A nickel plate identical to that of Method (1) was fixed vertically to the lower shim of the tensile and compression testing machine.

[002338] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The exchange membrane

Average 603/803 was calculated.

[002331] This average value was divided by the area of the overlapping portion of the electrode and the ion exchange membrane and the mass of the electrode of the portion overlapping the ion exchange membrane to calculate the force applied per unit mass-unit area (1) . The electrode mass of the portion superimposed on the ion exchange membrane was determined through proportional calculation from the value obtained in (2) Mass per unit area (mg / cm?) Described above.

[002332] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[002333] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to the ion exchange membrane that adhered to a nickel plate fixed vertically through the surface tension.

[002334] A schematic view of a method for evaluating the applied force (1) is shown in Figure 31.

[002335] The lower limit of measurement of the tensile testing machine was 0.01 (N). (4) Force applied per unit mass-unit area (2) (adhesive force) (N / mg: cm?)) [Method (ii)]

[002336] A tensile and compression test machine was used for measurement (Imada-SS Corporation, main testing machine: SDT-52NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[002337] A nickel plate identical to that of Method (1) was fixed vertically to the lower shim of the tensile and compression testing machine.

[002338] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The exchange membrane

604/803 ionic A was cut into a 170 mm square. One side of the electrode was sandwiched by two stainless steel plates (thickness: | mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[002339] The upper shim of the tensile and compression testing machine was lowered, and the electrode sample for electrolysis was allowed to adhere to the surface of the nickel plate through the surface tension of a solution. The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and the nickel plate entirely in order to sufficiently moisten the nickel plate and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess solution. The roll was laminated only once.

[002340] The electrode was raised at a rate of 10 mm / minute to start the load measurement, and the load when the size of the overlapping portion of the electrode and the nickel plate in the longitudinal direction reached 100 mm was

604/803 ionic A was cut into a 170 mm square. One side of the electrode was sandwiched by two stainless steel plates (thickness: | mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[002339] The upper shim of the tensile and compression testing machine was lowered, and the electrode sample for electrolysis was allowed to adhere to the surface of the nickel plate through the surface tension of a solution. The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and the nickel plate entirely in order to sufficiently moisten the nickel plate and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess solution. The roll was laminated only once.

[002340] The electrode was raised at a rate of 10 mm / minute to start the load measurement, and the load when the size of the overlapping portion of the electrode and the nickel plate in the longitudinal direction reached 100 mm was

605/803 registered. This measurement was repeated three times and the average value was calculated.

[002341] This average value was divided by the area of the overlapping portion of the electrode and the nickel plate and the mass of the electrode of the portion overlapping the nickel plate to calculate the force applied per unit mass-unit area (2). The electrode mass of the portion superimposed on the membrane was determined through proportional calculation from the value obtained in (2) Mass per unit area (mg / cm?) Described above.

[002342] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[002343] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to a nickel plate fixed vertically through the surface tension.

[002344] The lower limit of measurement of the tensile testing machine was 0.01 (N). (5) Method for assessing the winding around the 280 mm diameter column (1) (%) (Membrane and column)

[002345] The evaluation method (1) was conducted by the following procedure.

[002346] The ion exchange membrane A (membrane) produced in [Method (1)] was cut into a 170 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In Comparative Examples | and 2, the electrode was integrated with the ion exchange membrane by thermal pressing, and thus an integrated part of an ion exchange membrane and an electrode (130 mm square electrode) was provided. After the ion exchange membrane was sufficiently immersed in pure water, the membrane was placed on the curved surface of a plastic (polyethylene) tube with an outer diameter of 280

605/803 registered. This measurement was repeated three times and the average value was calculated.

[002341] This average value was divided by the area of the overlapping portion of the electrode and the nickel plate and the mass of the electrode of the portion overlapping the nickel plate to calculate the force applied per unit mass-unit area (2). The electrode mass of the portion superimposed on the membrane was determined through proportional calculation from the value obtained in (2) Mass per unit area (mg / cm?) Described above.

[002342] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[002343] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to a nickel plate fixed vertically through the surface tension.

[002344] The lower limit of measurement of the tensile testing machine was 0.01 (N). (5) Method for assessing the winding around the 280 mm diameter column (1) (%) (Membrane and column)

[002345] The evaluation method (1) was conducted by the following procedure.

[002346] The ion exchange membrane A (membrane) produced in [Method (1)] was cut into a 170 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In Comparative Examples | and 2, the electrode was integrated with the ion exchange membrane by thermal pressing, and thus an integrated part of an ion exchange membrane and an electrode (130 mm square electrode) was provided. After the ion exchange membrane was sufficiently immersed in pure water, the membrane was placed on the curved surface of a plastic (polyethylene) tube with an outer diameter of 280

606/803 mm. Subsequently, the excess solution was removed with a roller formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (external diameter: 38 mm). The roll was laminated over the ion exchange membrane from left to right from the schematic view shown in Figure 32. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the plastic tube electrode with an external diameter of 280 mm was measured. (6) Method for evaluating the winding around the 280 mm diameter column (2) (%) (Membrane and electrode)

[002347] The evaluation method (2) was conducted by the following procedure.

[002348] The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 280 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was laminated from left to right in the schematic view shown in Figure 33 with light pressure on the electrode to remove excess solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured.

606/803 mm. Subsequently, the excess solution was removed with a roller formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (external diameter: 38 mm). The roll was laminated over the ion exchange membrane from left to right from the schematic view shown in Figure 32. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the plastic tube electrode with an external diameter of 280 mm was measured. (6) Method for evaluating the winding around the 280 mm diameter column (2) (%) (Membrane and electrode)

[002347] The evaluation method (2) was conducted by the following procedure.

[002348] The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 280 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was laminated from left to right in the schematic view shown in Figure 33 with light pressure on the electrode to remove excess solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured.

607/803 (7) Method for assessing the winding around the 145 mm diameter column (3) (%) (Membrane and electrode)

[002349] The evaluation method (3) was conducted by the following procedure.

[002350] The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 145 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was laminated from left to right in the schematic view shown in Figure 34 with light pressure on the electrode to remove excess solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured. (8) Handling property (response assessment)

[002351] (A) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: aqueous sodium bicarbonate solution, aqueous 0.1 N NaOH solution and pure water, then laminated and placed immobile on a Teflon plate. The gap between the anode cell and the cathode cell

607/803 (7) Method for assessing the winding around the 145 mm diameter column (3) (%) (Membrane and electrode)

[002349] The evaluation method (3) was conducted by the following procedure.

[002350] The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 145 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was laminated from left to right in the schematic view shown in Figure 34 with light pressure on the electrode to remove excess solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured. (8) Handling property (response assessment)

[002351] (A) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: aqueous sodium bicarbonate solution, aqueous 0.1 N NaOH solution and pure water, then laminated and placed immobile on a Teflon plate. The gap between the anode cell and the cathode cell

608/803 used in electrolytic evaluation was set at about 3 cm. The laminate placed immobile was lifted and an insertion and retention operation of the laminate was carried out between them. This operation was performed while the electrode was checked for displacement and fall.

[002352] (B) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: an aqueous solution of sodium bicarbonate, an aqueous solution of NaOH 0.1 N and pure water, then laminated and placed immobile on a Teflon plate . The two adjacent corners of the membrane portion of the laminate were held by hands to lift the laminate so that it was vertical. The two corners held by the hands were moved from this state to be close to each other, so that the membrane was designed or embedded. This movement was repeated again to check the conformability of the electrode to the membrane. The results were evaluated on a four-level scale from 1 to 4, based on the following indices: 1: good manipulation property 2: able to be manipulated 3: difficult to manipulate 4: substantially unable to be manipulated

[002353] Here, the sample from Comparative Example 2-5, provided in a size equivalent to that of a large electrolytic cell including an electrode in a size of 1.3 mx 2.5 m and an ion exchange membrane in a size of 1 , 5 mx 2.8 m, was subjected to manipulation. The result of the evaluation of Comparative Example 5 (“3” as described below) was used as an index to assess the difference between the evaluation of (A) and (B) above

608/803 used in electrolytic evaluation was set at about 3 cm. The laminate placed immobile was lifted and an insertion and retention operation of the laminate was carried out between them. This operation was performed while the electrode was checked for displacement and fall.

[002352] (B) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: an aqueous solution of sodium bicarbonate, an aqueous solution of NaOH 0.1 N and pure water, then laminated and placed immobile on a Teflon plate . The two adjacent corners of the membrane portion of the laminate were held by hands to lift the laminate so that it was vertical. The two corners held by the hands were moved from this state to be close to each other, so that the membrane was designed or embedded. This movement was repeated again to check the conformability of the electrode to the membrane. The results were evaluated on a four-level scale from 1 to 4, based on the following indices: 1: good manipulation property 2: able to be manipulated 3: difficult to manipulate 4: substantially unable to be manipulated

[002353] Here, the sample from Comparative Example 2-5, provided in a size equivalent to that of a large electrolytic cell including an electrode in a size of 1.3 mx 2.5 m and an ion exchange membrane in a size of 1 , 5 mx 2.8 m, was subjected to manipulation. The result of the evaluation of Comparative Example 5 (“3” as described below) was used as an index to assess the difference between the evaluation of (A) and (B) above

609/803 and the largest. That is, in the case where the result of the evaluation of a small laminate was "1" or "2", it was considered that there was no problem in the handling property even if the laminate was provided in a larger size. (9) Electrolytic evaluation (voltage (V), current efficiency (%), common saline concentration in caustic soda (ppm, on the basis of 50%))

[002354] Electrolytic performance was assessed by the following electrolytic experiment.

[002355] A titanium anode cell with an anodic chamber in which an anode (anode cell) was provided and a cathode cell with a nickel cathode chamber in which a cathode (cathode cell) was provided were arranged opposite. A pair of gaskets were arranged between the cells, and a laminate (an I-exchange membrane laminate and an electrolysis electrode) was sandwiched between the gaskets. Then, the anodic cell, gasket, laminate, gasket and cathode were placed in close contact to obtain an electrolytic cell, and an electrolyzer including the cell was provided.

[002356] The anode was produced by applying a mixed solution of ruthenium chloride, iridium chloride and titanium tetrachloride on a titanium substrate subjected to pickling and acid attack treatment as a pretreatment, followed by drying and cooking. The anode was fixed to the anode chamber by welding. As a cathode, one described in each of the Examples and Comparative Examples was used. As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. Nickel mesh formed by simple weaving nickel wire with a diameter of 150 µm in a size 40 mesh was placed on top and a rope made of Teflon (R)

609/803 and the largest. That is, in the case where the result of the evaluation of a small laminate was "1" or "2", it was considered that there was no problem in the handling property even if the laminate was provided in a larger size. (9) Electrolytic evaluation (voltage (V), current efficiency (%), common saline concentration in caustic soda (ppm, on the basis of 50%))

[002354] Electrolytic performance was assessed by the following electrolytic experiment.

[002355] A titanium anode cell with an anode chamber in which an anode (anode cell) was provided and a cathode cell with a nickel cathode chamber in which a cathode (cathode cell) was provided were arranged opposite. A pair of gaskets were arranged between the cells, and a laminate (an I-exchange membrane laminate and an electrolysis electrode) was sandwiched between the gaskets. Then, the anodic cell, gasket, laminate, gasket and cathode were placed in close contact to obtain an electrolytic cell, and an electrolyzer including the cell was provided.

[002356] The anode was produced by applying a mixed solution of ruthenium chloride, iridium chloride and titanium tetrachloride on a titanium substrate subjected to pickling and acid attack treatment as a pretreatment, followed by drying and cooking. The anode was fixed to the anode chamber by welding. As a cathode, one described in each of the Examples and Comparative Examples was used. As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. Nickel mesh formed by simple weaving nickel wire with a diameter of 150 µm in a size 40 mesh was placed on top and a rope made of Teflon (R)

610/803 was used to fix the four corners of the Ni mesh to the collector. This Ni mesh was used as a supply conductor. This electrolytic cell has a zero interstice structure using the repulsive force of the mattress like the elastic metal body. Like gaskets, ethylene-propylene-diene rubber (EPDM) gaskets were used. As a membrane, the ion exchange membrane A (160 mm square) produced in [Method (i)] was used.

[002357] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and in the cathodic chamber was adjusted to allow the temperature in each electrolytic cell to reach 90ºC. Was common salt electrolysis performed at a current density of 6 kA / m? to measure voltage, current efficiency and common salt concentration in caustic soda. The current efficiency here is the ratio of the amount of caustic soda produced to the past stream, and when impurity fons and hydroxide fons instead of sodium ions move across the ion exchange membrane due to the passed current, the current efficiency decreases. The current efficiency was obtained by dividing the number of moles of caustic soda produced for a certain time by the number of moles of electrons in the current that passed during that time. The number of moles of caustic soda was obtained by recovering the caustic soda produced by electrolysis in a plastic container and measuring its mass. As the concentration of common salt in caustic soda, a value obtained by converting the concentration of caustic soda to the base of 50% was shown.

[002358] The specification of the electrode and the supply conductor used in each of the Examples and Comparative Examples is shown in Table 3. (11) Measurement of the thickness of the catalytic layer, substrate for electrode for

610/803 was used to fix the four corners of the Ni mesh to the collector. This Ni mesh was used as a supply conductor. This electrolytic cell has a zero interstice structure using the repulsive force of the mattress like the elastic metal body. Like gaskets, ethylene-propylene-diene rubber (EPDM) gaskets were used. As a membrane, the ion exchange membrane A (160 mm square) produced in [Method (i)] was used.

[002357] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and in the cathodic chamber was adjusted to allow the temperature in each electrolytic cell to reach 90ºC. Was common salt electrolysis performed at a current density of 6 kA / m? to measure voltage, current efficiency and common salt concentration in caustic soda. The current efficiency here is the ratio of the amount of caustic soda produced to the past stream, and when impurity fons and hydroxide fons instead of sodium ions move across the ion exchange membrane due to the passed current, the current efficiency decreases. The current efficiency was obtained by dividing the number of moles of caustic soda produced for a certain time by the number of moles of electrons in the current that passed during that time. The number of moles of caustic soda was obtained by recovering the caustic soda produced by electrolysis in a plastic container and measuring its mass. As the concentration of common salt in caustic soda, a value obtained by converting the concentration of caustic soda to the base of 50% was shown.

[002358] The specification of the electrode and the supply conductor used in each of the Examples and Comparative Examples is shown in Table 3. (11) Measurement of the thickness of the catalytic layer, substrate for electrode for

611/803 electrolysis and electrode thickness

[002359] For the thickness of the electrode substrate for electrolysis, a digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the substrate thickness for the electrolysis electrode (gauge thickness). For the electrode thickness, a digital thickness gauge was used to calculate an average value of 10 points obtained by measuring uniformly in the plane, in the same way as for the electrode substrate. The value was used as the electrode thickness (gauge thickness). The thickness of the catalytic layer was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness. (12) Test of elastic deformation of the electrode

[002360] The ion exchange membrane À (membrane) and the electrode produced in [Method (i)] were cut, each, in a 110 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. After the ion exchange membrane and the electrode were laminated to produce a laminate under conditions of a temperature: 23 + 2ºC and a relative humidity: 30 + 5%, the laminate was wrapped around a PVC tube with an outside diameter of 632 mm and a length of 20 cm without any interstice, as shown in Figure 35. The laminate was fixed using a polyethylene clamp so that the laminated wrap did not come out of the PVC tube or come loose. The laminate was retained in this state for 6 hours. Subsequently, the cable tie was removed and the laminate was unrolled from the PVC tube. Only the electrode was placed on a surface plate, and the heights L, 1 and L7 of a raised portion of the surface plate were measured to determine an average value. This value was used as the electrode strain index. In other words, a lower value means that it is unlikely that the laminate will

611/803 electrolysis and electrode thickness

[002359] For the thickness of the electrode substrate for electrolysis, a digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the substrate thickness for the electrolysis electrode (gauge thickness). For the electrode thickness, a digital thickness gauge was used to calculate an average value of 10 points obtained by measuring uniformly in the plane, in the same way as for the electrode substrate. The value was used as the electrode thickness (gauge thickness). The thickness of the catalytic layer was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness. (12) Test of elastic deformation of the electrode

[002360] The ion exchange membrane À (membrane) and the electrode produced in [Method (i)] were cut, each, in a 110 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. After the ion exchange membrane and the electrode were laminated to produce a laminate under conditions of a temperature: 23 + 2ºC and a relative humidity: 30 + 5%, the laminate was wrapped around a PVC tube with an outside diameter of 632 mm and a length of 20 cm without any interstice, as shown in Figure 35. The laminate was fixed using a polyethylene clamp so that the laminated wrap did not come out of the PVC tube or come loose. The laminate was retained in this state for 6 hours. Subsequently, the cable tie was removed and the laminate was unrolled from the PVC tube. Only the electrode was placed on a surface plate, and the heights L, 1 and L7 of a raised portion of the surface plate were measured to determine an average value. This value was used as the electrode strain index. In other words, a lower value means that it is unlikely that the laminate will

612/803 deformed.

[002361] When an expanded metal is used, there are two winding directions: the SW direction and the LW direction. In this test, the laminate was rolled in the SW direction.

[002362] The deformed electrodes (electrodes that did not return to their original flat state) were evaluated for smoothness after plastic deformation according to a method shown in Figure 36. That is, a deformed electrode was placed in a membrane sufficiently immersed in water. pure. One end of the electrode was attached, and the other raised end was pressed into the membrane to release a force, and an assessment was made as to whether the deformed electrode matched the membrane. (13) Assessment of membrane damage

[002363] Like the membrane, an ion exchange membrane B below was used.

[002364] As reinforcement core materials, those obtained by twisting 100 denier polytetrafluoroethylene (PTFE) tape threads 900 times / m in a thread form (hereinafter called PTFE threads) were used. As warp sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. As weft sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m were used. First, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric with a thickness of 100 µm.

[002365] Next, a polymer (Al) of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.92 mg equivalent / g, and a polymer (B1) of a dry resin that

612/803 deformed.

[002361] When an expanded metal is used, there are two winding directions: the SW direction and the LW direction. In this test, the laminate was rolled in the SW direction.

[002362] The deformed electrodes (electrodes that did not return to their original flat state) were evaluated for smoothness after plastic deformation according to a method shown in Figure 36. That is, a deformed electrode was placed in a membrane sufficiently immersed in water. pure. One end of the electrode was attached, and the other raised end was pressed into the membrane to release a force, and an assessment was made as to whether the deformed electrode matched the membrane. (13) Assessment of membrane damage

[002363] Like the membrane, an ion exchange membrane B below was used.

[002364] As reinforcement core materials, those obtained by twisting 100 denier polytetrafluoroethylene (PTFE) tape threads 900 times / m in a thread form (hereinafter called PTFE threads) were used. As warp sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. As weft sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m were used. First, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric with a thickness of 100 µm.

[002365] Next, a polymer (Al) of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.92 mg equivalent / g, and a polymer (B1) of a dry resin that

613/803 was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF; SO, F and had an ion exchange capacity of 1.10 mg equivalent / g. Using these polymers (Al) and (B1), a two-layer film X in which the thickness of a polymer layer (Al) was 25 µm and the thickness of a polymer layer (B1) was 89 µm was obtained by a coextrusion matrix method T. As the ion exchange capacity of each polymer, the ion exchange capacity was shown in the case of hydrolysis of the precursors of the ion exchange group of each polymer for conversion into ion exchange groups.

[002366] Separately, a polymer (B2) of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF3SO, F and had an ion exchange capacity of 1 , 10 mg equivalent / g. This polymer was extruded in a single layer to obtain a Y film with a thickness of 20 µm.

[002367] Subsequently, the release paper, film Y, a reinforcement material and film X were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate temperature of 225ºC and a reduced pressure degree of 0.022 MPa for two minutes, and then the release paper was removed to obtain a composite membrane. The resulting composite membrane was immersed in an aqueous solution comprising dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) for one hour for saponification. Then, the membrane was immersed in 0.5SN NaOH for one hour to replace the fons attached to the ion exchange groups with Na and then washed with water. In addition, the membrane was dried at 60ºC.

[002368] Additionally, a polymer (B3) of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF; SO, xF and had an ion exchange capacity of 1.05 mg equivalent / g was hydrolyzed and

613/803 was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF; SO, F and had an ion exchange capacity of 1.10 mg equivalent / g. Using these polymers (Al) and (B1), a two-layer film X in which the thickness of a polymer layer (Al) was 25 µm and the thickness of a polymer layer (B1) was 89 µm was obtained by a coextrusion matrix method T. As the ion exchange capacity of each polymer, the ion exchange capacity was shown in the case of hydrolysis of the precursors of the ion exchange group of each polymer for conversion into ion exchange groups.

[002366] Separately, a polymer (B2) of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF3SO, F and had an ion exchange capacity of 1 , 10 mg equivalent / g. This polymer was extruded in a single layer to obtain a Y film with a thickness of 20 µm.

[002367] Subsequently, the release paper, film Y, a reinforcement material and film X were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate temperature of 225ºC and a reduced pressure degree of 0.022 MPa for two minutes, and then the release paper was removed to obtain a composite membrane. The resulting composite membrane was immersed in an aqueous solution comprising dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) for one hour for saponification. Then, the membrane was immersed in 0.5SN NaOH for one hour to replace the fons attached to the ion exchange groups with Na and then washed with water. In addition, the membrane was dried at 60ºC.

[002368] Additionally, a polymer (B3) of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF; SO, xF and had an ion exchange capacity of 1.05 mg equivalent / g was hydrolyzed and

614/803 then transformed into an acidic type with hydrochloric acid. Zirconium oxide particles with an average particle size of primary particles of 0.02 µm were added to a mixed solution of water and ethanol 50/50 (mass ratio) in which the polymer (B3 ') of this acid type was dissolved in a proportion of 5% by mass so that the mass ratio of the polymer (B3 ') to the zirconium oxide particles was 20/80. Subsequently, the polymer (B3 ') was dispersed in a suspension of the zirconium oxide particles with a ball mill to obtain a suspension.

[002369] This suspension was applied by a spray method on both surfaces of the dry and ion exchange membrane to obtain an ion exchange membrane B with a coating layer containing the polymer (B3 ') and the oxide particles of zirconium. The coating density of zirconium oxide measured by X-ray fluorescence measurement was 0.35 mg / em ?.

[002370] The anode used was the same as for (9) Electrolytic evaluation.

[002371] The cathode used was one described in each of the Examples and Comparative Examples. The collector, mattress and feeding conductor of the cathodic chamber used were the same as in (9) Electrolytic evaluation. That is, a zero interstice structure was provided by the use of Ni mesh as the feed conductor and the repulsive force of the mattress as the elastic metal body. The gaskets used were the same as for (9) Electrolytic evaluation. As a membrane, ion exchange membrane B produced by the method mentioned above was used. That is, an electrolyzer equivalent to that of (9) was provided, except that the laminate of the ion exchange membrane B and the electrolysis electrode were sandwiched between a pair of gaskets.

[002372] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of

614/803 then transformed into an acidic type with hydrochloric acid. Zirconium oxide particles with an average particle size of primary particles of 0.02 µm were added to a mixed solution of water and ethanol 50/50 (mass ratio) in which the polymer (B3 ') of this acid type was dissolved in a proportion of 5% by mass so that the mass ratio of the polymer (B3 ') to the zirconium oxide particles was 20/80. Subsequently, the polymer (B3 ') was dispersed in a suspension of the zirconium oxide particles with a ball mill to obtain a suspension.

[002369] This suspension was applied by a spray method on both surfaces of the dry and ion exchange membrane to obtain an ion exchange membrane B with a coating layer containing the polymer (B3 ') and the oxide particles of zirconium. The coating density of zirconium oxide measured by X-ray fluorescence measurement was 0.35 mg / em ?.

[002370] The anode used was the same as for (9) Electrolytic evaluation.

[002371] The cathode used was one described in each of the Examples and Comparative Examples. The collector, mattress and feeding conductor of the cathodic chamber used were the same as in (9) Electrolytic evaluation. That is, a zero interstice structure was provided by the use of Ni mesh as the feed conductor and the repulsive force of the mattress as the elastic metal body. The gaskets used were the same as for (9) Electrolytic evaluation. As a membrane, ion exchange membrane B produced by the method mentioned above was used. That is, an electrolyzer equivalent to that of (9) was provided, except that the laminate of the ion exchange membrane B and the electrolysis electrode were sandwiched between a pair of gaskets.

[002372] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of

615/803 sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and the cathodic chamber was adjusted so that the temperature in each electrolytic cell reached 70ºC. Common salt electrolysis was carried out at a current density of 8 kKA / m ?. Electrolysis was interrupted 12 hours after the start of electrolysis, and the ion exchange membrane B was removed and observed for its damage condition.

[002373] "0" means no damage. "1 to 3" means that the damage was present and a higher number means a greater degree of damage. (14) Electrode ventilation resistance

[002374] The ventilation resistance of the electrode was measured using a KES-F8 air permeability tester (trade name, KATO TECH CO., LTD.). The unit for the ventilation resistance value is kKPa-s / m. The measurement was repeated 5 times and the average value was listed in Table 4. The measurement was conducted following two conditions. The temperature of the measuring chamber was 24ºC and the relative humidity was 32%. “Measuring condition 1 (ventilation resistance 1) Piston speed: 0.2 cm / s Vent volume: 0.4 cc / in? / S Measuring range: SENSE L (low) Sample size: 50 mm x 50 mm “Measuring condition 2 (ventilation resistance 2) Piston speed: 2 cm / s Ventilation volume: 4 cc / in? / S Measuring range: SENSE M (high) or H (high) Sample size: 50 mm x 50 mm [Example 2-1]

[002375] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 16 µm was provided. A surface of this nickel blade was subjected to a treatment of

615/803 sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and the cathodic chamber was adjusted so that the temperature in each electrolytic cell reached 70ºC. Common salt electrolysis was carried out at a current density of 8 kKA / m ?. Electrolysis was interrupted 12 hours after the start of electrolysis, and the ion exchange membrane B was removed and observed for its damage condition.

[002373] "0" means no damage. "1 to 3" means that the damage was present and a higher number means a greater degree of damage. (14) Electrode ventilation resistance

[002374] The ventilation resistance of the electrode was measured using a KES-F8 air permeability tester (trade name, KATO TECH CO., LTD.). The unit for the ventilation resistance value is kKPa-s / m. The measurement was repeated 5 times and the average value was listed in Table 4. The measurement was conducted following two conditions. The temperature of the measuring chamber was 24ºC and the relative humidity was 32%. “Measuring condition 1 (ventilation resistance 1) Piston speed: 0.2 cm / s Vent volume: 0.4 cc / in? / S Measuring range: SENSE L (low) Sample size: 50 mm x 50 mm “Measuring condition 2 (ventilation resistance 2) Piston speed: 2 cm / s Ventilation volume: 4 cc / in? / S Measuring range: SENSE M (high) or H (high) Sample size: 50 mm x 50 mm [Example 2-1]

[002375] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 16 µm was provided. A surface of this nickel blade was subjected to a treatment of

616/803 roughness by electrolytic nickel plating. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002376] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 49%.

[002377] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002378] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A number of these coating, drying, preliminary cooking and baking operations have been

616/803 roughness by electrolytic nickel plating. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002376] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 49%.

[002377] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002378] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A number of these coating, drying, preliminary cooking and baking operations have been

617/803 repeated until a predetermined amount of coating is obtained. The thickness of the electrode produced in Example 2-1 was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface. The thickness was the total thickness of ruthenium oxide and cerium oxide.

[002379] The results of measuring the adhesive force of the electrode produced by the above method are shown in Table 4. A sufficient adhesive force was observed.

[002380] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002381] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

[002382] The electrode produced by the above method was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was placed in an opposite position in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane A (size: 160 mm x 160 mm), produced in [Method (1)] and balanced with a aqueous solution of 0.1 N NaOH and allowed to adhere to it through the surface tension of the aqueous solution.

[002383] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in

617/803 repeated until a predetermined amount of coating is obtained. The thickness of the electrode produced in Example 2-1 was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface. The thickness was the total thickness of ruthenium oxide and cerium oxide.

[002379] The results of measuring the adhesive force of the electrode produced by the above method are shown in Table 4. A sufficient adhesive force was observed.

[002380] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002381] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

[002382] The electrode produced by the above method was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was placed in an opposite position in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane A (size: 160 mm x 160 mm), produced in [Method (1)] and balanced with a aqueous solution of 0.1 N NaOH and allowed to adhere to it through the surface tension of the aqueous solution.

[002383] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in

618/803 relative to the ground, the electrode did not come loose or was not moved.

[002384] The electrode integrated into the above membrane was sandwiched between the anode cell and the cathode cell in such a way that the surface on which the electrode was affixed was left facing the side of the cathode chamber. In the sectional structure, the collector, mattress, nickel mesh feed conductor, electrode, membrane and anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure.

[002385] The resulting electrode was subjected to electrolytic evaluation. The results are shown in Table 4.

[002386] The electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "o".

[002387] When the amount of coating after electrolysis was measured by X-ray fluorescence analysis (XRF), substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 2-2]

[002388] In Example 2-2, an electrolytic nickel blade with a gauge thickness of 22 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 0.96 µm. The surface roughness measurement was performed under the same conditions

618/803 relative to the ground, the electrode did not come loose or was not moved.

[002384] The electrode integrated into the above membrane was sandwiched between the anode cell and the cathode cell in such a way that the surface on which the electrode was affixed was left facing the side of the cathode chamber. In the sectional structure, the collector, mattress, nickel mesh feed conductor, electrode, membrane and anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure.

[002385] The resulting electrode was subjected to electrolytic evaluation. The results are shown in Table 4.

[002386] The electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "o".

[002387] When the amount of coating after electrolysis was measured by X-ray fluorescence analysis (XRF), substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 2-2]

[002388] In Example 2-2, an electrolytic nickel blade with a gauge thickness of 22 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 0.96 µm. The surface roughness measurement was performed under the same conditions

619/803 of the surface roughness measurement of the nickel plate subjected to pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002389] The thickness of the electrode was 29 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[002390] Sufficient adhesive strength has been observed.

[002391] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002392] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0033 (kPa-s / m) in the condition of measurement 2.

[002393] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". The damage to the membrane was also rated as good: "0".

[002394] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 2-3]

[002395] In Example 2-3, an electrolytic nickel blade with a gauge thickness of 30 µm was used as a substrate for the electrode to

619/803 of the surface roughness measurement of the nickel plate subjected to pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002389] The thickness of the electrode was 29 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[002390] Sufficient adhesive strength has been observed.

[002391] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002392] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0033 (kPa-s / m) in the condition of measurement 2.

[002393] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". The damage to the membrane was also rated as good: "0".

[002394] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 2-3]

[002395] In Example 2-3, an electrolytic nickel blade with a gauge thickness of 30 µm was used as a substrate for the electrode to

620/803 electrolysis of the cathode. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 1.38 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002396] The thickness of the electrode was 38 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface.

[002397] Sufficient adhesive strength has been observed.

[002398] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002399] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002400] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002401] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is

620/803 electrolysis of the cathode. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 1.38 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002396] The thickness of the electrode was 38 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface.

[002397] Sufficient adhesive strength has been observed.

[002398] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002399] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002400] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002401] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is

621/803 small or no coating is present. [Example 2-4]

[002402] In Example 2-4, an electrolytic nickel blade with a gauge thickness of 16 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 75%. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002403] The thickness of the electrode was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002404] Sufficient adhesive strength has been observed.

[002405] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002406] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002407] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002408] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. That

621/803 small or no coating is present. [Example 2-4]

[002402] In Example 2-4, an electrolytic nickel blade with a gauge thickness of 16 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 75%. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002403] The thickness of the electrode was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002404] Sufficient adhesive strength has been observed.

[002405] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002406] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002407] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002408] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. That

622/803 indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 2-5]

[002409] In Example 2-5, an electrolytic nickel blade with a thickness of 20 µm was provided as a substrate for the electrode for cathode electrolysis. Both surfaces of this nickel blade were subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.96 µm. Both surfaces had the same roughness. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 49%. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002410] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm. The coating was also formed on the non-roughened surface.

[002411] Sufficient adhesive strength has been observed.

[002412] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002413] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002414] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. THE

622/803 indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 2-5]

[002409] In Example 2-5, an electrolytic nickel blade with a thickness of 20 µm was provided as a substrate for the electrode for cathode electrolysis. Both surfaces of this nickel blade were subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.96 µm. Both surfaces had the same roughness. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 49%. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002410] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm. The coating was also formed on the non-roughened surface.

[002411] Sufficient adhesive strength has been observed.

[002412] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002413] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002414] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. THE

623/803 manipulation property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002415] Additionally, when the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on both surfaces. In consideration of the comparison with Examples 2-1 to 2-4, this indicates that the other surface not opposed to the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 2-6]

[002416] In Example 2-6, the evaluation was carried out in the same way as in Example 2-1, except that the coating of the substrate for the electrode for electrode cathode was carried out by ion galvanizing, and the results are shown in Table 4 In ion galvanizing, the film formation was carried out using a heating temperature of 200ºC and Ru metal target under an argon / oxygen atmosphere at a film formation pressure of 7 x 10? Pa. The coating formed was ruthenium oxide.

[002417] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002418] Sufficient adhesive strength has been observed.

[002419] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002420] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

[002421] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. Membrane damage

623/803 manipulation property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002415] Additionally, when the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on both surfaces. In consideration of the comparison with Examples 2-1 to 2-4, this indicates that the other surface not opposed to the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 2-6]

[002416] In Example 2-6, the evaluation was carried out in the same way as in Example 2-1, except that the coating of the substrate for the electrode for electrode cathode was carried out by ion galvanizing, and the results are shown in Table 4 In ion galvanizing, the film formation was carried out using a heating temperature of 200ºC and Ru metal target under an argon / oxygen atmosphere at a film formation pressure of 7 x 10? Pa. The coating formed was ruthenium oxide.

[002417] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002418] Sufficient adhesive strength has been observed.

[002419] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002420] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

[002421] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. Membrane damage

624/803 was also rated as good: “0”. [Example 2-7]

[002422] In Example 2-7, the electrode substrate for cathode electrolysis was produced by an electroforming method. The photomask had a shape formed by a vertical and horizontal arrangement of 0.485 mm x 0.485 mm square in a range of 0.15 mm. Exposure, development and electroplating were performed sequentially to obtain a porous nickel film with a gauge thickness of 20 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002423] The thickness of the electrode was 37 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 17 µm.

[002424] Sufficient adhesive strength has been observed.

[002425] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002426] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002427] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-8]

624/803 was also rated as good: “0”. [Example 2-7]

[002422] In Example 2-7, the electrode substrate for cathode electrolysis was produced by an electroforming method. The photomask had a shape formed by a vertical and horizontal arrangement of 0.485 mm x 0.485 mm square in a range of 0.15 mm. Exposure, development and electroplating were performed sequentially to obtain a porous nickel film with a gauge thickness of 20 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002423] The thickness of the electrode was 37 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 17 µm.

[002424] Sufficient adhesive strength has been observed.

[002425] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002426] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002427] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-8]

625/803

[002428] In Example 2-8, the electrode substrate for cathode electrolysis was produced by an electroforming method. The substrate had a gauge thickness of 50 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.73 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002429] The thickness of the electrode was 60 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002430] Sufficient adhesive strength has been observed.

[002431] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002432] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002433] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-9]

[002434] In Example 2-9, a nickel nonwoven fabric with a gauge thickness of 150 µm and a void ratio of 76% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrolyte electrode cathode. The nonwoven fabric had a nickel fiber diameter of about 40 µm and a base weight of 300 g / m2. Except as described above, the evaluation was carried out in the same manner as in Example 2-1, and

625/803

[002428] In Example 2-8, the electrode substrate for cathode electrolysis was produced by an electroforming method. The substrate had a gauge thickness of 50 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.73 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002429] The thickness of the electrode was 60 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002430] Sufficient adhesive strength has been observed.

[002431] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002432] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002433] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-9]

[002434] In Example 2-9, a nickel nonwoven fabric with a gauge thickness of 150 µm and a void ratio of 76% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrolyte electrode cathode. The nonwoven fabric had a nickel fiber diameter of about 40 µm and a base weight of 300 g / m2. Except as described above, the evaluation was carried out in the same manner as in Example 2-1, and

626/803 results are shown in Table 4.

[002435] The thickness of the electrode was 165 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 15 µm.

[002436] Sufficient adhesive strength has been observed.

[002437] When an electrode deformation test was performed, the average value of L, and L, was 29 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002438] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0612 (kPa-s / m) in the condition of measurement 2.

[002439] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 2-10]

[002440] In Example 2-10, a nickel non-woven fabric with a gauge thickness of 200 µm and a void ratio of 72% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrolyte electrode cathode. The non-woven fabric had a nickel fiber diameter of about 40 µm and a base weight of 500 g / m2. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002441] The thickness of the electrode was 215 µm. The layer thickness

626/803 results are shown in Table 4.

[002435] The thickness of the electrode was 165 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 15 µm.

[002436] Sufficient adhesive strength has been observed.

[002437] When an electrode deformation test was performed, the average value of L, and L, was 29 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002438] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0612 (kPa-s / m) in the condition of measurement 2.

[002439] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 2-10]

[002440] In Example 2-10, a nickel non-woven fabric with a gauge thickness of 200 µm and a void ratio of 72% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrolyte electrode cathode. The non-woven fabric had a nickel fiber diameter of about 40 µm and a base weight of 500 g / m2. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002441] The thickness of the electrode was 215 µm. The layer thickness

627/803 catalytic, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 15 µm.

[002442] Sufficient adhesive strength has been observed.

[002443] When an electrode deformation test was performed, the average value of L, and L, was 40 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002444] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0164 (kPa-s / m) in the condition of measurement 2.

[002445] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 2-11]

[002446] In Example 2-11, a foamed nickel with a 200 µm gauge thickness and a 72% void ratio (manufactured by Mitsubishi Materials Corporation) was used as the substrate for the electrode for cathode electrolysis. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table

4.

[002447] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002448] Sufficient adhesive strength has been observed.

627/803 catalytic, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 15 µm.

[002442] Sufficient adhesive strength has been observed.

[002443] When an electrode deformation test was performed, the average value of L, and L, was 40 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002444] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0164 (kPa-s / m) in the condition of measurement 2.

[002445] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 2-11]

[002446] In Example 2-11, a foamed nickel with a 200 µm gauge thickness and a 72% void ratio (manufactured by Mitsubishi Materials Corporation) was used as the substrate for the electrode for cathode electrolysis. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table

4.

[002447] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002448] Sufficient adhesive strength has been observed.

628/803

[002449] When an electrode deformation test was performed, the average value of L, and L, was 17 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002450] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0402 (kPa-s / m) in the condition of measurement 2.

[002451] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 2-12]

[002452] In Example 2-12, a 200 mesh nickel mesh with a line diameter of 50 µm, a gauge thickness of 100 µm and an opening ratio of 37% was used as a substrate for the electrolyte of the electrode. cathode. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 2-12, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The average arithmetic roughness Ra of a piece of wire of the wire mesh was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the treatment by

628/803

[002449] When an electrode deformation test was performed, the average value of L, and L, was 17 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002450] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0402 (kPa-s / m) in the condition of measurement 2.

[002451] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 2-12]

[002452] In Example 2-12, a 200 mesh nickel mesh with a line diameter of 50 µm, a gauge thickness of 100 µm and an opening ratio of 37% was used as a substrate for the electrolyte of the electrode. cathode. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 2-12, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The average arithmetic roughness Ra of a piece of wire of the wire mesh was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the treatment by

629/803 pickling. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002453] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002454] Sufficient adhesive strength has been observed.

[002455] When an electrode deformation test was performed, the average value of L, and L, was 0.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002456] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0154 (kPa-s / m) in the condition of measurement 2.

[002457] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". The damage to the membrane was rated as good: "0". [Example 2-13]

[002458] In Example 2-13, a 150 mesh nickel mesh with a line diameter of 65 µm, a gauge thickness of 130 µm and an opening ratio of 38% was used as a substrate for the electrolyte of the electrode. cathode. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 2-13, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.66 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the

629/803 pickling. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002453] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002454] Sufficient adhesive strength has been observed.

[002455] When an electrode deformation test was performed, the average value of L, and L, was 0.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002456] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0154 (kPa-s / m) in the condition of measurement 2.

[002457] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". The damage to the membrane was rated as good: "0". [Example 2-13]

[002458] In Example 2-13, a 150 mesh nickel mesh with a line diameter of 65 µm, a gauge thickness of 130 µm and an opening ratio of 38% was used as a substrate for the electrolyte of the electrode. cathode. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 2-13, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.66 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the

630/803 nickel plate subjected to pickling treatment. Except as described above, the above assessment was carried out in the same manner as in Example 2- 1, and the results are shown in Table 4.

[002459] The thickness of the electrode was 133 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 3 µm.

[002460] Sufficient adhesive strength has been observed.

[002461] When an electrode deformation test was performed, the average value of L, and L, was 6.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002462] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0124 (kPa-s / m) in the condition of measurement 2.

[002463] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was also rated as good: "0". [Example 2-14]

[002464] In Example 2-14, a substrate identical to that of Example 2-3 (gauge thickness of 30 µm and an opening ratio of 44%) was used as the substrate for the electrode for cathode electrolysis. The electrolytic evaluation was carried out with a structure identical to that of Example 2-1, except that no nickel mesh feed conductor was included. That is, in the sectional structure of the cell, the collector, the mattress, the electrode integrated into the membrane and the anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the mattress serves as the conductor feed. Except as described above, the evaluation was carried out in the same manner as in Example 2-1, and

630/803 nickel plate subjected to pickling treatment. Except as described above, the above assessment was carried out in the same manner as in Example 2- 1, and the results are shown in Table 4.

[002459] The thickness of the electrode was 133 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 3 µm.

[002460] Sufficient adhesive strength has been observed.

[002461] When an electrode deformation test was performed, the average value of L, and L, was 6.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002462] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0124 (kPa-s / m) in the condition of measurement 2.

[002463] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was also rated as good: "0". [Example 2-14]

[002464] In Example 2-14, a substrate identical to that of Example 2-3 (gauge thickness of 30 µm and an opening ratio of 44%) was used as the substrate for the electrode for cathode electrolysis. The electrolytic evaluation was carried out with a structure identical to that of Example 2-1, except that no nickel mesh feed conductor was included. That is, in the sectional structure of the cell, the collector, the mattress, the electrode integrated into the membrane and the anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the mattress serves as the conductor feed. Except as described above, the evaluation was carried out in the same manner as in Example 2-1, and

631/803 results are shown in Table 4.

[002465] Sufficient adhesive strength has been observed.

[002466] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002467] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002468] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-15]

[002469] In Example 2-15, a substrate identical to that of Example 2-3 (gauge thickness of 30 µm and an opening ratio of 44%) was used as substrate for the electrode for cathode electrolysis. The cathode used in Reference Example 1, which was degraded and had an intensified electrolytic voltage, was placed instead of the nickel mesh feed conductor. With the exception of that described above, the electrolyte evaluation was carried out with a structure identical to that of Example 2-1. That is, in the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage (serves as a supply conductor), the electrolyte electrode (cathode), the membrane and the anode are arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure, and the cathode that is degraded and has an intensified electrolytic voltage serves as the supply conductor. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002470] Sufficient adhesive strength has been observed.

631/803 results are shown in Table 4.

[002465] Sufficient adhesive strength has been observed.

[002466] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002467] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002468] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-15]

[002469] In Example 2-15, a substrate identical to that of Example 2-3 (gauge thickness of 30 µm and an opening ratio of 44%) was used as substrate for the electrode for cathode electrolysis. The cathode used in Reference Example 1, which was degraded and had an intensified electrolytic voltage, was placed instead of the nickel mesh feed conductor. With the exception of that described above, the electrolyte evaluation was carried out with a structure identical to that of Example 2-1. That is, in the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage (serves as a supply conductor), the electrolyte electrode (cathode), the membrane and the anode are arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure, and the cathode that is degraded and has an intensified electrolytic voltage serves as the supply conductor. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002470] Sufficient adhesive strength has been observed.

632/803

[002471] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002472] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002473] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-16]

[002474] A titanium blade with a thickness of 20 µm was provided as a substrate for the electrode for electrolysis of the anode. Both surfaces of the titanium sheet were subjected to a roughness treatment. A porous sheet was formed by drilling this titanium sheet with circular holes by drilling. The diameter of the hole was 1 mm, and the opening ratio was 14%. The arithmetic mean roughness Ra of the surface was 0.37 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002475] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anodic coating liquid.

632/803

[002471] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002472] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002473] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-16]

[002474] A titanium blade with a thickness of 20 µm was provided as a substrate for the electrode for electrolysis of the anode. Both surfaces of the titanium sheet were subjected to a roughness treatment. A porous sheet was formed by drilling this titanium sheet with circular holes by drilling. The diameter of the hole was 1 mm, and the opening ratio was 14%. The arithmetic mean roughness Ra of the surface was 0.37 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002475] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anodic coating liquid.

633/803

[002476] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, preliminary cooking and cooking operations were carried out repeatedly, and then cooking at 520ºC was carried out for one hour.

[002477] The electrode produced by the above method was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The cut electrode was allowed to adhere through the surface tension of the aqueous solution to a substantial central position on the side of the sulfonic acid layer of the ion exchange membrane A (size: 160 mm x 160 mm) produced in [Method (1)] and balanced with a 0.1 N aqueous solution of NaOH.

[002478] The cathode was prepared in the following procedure. First, a 40 mesh nickel wire mesh with a line diameter of 150 µm was provided as a substrate. After stripping with alumina as a pretreatment, the wire mesh was immersed in 6 N hydrochloric acid for 5 minutes, washed sufficiently with pure, dry water.

633/803

[002476] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, preliminary cooking and cooking operations were carried out repeatedly, and then cooking at 520ºC was carried out for one hour.

[002477] The electrode produced by the above method was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The cut electrode was allowed to adhere through the surface tension of the aqueous solution to a substantial central position on the side of the sulfonic acid layer of the ion exchange membrane A (size: 160 mm x 160 mm) produced in [Method (1)] and balanced with a 0.1 N aqueous solution of NaOH.

[002478] The cathode was prepared in the following procedure. First, a 40 mesh nickel wire mesh with a line diameter of 150 µm was provided as a substrate. After stripping with alumina as a pretreatment, the wire mesh was immersed in 6 N hydrochloric acid for 5 minutes, washed sufficiently with pure, dry water.

634/803

[002479] Next, a ruthenium chloride solution with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and cerium chloride (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the ruthenium element and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002480] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was performed at 300ºC for 3 minutes and cooking at 550ºC for 10 minutes. Then, cooking was carried out at 550ºC for one hour. A series of these coating, drying, preliminary cooking and cooking operations were repeated.

[002481] As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. The cathode produced by the above method was placed on it, and a rope made of Teflon (R) was used to fix the four corners of the mesh to the collector.

634/803

[002479] Then a solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and cerium chloride (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the ruthenium element and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002480] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was performed at 300ºC for 3 minutes and cooking at 550ºC for 10 minutes. Then, cooking was carried out at 550ºC for one hour. A series of these coating, drying, preliminary cooking and cooking operations were repeated.

[002481] As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. The cathode produced by the above method was placed on it, and a rope made of Teflon (R) was used to fix the four corners of the mesh to the collector.

635/803

[002482] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the anodes, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002483] The anode used in Reference Example 3, which was degraded and had an intensified electrolytic voltage, was attached to the anode cell by welding, and the electrode integrated into the above membrane was placed between the anode cell and the cathode cell so that the surface on which the electrode was attached was left facing the side of the anodic chamber. That is, in the sectional structure of the cell, the collector, the mattress, the cathode, the membrane, the electrolysis electrode (porous titanium sheet anode) and the anode that was degraded and had an intensified electrolytic voltage were arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure. The anode that was degraded and had an intensified electrolytic voltage served as the supply conductor. The porous titanium blade anode and the anode that was degraded and had an intensified electrolytic voltage were only in physical contact with each other and were not fixed to each other by welding.

[002484] The evaluation in this structure was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002485] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 6 µm.

[002486] Sufficient adhesive strength has been observed.

[002487] When an electrode deformation test was performed, the

635/803

[002482] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the anodes, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002483] The anode used in Reference Example 3, which was degraded and had an intensified electrolytic voltage, was attached to the anode cell by welding, and the electrode integrated into the above membrane was placed between the anode cell and the cathode cell so that the surface on which the electrode was attached was left facing the side of the anodic chamber. That is, in the sectional structure of the cell, the collector, the mattress, the cathode, the membrane, the electrolysis electrode (porous titanium sheet anode) and the anode that was degraded and had an intensified electrolytic voltage were arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure. The anode that was degraded and had an intensified electrolytic voltage served as the supply conductor. The porous titanium blade anode and the anode that was degraded and had an intensified electrolytic voltage were only in physical contact with each other and were not fixed to each other by welding.

[002484] The evaluation in this structure was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002485] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 6 µm.

[002486] Sufficient adhesive strength has been observed.

[002487] When an electrode deformation test was performed, the

636/803 mean value of L, and L, was 4 mm. It was found that the electrode had a wide region of elastic deformation.

[002488] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0060 (kPa-s / m) in the condition of measurement 2.

[002489] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-17]

[002490] In Example 2-17, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 30% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.37 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002491] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002492] Sufficient adhesive strength has been observed.

[002493] When an electrode deformation test was performed, the average value of L, and L, was 5 mm. It was found that the electrode had a wide region of elastic deformation.

[002494] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2.

[002495] Additionally, the electrode had low voltage, high

636/803 mean value of L, and L, was 4 mm. It was found that the electrode had a wide region of elastic deformation.

[002488] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0060 (kPa-s / m) in the condition of measurement 2.

[002489] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-17]

[002490] In Example 2-17, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 30% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.37 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002491] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002492] Sufficient adhesive strength has been observed.

[002493] When an electrode deformation test was performed, the average value of L, and L, was 5 mm. It was found that the electrode had a wide region of elastic deformation.

[002494] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2.

[002495] Additionally, the electrode had low voltage, high

637/803 current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-18]

[002496] In Example 2-18, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 42% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.38 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002497] The thickness of the electrode was 32 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 12 µm.

[002498] Sufficient adhesive strength has been observed.

[002499] When an electrode deformation test was performed, the average value of L, and L, was 2.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002500] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0022 (kPa: s / m) in the condition of measurement 2.

[002501] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-19]

[002502] In Example 2-19, a titanium blade with a caliber thickness of 50 µm and an opening ratio of 47% was used as

637/803 current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-18]

[002496] In Example 2-18, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 42% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.38 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002497] The thickness of the electrode was 32 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 12 µm.

[002498] Sufficient adhesive strength has been observed.

[002499] When an electrode deformation test was performed, the average value of L, and L, was 2.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002500] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0022 (kPa: s / m) in the condition of measurement 2.

[002501] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-19]

[002502] In Example 2-19, a titanium blade with a caliber thickness of 50 µm and an opening ratio of 47% was used as

638/803 substrate for the electrode for electrolysis of the anode. The arithmetic mean roughness Ra of the surface was 0.40 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002503] The thickness of the electrode was 69 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 19 µm.

[002504] Sufficient adhesive strength has been observed.

[002505] When an electrode deformation test was performed, the average value of L, and L, was 8 mm. It was found that the electrode had a wide region of elastic deformation.

[002506] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0024 (kPa-s / m) in the condition of measurement 2.

[002507] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-20]

[002508] In Example 2-20, a titanium nonwoven fabric with a gauge thickness of 100 µm, a titanium fiber diameter of one, a base weight of 100 g / m?, And an opening ratio was used 78% as a substrate for the electrode for electrolysis of the anode. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002509] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the substrate for

638/803 substrate for the electrode for electrolysis of the anode. The arithmetic mean roughness Ra of the surface was 0.40 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002503] The thickness of the electrode was 69 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 19 µm.

[002504] Sufficient adhesive strength has been observed.

[002505] When an electrode deformation test was performed, the average value of L, and L, was 8 mm. It was found that the electrode had a wide region of elastic deformation.

[002506] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0024 (kPa-s / m) in the condition of measurement 2.

[002507] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-20]

[002508] In Example 2-20, a titanium nonwoven fabric with a gauge thickness of 100 µm, a titanium fiber diameter of one, a base weight of 100 g / m?, And an opening ratio was used 78% as a substrate for the electrode for electrolysis of the anode. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002509] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the substrate for

639/803 electrode for electrolysis of the electrode thickness, was 14 µm.

[002510] Sufficient adhesive strength has been observed.

[002511] When an electrode deformation test was performed, the average value of L, and L, was 2 mm. It was found that the electrode had a wide region of elastic deformation.

[002512] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0228 (kPa-s / m) in the condition of measurement 2.

[002513] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-21]

[002514] In Example 2-21, a 150 mesh titanium wire mesh with a gauge thickness of 120 µm and a titanium fiber diameter of about 60 µm was used as a substrate for the electrode for electrode the anode. The opening ratio was 42%. A pickling treatment was carried out with grain size alumina number 320. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 2-21, a titanium plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. . The average arithmetic roughness Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002515] The thickness of the electrode was 140 µm. The layer thickness

639/803 electrode for electrolysis of the electrode thickness, was 14 µm.

[002510] Sufficient adhesive strength has been observed.

[002511] When an electrode deformation test was performed, the average value of L, and L, was 2 mm. It was found that the electrode had a wide region of elastic deformation.

[002512] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0228 (kPa-s / m) in the condition of measurement 2.

[002513] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-21]

[002514] In Example 2-21, a 150 mesh titanium wire mesh with a gauge thickness of 120 µm and a titanium fiber diameter of about 60 µm was used as a substrate for the electrode for electrode the anode. The opening ratio was 42%. A pickling treatment was carried out with grain size alumina number 320. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 2-21, a titanium plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. . The average arithmetic roughness Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002515] The thickness of the electrode was 140 µm. The layer thickness

640/803 catalytic, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 20 µm.

[002516] Sufficient adhesive strength has been observed.

[002517] When an electrode deformation test was performed, the average value of L, and L, was 10 mm. It was found that the electrode had a wide region of elastic deformation.

[002518] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0132 (kPa-s / m) in the condition of measurement 2.

[002519] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-22]

[002520] In Example 2-22, an anode was used which was degraded and had an intensified electrolytic voltage in the same way as in Example 2-16 as the anode supply conductor, and a titanium non-woven fabric identical to that of Example 2-20 as an anode. A cathode that was degraded and had an intensified electrolytic voltage was used in the same way as in Example 2-15 as the cathode supply conductor, and a nickel blade electrode identical to that in Example 2-3 was used as the cathode. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified tension, the cathode of the porous nickel blade, the membrane, the anode of the titanium non-woven fabric, and the anode that was degraded and had an intensified electrolytic voltage are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the cathode and anode which is degraded and has an intensified electrolytic voltage serve as the supply conductor. Except for what was described above, the evaluation was carried out in the same way

640/803 catalytic, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 20 µm.

[002516] Sufficient adhesive strength has been observed.

[002517] When an electrode deformation test was performed, the average value of L, and L, was 10 mm. It was found that the electrode had a wide region of elastic deformation.

[002518] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0132 (kPa-s / m) in the condition of measurement 2.

[002519] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 2-22]

[002520] In Example 2-22, an anode was used which was degraded and had an intensified electrolytic voltage in the same way as in Example 2-16 as the anode supply conductor, and a titanium non-woven fabric identical to that of Example 2-20 as an anode. A cathode that was degraded and had an intensified electrolytic voltage was used in the same way as in Example 2-15 as the cathode supply conductor, and a nickel blade electrode identical to that in Example 2-3 was used as the cathode. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified tension, the cathode of the porous nickel blade, the membrane, the anode of the titanium non-woven fabric, and the anode that was degraded and had an intensified electrolytic voltage are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the cathode and anode which is degraded and has an intensified electrolytic voltage serve as the supply conductor. Except for what was described above, the evaluation was carried out in the same way

641/803 in Example 2-1, and the results are shown in Table 4.

[002521] The thickness of the electrode (anode) was 114 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode (anode) thickness, was 14 µm. The thickness of the electrode (cathode) was 38 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the substrate for the electrode from the electrode thickness (cathode), was 8 µm.

[002522] Sufficient adhesive force was observed both on the anode and on the cathode.

[002523] When a deformation test of the electrode (anode) was performed, the average value of L, and L7 was 2 mm. When an electrode deformation test (cathode) was performed, the average value of L, and L, was 0 mm.

[002524] When the ventilation resistance of the electrode (anode) was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0228 (kPa-s / m) in measurement condition 2. When the ventilation resistance of the electrode (cathode) was measured, the ventilation resistance was 0.07 (kPa-s / m) or less in measurement condition 1 and 0.0027 (kKPa-s / m) in measurement condition 2.

[002525] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: “0” at both the anode and the cathode. In Example 2-22, the cathode and anodes were combined by affixing the cathode to one surface of the membrane and the anode to the other surface and subjecting them to membrane damage assessment. [Example 2-23]

[002526] In Example 2-23, a microporous membrane was used

641/803 in Example 2-1, and the results are shown in Table 4.

[002521] The thickness of the electrode (anode) was 114 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode (anode) thickness, was 14 µm. The thickness of the electrode (cathode) was 38 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the substrate for the electrode from the electrode thickness (cathode), was 8 µm.

[002522] Sufficient adhesive force was observed both on the anode and on the cathode.

[002523] When a deformation test of the electrode (anode) was performed, the average value of L, and L7 was 2 mm. When an electrode deformation test (cathode) was performed, the average value of L, and L, was 0 mm.

[002524] When the ventilation resistance of the electrode (anode) was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0228 (kPa-s / m) in measurement condition 2. When the ventilation resistance of the electrode (cathode) was measured, the ventilation resistance was 0.07 (kPa-s / m) or less in measurement condition 1 and 0.0027 (kKPa-s / m) in measurement condition 2.

[002525] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: “0” at both the anode and the cathode. In Example 2-22, the cathode and anodes were combined by affixing the cathode to one surface of the membrane and the anode to the other surface and subjecting them to membrane damage assessment. [Example 2-23]

[002526] In Example 2-23, a microporous membrane was used

642/803 “Zirfon Perl UTP 500” manufactured by Agfa.

[002527] The Zirfon membrane was immersed in pure water for 12 hours or more and used for the test. Except as described above, the above assessment was performed in the same manner as in Example 2-3, and the results are shown in Table 4.

[002528] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002529] Similar to the case where an ion exchange membrane was used as a membrane, sufficient adhesive strength was observed. The microporous membrane was placed in close contact with the electrode through surface tension, and the manipulation property was good: “1”. [Example 2-24]

[002530] A carbon cloth obtained by weaving a carbon fiber with a gauge thickness of 566 µm was provided as a substrate for the electrode for electrolysis of the cathode. A coating liquid for use in forming an electrode catalyst on this carbon cloth was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002531] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088 (trade name), thickness 10 mm) in around a polychloride cylinder

642/803 “Zirfon Perl UTP 500” manufactured by Agfa.

[002527] The Zirfon membrane was immersed in pure water for 12 hours or more and used for the test. Except as described above, the above assessment was performed in the same manner as in Example 2-3, and the results are shown in Table 4.

[002528] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002529] Similar to the case where an ion exchange membrane was used as a membrane, sufficient adhesive strength was observed. The microporous membrane was placed in close contact with the electrode through surface tension, and the manipulation property was good: “1”. [Example 2-24]

[002530] A carbon cloth obtained by weaving a carbon fiber with a gauge thickness of 566 µm was provided as a substrate for the electrode for electrolysis of the cathode. A coating liquid for use in forming an electrode catalyst on this carbon cloth was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002531] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088 (trade name), thickness 10 mm) in around a polychloride cylinder

643/803 vinyl (PVC) was always in contact with the above coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the produced electrode was 570 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 4 µm. The thickness of the catalytic layer was the total thickness of ruthenium oxide and cerium oxide.

[002532] The resulting electrode was subjected to electrolytic evaluation. The results are shown in Table 4.

[002533] When an electrode deformation test was performed, the average value of L, and L> was O mm.

[002534] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.19 (kPa-s / m) in the measurement condition | and 0.176 (kPa-s / m) in measurement condition 2.

[002535] The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate.

[002536] The tension was high, the damage to the membrane was rated “1” and the damage to the membrane was observed. It was conceived that this is due to the fact that the NaOH that was generated in the electrode accumulated at the interface between the electrode and the membrane to increase its concentration, due to the high ventilation resistance of the electrode of Example 2-24.

643/803 vinyl (PVC) was always in contact with the above coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the produced electrode was 570 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 4 µm. The thickness of the catalytic layer was the total thickness of ruthenium oxide and cerium oxide.

[002532] The resulting electrode was subjected to electrolytic evaluation. The results are shown in Table 4.

[002533] When an electrode deformation test was performed, the average value of L, and L> was O mm.

[002534] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.19 (kPa-s / m) in the measurement condition | and 0.176 (kPa-s / m) in measurement condition 2.

[002535] The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate.

[002536] The tension was high, the damage to the membrane was rated “1” and the damage to the membrane was observed. It was conceived that this is due to the fact that the NaOH that was generated in the electrode accumulated at the interface between the electrode and the membrane to increase its concentration, due to the high ventilation resistance of the electrode of Example 2-24.

644/803 [Reference example 1]

[002537] In Reference Example 1, a cathode was used as a cathode in a large electrolyzer for eight years, degraded and with an intensified electrolytic voltage. The above cathode was placed instead of the nickel mesh feed conductor on the cathode chamber mattress, and the ion exchange membrane A produced in [Method (1)] was sandwiched between them. Then, electrolytic evaluation was performed. In Reference Example 1, no electrodes integrated into the membrane were used. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage, the ion exchange membrane A and the anodes were arranged in the order mentioned from the side of the cathode chamber to form a structure of zero interstice.

[002538] As a result of the electrolytic evaluation with this structure, the voltage was 3.04 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) 20 ppm. Consequently, due to the cathode degradation, the voltage was high. [Reference example 2]

[002539] In Reference Example 2, a nickel mesh feed conductor was used as the cathode. In other words, electrolysis was performed on a nickel mesh without a catalyst coating.

[002540] The nickel mesh cathode was placed on the mattress of the cathodic chamber, and the ion exchange membrane A produced in [Method (i)] was sandwiched between them. Then, electrolytic evaluation was performed. In the sectional structure of the electrical cell of Reference Example 2, the collector, mattress, nickel mesh, ion exchange membrane A and anodes were arranged in the order mentioned from the side of the cathode chamber to form an interstitial structure zero.

[002541] As a result of the electrolytic evaluation with this structure, the voltage was 3.38 V, the current efficiency was 97.7%, the concentration of

644/803 [Reference example 1]

[002537] In Reference Example 1, a cathode was used as a cathode in a large electrolyzer for eight years, degraded and with an intensified electrolytic voltage. The above cathode was placed instead of the nickel mesh feed conductor on the cathode chamber mattress, and the ion exchange membrane A produced in [Method (1)] was sandwiched between them. Then, electrolytic evaluation was performed. In Reference Example 1, no electrodes integrated into the membrane were used. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage, the ion exchange membrane A and the anodes were arranged in the order mentioned from the side of the cathode chamber to form a structure of zero interstice.

[002538] As a result of the electrolytic evaluation with this structure, the voltage was 3.04 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) 20 ppm. Consequently, due to the cathode degradation, the voltage was high. [Reference example 2]

[002539] In Reference Example 2, a nickel mesh feed conductor was used as the cathode. In other words, electrolysis was performed on a nickel mesh without a catalyst coating.

[002540] The nickel mesh cathode was placed on the mattress of the cathodic chamber, and the ion exchange membrane A produced in [Method (i)] was sandwiched between them. Then, electrolytic evaluation was performed. In the sectional structure of the electrical cell of Reference Example 2, the collector, mattress, nickel mesh, ion exchange membrane A and anodes were arranged in the order mentioned from the side of the cathode chamber to form an interstitial structure zero.

[002541] As a result of the electrolytic evaluation with this structure, the voltage was 3.38 V, the current efficiency was 97.7%, the concentration of

645/803 common salt in caustic soda (value converted to 50% base) was 24 ppm. Consequently, the tension was high because the cathode catalyst was uncoated. [Reference example 3]

[002542] In Reference Example 3, an anode used as an anode in a large electrolyzer for about eight years was used, degraded and with an intensified electrolytic voltage.

[002543] In the sectional structure of the electrolytic cell of Reference Example 3, the collector, the mattress, the cathode, the ion exchange membrane À produced in [Method (1i)], and the anode that was degraded and had an electrolytic voltage intensified were arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure.

[002544] As a result of the electrolytic evaluation with this structure, the voltage was 3.18 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) of 22 ppm. Consequently, due to degradation of the anode, the voltage was high. [Example 2-25]

[002545] In Example 2-25, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 33% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-25, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.68 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the

645/803 common salt in caustic soda (value converted to 50% base) was 24 ppm. Consequently, the tension was high because the cathode catalyst was uncoated. [Reference example 3]

[002542] In Reference Example 3, an anode used as an anode in a large electrolyzer for about eight years was used, degraded and with an intensified electrolytic voltage.

[002543] In the sectional structure of the electrolytic cell of Reference Example 3, the collector, the mattress, the cathode, the ion exchange membrane À produced in [Method (1i)], and the anode that was degraded and had an electrolytic voltage intensified were arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure.

[002544] As a result of the electrolytic evaluation with this structure, the voltage was 3.18 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) of 22 ppm. Consequently, due to degradation of the anode, the voltage was high. [Example 2-25]

[002545] In Example 2-25, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 33% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-25, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.68 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the

646/803 nickel plate subjected to pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002546] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002547] The mass per unit area was 67.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.05 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was 64%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was 22%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002548] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002549] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Example 2-26]

[002550] In Example 2-26, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 16% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal.

646/803 nickel plate subjected to pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002546] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002547] The mass per unit area was 67.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.05 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was 64%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was 22%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002548] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002549] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Example 2-26]

[002550] In Example 2-26, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 16% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal.

647/803 Thus, in Example 2-26, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the surface. wire mesh. The arithmetic mean roughness Ra of the surface was 0.604 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002551] The thickness of the electrode was 107 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm.

[002552] The mass per unit area was 78.1 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.04 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was 37%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was 25%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002553] When an electrode deformation test was performed, the average value of L, and L> was 18.5 mm.

[002554] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0176 (kPa-s / m) in the condition of measurement 2. [Example 2-27]

647/803 Thus, in Example 2-26, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the surface. wire mesh. The arithmetic mean roughness Ra of the surface was 0.604 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002551] The thickness of the electrode was 107 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm.

[002552] The mass per unit area was 78.1 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.04 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was 37%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was 25%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002553] When an electrode deformation test was performed, the average value of L, and L> was 18.5 mm.

[002554] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0176 (kPa-s / m) in the condition of measurement 2. [Example 2-27]

648/803

[002555] In Example 2-27, a fully rolled expanded nickel metal with a gauge thickness of 100 µm and an opening ratio of 40% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-27, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.70 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The substrate coating for the electrolysis electrode was carried out by ion plating in the same manner as in Example 2-6. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002556] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002557] The force applied per unit mass-unit area (1) was a small value like 0.07 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 80%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 32%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The manipulation property was “3”, which was also

648/803

[002555] In Example 2-27, a fully rolled expanded nickel metal with a gauge thickness of 100 µm and an opening ratio of 40% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-27, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.70 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The substrate coating for the electrolysis electrode was carried out by ion plating in the same manner as in Example 2-6. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002556] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002557] The force applied per unit mass-unit area (1) was a small value like 0.07 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 80%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 32%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The manipulation property was “3”, which was also

649/803 problematic. The membrane damage was rated “0”.

[002558] When an electrode deformation test was performed, the average value of L, and L> was 11 mm.

[002559] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2. [Example 2-28]

[002560] In Example 2-28, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 58% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-28, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002561] The thickness of the electrode was 109 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 9 µm.

[002562] The force applied per unit mass-unit area (1) was a small value such as 0.06 (N / mg: cm?). Thus, the result of the assessment of the winding around the 280 mm diameter column (2) was 69%, and the result of the assessment of the winding around the 145 mm column in

649/803 problematic. The membrane damage was rated “0”.

[002558] When an electrode deformation test was performed, the average value of L, and L> was 11 mm.

[002559] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2. [Example 2-28]

[002560] In Example 2-28, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 58% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-28, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002561] The thickness of the electrode was 109 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 9 µm.

[002562] The force applied per unit mass-unit area (1) was a small value such as 0.06 (N / mg: cm?). Thus, the result of the assessment of the winding around the 280 mm diameter column (2) was 69%, and the result of the assessment of the winding around the 145 mm column in

650/803 diameter (3) was 39%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "3", which was also problematic. The membrane damage was rated “0”.

[002563] When an electrode deformation test was performed, the average value of L, and L> was 11.5 mm.

[002564] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2. [Example 2-29]

[002565] In Example 2-29, a nickel wire mesh with a gauge thickness of 300 µm and an opening ratio of 56% was used as a substrate for the electrode for cathode electrolysis. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 2-29, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. The arithmetic mean roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002566] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the substrate for

650/803 diameter (3) was 39%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "3", which was also problematic. The membrane damage was rated “0”.

[002563] When an electrode deformation test was performed, the average value of L, and L> was 11.5 mm.

[002564] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2. [Example 2-29]

[002565] In Example 2-29, a nickel wire mesh with a gauge thickness of 300 µm and an opening ratio of 56% was used as a substrate for the electrode for cathode electrolysis. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 2-29, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. The arithmetic mean roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 2-1, and the results are shown in Table 4.

[002566] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the substrate for

651/803 electrode for electrolysis of the electrode thickness, was 8 µm.

[002567] The mass per unit area was 49.2 (mg / in?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 88%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 42%. The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. When the large size electrode was actually operated, it was possible to evaluate the handling property as “3”. The membrane damage was rated “0”.

[002568] When an electrode deformation test was performed, the average value of L, and L> was 23 mm.

[002569] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in the condition of measurement 2. [Example 2-30]

[002570] In Example 2-30, a nickel wire mesh with a gauge thickness of 200 µm and an opening ratio of 37% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 2-30, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.65 µm. The measurement of the surface roughness was

651/803 electrode for electrolysis of the electrode thickness, was 8 µm.

[002567] The mass per unit area was 49.2 (mg / in?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 88%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 42%. The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. When the large size electrode was actually operated, it was possible to evaluate the handling property as “3”. The membrane damage was rated “0”.

[002568] When an electrode deformation test was performed, the average value of L, and L> was 23 mm.

[002569] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in the condition of measurement 2. [Example 2-30]

[002570] In Example 2-30, a nickel wire mesh with a gauge thickness of 200 µm and an opening ratio of 37% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 2-30, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.65 µm. The measurement of the surface roughness was

652/803 performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to pickling treatment. With the exception of the one described above, the assessment of electrode electrolysis, the results of the measurement of adhesive strength and adhesiveness were performed in the same manner as in Example 2-1. The results are shown in Table 4.

[002571] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002572] The mass per unit area was 56.45 mg / in ?. Thus, the result of the method of assessing the winding around the 145 mm diameter column (3) was 63%, and the adhesion between the electrode and the membrane was poor. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. The membrane damage was rated “0”.

[002573] When an electrode deformation test was performed, the average value of L, and L> was 19 mm.

[002574] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0096 (kPa-s / m) in the condition of measurement 2. [Example 2-31]

[002575] In Example 2-31, a fully rolled titanium expanded metal with a gauge thickness of 500 µm and an opening ratio of 17% was used as a substrate for the electrode for electrolysis of the anode. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-31, a titanium plate with a thickness of |

652/803 performed under the same conditions as the measurement of the surface roughness of the nickel plate subjected to pickling treatment. With the exception of the one described above, the assessment of electrode electrolysis, the results of the measurement of adhesive strength and adhesiveness were performed in the same manner as in Example 2-1. The results are shown in Table 4.

[002571] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002572] The mass per unit area was 56.45 mg / in ?. Thus, the result of the method of assessing the winding around the 145 mm diameter column (3) was 63%, and the adhesion between the electrode and the membrane was poor. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. The membrane damage was rated “0”.

[002573] When an electrode deformation test was performed, the average value of L, and L> was 19 mm.

[002574] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0096 (kPa-s / m) in the condition of measurement 2. [Example 2-31]

[002575] In Example 2-31, a fully rolled titanium expanded metal with a gauge thickness of 500 µm and an opening ratio of 17% was used as a substrate for the electrode for electrolysis of the anode. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-31, a titanium plate with a thickness of |

653/803 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002576] The thickness of the electrode was 508 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002577] The mass per unit area was 152.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002578] When an electrode deformation test was carried out, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002579] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0072 (kPa-s / m) in the condition of measurement 2. [Example 2-32]

653/803 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002576] The thickness of the electrode was 508 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002577] The mass per unit area was 152.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002578] When an electrode deformation test was carried out, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002579] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0072 (kPa-s / m) in the condition of measurement 2. [Example 2-32]

654/803

[002580] In Example 2-32, a fully rolled titanium expanded metal with a caliber thickness of 800 µm and an opening ratio of 8% was used as a substrate for the electrode for electrolysis of the anode. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-32, a titanium plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.61 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except for what was described above, the above assessment was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002581] The thickness of the electrode was 808 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002582] The mass per unit area was 251.3 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

654/803

[002580] In Example 2-32, a fully rolled titanium expanded metal with a caliber thickness of 800 µm and an opening ratio of 8% was used as a substrate for the electrode for electrolysis of the anode. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-32, a titanium plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.61 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except for what was described above, the above assessment was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002581] The thickness of the electrode was 808 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002582] The mass per unit area was 251.3 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

655/803

[002583] When an electrode deformation test was carried out, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002584] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0172 (kPa-s / m) in the condition of measurement 2. [Example 2-33]

[002585] In Example 2-33, a fully laminated titanium expanded metal with a caliber thickness of 1000 µm and an opening ratio of 46% was used as the substrate for the electrode for anode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-33, a titanium plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.59 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except for what was described above, the above assessment was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002586] The thickness of the electrode was 1011 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 11 µm.

[002587] The mass per unit area was 245.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was less than 5%, and the result

655/803

[002583] When an electrode deformation test was carried out, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002584] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0172 (kPa-s / m) in the condition of measurement 2. [Example 2-33]

[002585] In Example 2-33, a fully laminated titanium expanded metal with a caliber thickness of 1000 µm and an opening ratio of 46% was used as the substrate for the electrode for anode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 2-33, a titanium plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.59 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except for what was described above, the above assessment was performed in the same way as in Example 2-16, and the results are shown in Table 4.

[002586] The thickness of the electrode was 1011 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 11 µm.

[002587] The mass per unit area was 245.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was less than 5%, and the result

656/803 of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5%. The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002588] When a deformation test of the electrode was performed, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002589] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2. [Example 2-34]

[002590] A nickel line with a thickness of 150 µm was provided as a substrate for the electrode for cathode electrolysis. A roughness treatment by this nickel line was carried out. It is difficult to measure the surface roughness of the nickel line. Thus, in Example 2-34, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the nickel line. . A pickling treatment was carried out with grain size alumina number 320. The arithmetic mean roughness Ra was 0.64 µm.

[002591] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and O

656/803 of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5%. The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002588] When a deformation test of the electrode was performed, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002589] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2. [Example 2-34]

[002590] A nickel line with a thickness of 150 µm was provided as a substrate for the electrode for cathode electrolysis. A roughness treatment by this nickel line was carried out. It is difficult to measure the surface roughness of the nickel line. Thus, in Example 2-34, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the nickel line. . A pickling treatment was carried out with grain size alumina number 320. The arithmetic mean roughness Ra was 0.64 µm.

[002591] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and O

657/803 cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002592] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088 (trade name), thickness 10 mm) in around a polyvinyl chloride (PVC) cylinder was always in contact with the above coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the nickel line produced in Example 2-34 was 158 µm.

[002593] The nickel line produced by the above method was cut to a length of 110 mm and a length of 95 mm. As shown in Figure 37, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and the results are shown in Table 4.

[002594] The portion of the electrode where the nickel lines were

657/803 cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002592] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088 (trade name), thickness 10 mm) in around a polyvinyl chloride (PVC) cylinder was always in contact with the above coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the nickel line produced in Example 2-34 was 158 µm.

[002593] The nickel line produced by the above method was cut to a length of 110 mm and a length of 95 mm. As shown in Figure 37, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and the results are shown in Table 4.

[002594] The portion of the electrode where the nickel lines were

658/803 superimposed had the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.7%.

[002595] The mass per unit area of the electrode was 0.5 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002596] When an electrode deformation test was performed, the average value of L, and L> was 15 mm.

[002597] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance value was 0.0002 (kPa-s / m).

[002598] In addition, the structure shown in Figure 38 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.16 V. [Example 2-35]

[002599] In Example 2-35, the electrode produced in Example 2-34 was used. As shown in Figure 39, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and the results are shown in Table 4.

658/803 superimposed had the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.7%.

[002595] The mass per unit area of the electrode was 0.5 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002596] When an electrode deformation test was performed, the average value of L, and L> was 15 mm.

[002597] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance value was 0.0002 (kPa-s / m).

[002598] In addition, the structure shown in Figure 38 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.16 V. [Example 2-35]

[002599] In Example 2-35, the electrode produced in Example 2-34 was used. As shown in Figure 39, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and the results are shown in Table 4.

659/803

[002600] The portion of the electrode on which the nickel lines overlapped was the largest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.4%.

[002601] The mass per unit area of the electrode was 0.9 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002602] When an electrode deformation test was performed, the average value of L, and L> was 16 mm.

[002603] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0004 (kPa-s / m).

[002604] In addition, the structure shown in Figure 40 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Example 2-36]

[002605] In Example 2-36, the electrode produced in Example 2-34 was used. As shown in Figure 41, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and

659/803

[002600] The portion of the electrode on which the nickel lines overlapped was the largest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.4%.

[002601] The mass per unit area of the electrode was 0.9 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002602] When an electrode deformation test was performed, the average value of L, and L> was 16 mm.

[002603] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0004 (kPa-s / m).

[002604] In addition, the structure shown in Figure 40 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Example 2-36]

[002605] In Example 2-36, the electrode produced in Example 2-34 was used. As shown in Figure 41, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with an instant adhesive (Aron Alpha (R), TOAGOSEI CO., LTD.) to produce an electrode. The electrode was evaluated, and

660/803 the results are shown in Table 4.

[002606] The portion of the electrode in which the nickel lines were superimposed was of the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 98.8%.

[002607] The mass per unit area of the electrode was 1.9 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002608] When an electrode deformation test was performed, the average value of L, and L> was 14 mm.

[002609] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0005 (kPa-s / m).

[002610] In addition, the structure shown in Figure 42 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Comparative Example 2-1]

[002611] In Comparative Example 2-1, a thermally compressed assembly was produced by thermal compression of an electrode on a membrane with reference to a prior art document (Examples of Japanese Patent Open to the Public No. 58-48686).

[002612] A fully laminated nickel expanded metal was used

660/803 the results are shown in Table 4.

[002606] The portion of the electrode in which the nickel lines were superimposed was of the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 98.8%.

[002607] The mass per unit area of the electrode was 1.9 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002608] When an electrode deformation test was performed, the average value of L, and L> was 14 mm.

[002609] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0005 (kPa-s / m).

[002610] In addition, the structure shown in Figure 42 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Comparative Example 2-1]

[002611] In Comparative Example 2-1, a thermally compressed assembly was produced by thermal compression of an electrode on a membrane with reference to a prior art document (Examples of Japanese Patent Open to the Public No. 58-48686).

[002612] A fully laminated nickel expanded metal was used

661/803 with a gauge thickness of 100 µm and an opening ratio of 33% as a substrate for the electrode for electrolysis of the cathode to perform electrode coating in the same manner as in Example 2-1. Subsequently, an electrode surface was subjected to an inactivation treatment in the following procedure. Polyimide adhesive tape (Chukoh Chemical Industries, Ltd.) was affixed to an electrode surface. A dispersion of PTFE (Dupont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was applied to the other surface and dried in a muffle at 120ºC for 10 minutes. The polyimide tape was peeled and a sintering treatment was carried out in a muffle at 380ºC for 10 minutes. This operation was repeated twice to inactivate the electrode surface.

[002613] A membrane formed by two layers of a perfluorocarbon polymer whose terminal functional group is "-COOCH; 3" (polymer C) and a perfluorocarbon polymer whose terminal functional group is "-SOzF" (polymer S) was produced . The thickness of polymer layer C was 3 mils and the thickness of polymer layer S was 4 mils. This two-layer membrane was subjected to a saponification treatment to introduce ion exchange groups at the polymer terminals by hydrolysis. The polymer C terminals were hydrolyzed in carboxylic acid groups and the polymer S terminals in sulfo groups. The ion exchange capacity, like the sulfonic acid group, was 1.0 meq / g, and the ion exchange capacity, like the carboxylic acid group, was 0.9 meq / g.

[002614] The surface of the inactivated electrode was arranged in the opposite way and thermally pressed on the surface with carboxylic acid groups such as ion exchange groups to integrate the ion exchange membrane and the electrode. The electrode surface was exposed even after thermal compression, and the electrode passed through no portion of the membrane.

[002615] Subsequently, in order to suppress the affixing of bubbles to be generated during electrolysis to the membrane, a mixture of zirconium oxide and

661/803 with a gauge thickness of 100 µm and an opening ratio of 33% as a substrate for the electrode for electrolysis of the cathode to perform electrode coating in the same manner as in Example 2-1. Subsequently, an electrode surface was subjected to an inactivation treatment in the following procedure. Polyimide adhesive tape (Chukoh Chemical Industries, Ltd.) was affixed to an electrode surface. A dispersion of PTFE (Dupont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was applied to the other surface and dried in a muffle at 120ºC for 10 minutes. The polyimide tape was peeled and a sintering treatment was carried out in a muffle at 380ºC for 10 minutes. This operation was repeated twice to inactivate the electrode surface.

[002613] A membrane formed by two layers of a perfluorocarbon polymer whose terminal functional group is "-COOCH; 3" (polymer C) and a perfluorocarbon polymer whose terminal functional group is "-SOzF" (polymer S) was produced . The thickness of polymer layer C was 3 mils and the thickness of polymer layer S was 4 mils. This two-layer membrane was subjected to a saponification treatment to introduce ion exchange groups at the polymer terminals by hydrolysis. The polymer C terminals were hydrolyzed in carboxylic acid groups and the polymer S terminals in sulfo groups. The ion exchange capacity, like the sulfonic acid group, was 1.0 meq / g, and the ion exchange capacity, like the carboxylic acid group, was 0.9 meq / g.

[002614] The surface of the inactivated electrode was arranged in the opposite way and thermally pressed on the surface with carboxylic acid groups such as ion exchange groups to integrate the ion exchange membrane and the electrode. The electrode surface was exposed even after thermal compression, and the electrode passed through no portion of the membrane.

[002615] Subsequently, in order to suppress the affixing of bubbles to be generated during electrolysis to the membrane, a mixture of zirconium oxide and

662/803 a perfluorocarbon polymer into which sulfo groups were introduced was applied to both surfaces. Thus, the thermally compressed set of Comparative Example 2-1 was produced.

[002616] When the force applied per unit mass-unit area (1) was measured using this thermally compressed assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression. Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.50 (N / mg: in?) Was applied, a portion of the membrane was broken. The thermally compressed assembly of Comparative Example 2-1 had a force applied per unit mass-unit area (1) of at least 1.50 (N / mg: cm?) And was strongly bonded.

[002617] When the winding was evaluated around the 280 mm diameter column (1), the area in contact with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and the membrane were 100% connected to each other, but the membrane was not wound around the column in the first place. The result of the assessment of the winding around the 145 mm diameter column (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The handling property was "3", which was problematic. The membrane damage was rated “0”. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda (value converted to the base of 50%) was increased and the electrolytic performance deteriorated.

[002618] The thickness of the electrode was 114 µm. The layer thickness

662/803 a perfluorocarbon polymer into which sulfo groups were introduced was applied to both surfaces. Thus, the thermally compressed set of Comparative Example 2-1 was produced.

[002616] When the force applied per unit mass-unit area (1) was measured using this thermally compressed assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression. Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.50 (N / mg: in?) Was applied, a portion of the membrane was broken. The thermally compressed assembly of Comparative Example 2-1 had a force applied per unit mass-unit area (1) of at least 1.50 (N / mg: cm?) And was strongly bonded.

[002617] When the winding was evaluated around the 280 mm diameter column (1), the area in contact with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and the membrane were 100% connected to each other, but the membrane was not wound around the column in the first place. The result of the assessment of the winding around the 145 mm diameter column (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The handling property was "3", which was problematic. The membrane damage was rated “0”. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda (value converted to the base of 50%) was increased and the electrolytic performance deteriorated.

[002618] The thickness of the electrode was 114 µm. The layer thickness

663/803 catalytic, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 14 µm.

[002619] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002620] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Comparative Example 2-2]

[002621] In Comparative Example 2-2, a 40 mesh nickel mesh with a line diameter of 150 µm, a gauge thickness of 300 µm and an opening ratio of 58% was used as a substrate for the electrolyte electrode of the cathode. Except for the above, a thermally compressed assembly was produced in the same manner as in Comparative Example 2-1.

[002622] When the force applied per unit mass-unit area (1) was measured using this thermally compressed assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression. Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.60 (N / mg: ecm?) Was applied, a portion of the membrane was broken. The thermally compressed set of Comparative Example 2-2 had a force applied per unit mass-unit area (1) of at least 1.60 (N / mg: cm?) And was strongly bonded.

[002623] When the winding was evaluated around the 280 mm diameter column (1) using this thermally compressed set, the contact area with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and membrane were 100%

663/803 catalytic, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 14 µm.

[002619] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002620] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Comparative Example 2-2]

[002621] In Comparative Example 2-2, a 40 mesh nickel mesh with a line diameter of 150 µm, a gauge thickness of 300 µm and an opening ratio of 58% was used as a substrate for the electrolyte electrode of the cathode. Except for the above, a thermally compressed assembly was produced in the same manner as in Comparative Example 2-1.

[002622] When the force applied per unit mass-unit area (1) was measured using this thermally compressed assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression. Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.60 (N / mg: ecm?) Was applied, a portion of the membrane was broken. The thermally compressed set of Comparative Example 2-2 had a force applied per unit mass-unit area (1) of at least 1.60 (N / mg: cm?) And was strongly bonded.

[002623] When the winding was evaluated around the 280 mm diameter column (1) using this thermally compressed set, the contact area with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and membrane were 100%

664/803 connected to each other, but the membrane was not wrapped around the column in the first place. The result of the evaluation of the winding around the 145 mm column (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The handling property was "3", which was problematic. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda was increased and the electrolytic performance deteriorated.

[002624] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002625] When an electrode deformation test was performed, the average value of L, and L> was 23 mm.

[002626] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in the condition of measurement 2. [Table 3] ubstrat Ema of substrate for ITR Conductor Method mm ih TE PETR fem fe rms | mr fe fe leme | ER fem fm rudders | ER fem fm rudders | AR fem fm rudders | BEING for months. | PTN fame fe lemes | BEING fe fe lee | PERO smoke fre leme | IR fame bre leme |

664/803 connected to each other, but the membrane was not wrapped around the column in the first place. The result of the evaluation of the winding around the 145 mm column (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The handling property was "3", which was problematic. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda was increased and the electrolytic performance deteriorated.

[002624] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002625] When an electrode deformation test was performed, the average value of L, and L> was 23 mm.

[002626] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in the condition of measurement 2. [Table 3] ubstrat Ema of substrate for ITR Conductor Method mm ih TE PETR fem fe rms | mr fe fe leme | ER fem fm rudders | ER fem fm rudders | AR fem fm rudders | BEING for months. | PTN fame fe lemes | BEING fe fe lee | PERO smoke fre leme | IR fame bre leme |

665/803 [example Ni - Foam Pyrolysis Ni Mesh Example 2) Drilling (same as Exemplop; ró1ise 'olchão 14 p-3) Example 2- | Perforation (same as Exemplob ,. ,,. Atodo com) P Pyrolysis "2-3) increase in tension Example 2- | x cas Anode com) Perforation Pyrolysis - 16 increase in tension [example 2- Perforation Pyrolysis Anode with 17 h tension [Example 27 Perforation Pyrolysis Anode with increase in tension lExample 2- | oo: Anode with Perforation Pyrolysis z 19 increase in tension [Example 27 Non-woven fabric irolysis Anode with increase in tension Example 2- Mesh irolysis Anode with | pl in voltage lExample 2-1 ... Combination of Example 2-3 el. anode and NvTi z an irolysis with increase in b2 lExample 2-20.

tension [Example 2-, Perforation Pyrolysis p3 [Example 27 Expanded Pyrolysis Anode with Bl in tension Example 27 lExpanded irolysis Anode with | B2 increase in tension Example 27 lExpanded irolysis Anode with | B3 voltage increase [Comparative example) Expanded Pyrolysis Ni mesh p-1 Comparative example | Pyrolysis Mesh Ni Mesh p-2

665/803 [example Ni - Foam Pyrolysis Ni Mesh Example 2) Drilling (same as Exemplop; ró1ise 'olchão 14 p-3) Example 2- | Perforation (same as Exemplob ,. ,,. Atodo com) P Pyrolysis "2-3) increase in tension Example 2- | x cas Anode com) Perforation Pyrolysis - 16 increase in tension [example 2- Perforation Pyrolysis Anode with 17 h tension [Example 27 Perforation Pyrolysis Anode with increase in tension lExample 2- | oo: Anode with Perforation Pyrolysis z 19 increase in tension [Example 27 Non-woven fabric irolysis Anode with increase in tension Example 2- Mesh irolysis Anode with | pl in voltage lExample 2-1 ... Combination of Example 2-3 el. anode and NvTi z an irolysis with increase in b2 lExample 2-20.

tension [Example 2-, Perforation Pyrolysis p3 [Example 27 Expanded Pyrolysis Anode with Bl in tension Example 27 lExpanded irolysis Anode with | B2 increase in tension Example 27 lExpanded irolysis Anode with | B3 voltage increase [Comparative example) Expanded Pyrolysis Ni mesh p-1 Comparative example | Pyrolysis Mesh Ni Mesh p-2

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X 3% s & 2 s <S Ss ss select elx l el lala Ss Ss / g / 8 ala / & / e SE Sel 8 / 8/8 8 ZE / 8/8 | S 3 3 sy 8/8 Ss S / S Ss Ss es S / S [/ S / S / S / | S / 58/8 | 8 8 a / 8/8/8/8 | S | sa / EsN Sm a / | s / 8 [/ 8/8/8/8 [a / 8, & ê Fa TB TETE EE ETs Z EF IT BFT Eee Te 12 7 2 2 E 8 [8 | E [8 | | 2 | 2 | | | 8 | [8 E [E | êz 3 sm ls ls É ls ls É é é é fas ds ds ds ds ds 5 és 5 ds 8) se | se & 2) 2/8 2/8 2/9 2/0 3/9 2) 2) o 2/42/8 2/0 2/0 2/8 2) o 2 / S 2/8 2/0 23) 0 2) S 2 sa

FREE 8 ET Edf -o FER SSs

NS E ESSZAS els els CESPIESESENERT TEC v Ss e eee. 2 s / a ls sas / | s / | 8/8 | 5 sa als and lt S / S 2/8 Ss 2 yes lele / lela in le le and he already she; = = sl el and sl el Ss select and he and he <= <Ss alswlals selalel alle ala = se 2 RA J / AjS AJ A | RA ABAS 8 sa la ã 8 [8 | s if sle / sl sis ES ES ES 8 8/8 Ss / S / S Salsa la o | eg ESSESES 8 PESPENP Ss âvláv | ê ss 8j / 8/8/8 | 8/8/8 | 8/8 x | 5 to 8 Ee Es8s - - ro Z 3 o E 3 8 za 8 8 8 ss s | s8 / s8 / s | / s8 / s8 / S / s / 8s8s | sjs | s / sjs | s / 8sjs | is: 8 ° É [8º º 2a É 2

E ET ET Ss 2ã8 à PERSERS FER PENSE s els le 4 E 2282 ESSESENSS E 8/23/2 /. 2 / S / 2/3/24/2/8/8/28/23422824 s / s / s / = / S / S / S | sls | IsS / S / S / S / | = | S [/ S / [S | / S BE ES 3rd [8th o BÉ 3 gEB | g8S to 258 | 8F8 a É | You are S and TELS 7E2S slelelz lala lv Ss / «lBelzls sl alz / = | 2/7 843884 TZ 8/4 [S | 2/8 [= | 4/8] 8/8 | S 2/8 | s 3/2 | E2 22382 sisls / s / | sl / s | s | Ss | ss sl! ss s / | s / | s / | s | s | BESAZES = e lalej aj | 4j he s / l she a = [3/34 sm Aa = | SC da = || == re / gs CT Sol o & | Sl loalo | x o Y zl € e ce SS = / zZzZistsvlEe sm | | g / ÉS [5/4/8 / S 3 = * Tx he lv e es Tisme | ls FESRSESEA s | É = el lala lzls | SE ee = so aejlala z 8 Ss "THESE s = o Ss = E ss and sm lelals / ol - ss E z he ge 2 S / a« (SE S / S / 38/38/28 2) 8 ê E 2 2 3 s | = 8 It is slsle | 8 / 8/5 eisls s / s / s êÊ & nv lo | rj el a | Ss | = a | niFla | o | = | es a | o | = | a | xo Ss sl 3 sis Zls [a sl saddle aa | ala Ss SIS & <3 alalala lalala alada lala | dlal act alala «á S sl and the room / a ea s / a / sale a la sa / wing ls a / ale 2 s E & | E] E e] eeae ez elo ee / 2/2 / 2 |) 2 É E s 8/5/8/8/38/8/8 | / 8 / 8S / 8 38/85/8/8/8/5/8 | / 65 |: $ ê T e | e | x | e | e | e | e | e E] | so e | & | 8] e] e ] e] e] The xz Sa S / AS / S / 8 / A / S / BASS S / A / S / S / A 5/8 / ÁA healthy Á 3

X 3% s & 2

8 Ê Z 8 8 8 ê 2 | 8

É É É 3 3 êz sé lsêlçá ss [823/83 z s 8 s 8 S * Re e]. <<z e = = = <Ds z z z 3 3 E 8 8 8 8 8 E Bos 28 g EE Es iss ê

HE o 2 28 E 8 E 28 2 224] o Ss ê 8 8 Es Ss | n / a Le = o = S Z

It's Ped.

E s s to E E | And the 2 ê & FF | = & & es º ã a Z Z 8 <s | eE a E & | ES 8 3 & | S2 88 2 x | E ET RES = bad there FE 3

X 3% s & 2

8 Ê Z 8 8 8 ê 2 | 8

É É É 3 3 êz sé lsêlçá ss [823/83 z s 8 s 8 S * Re e]. <<z e = = = <Ds z z z 3 3 E 8 8 8 8 8 E Bos 28 g EE Es iss ê

HE o 2 28 E 8 E 28 2 224] o Ss ê 8 8 Es Ss | n / a Le = o = S Z

It's Ped.

E s s to E E | And the 2 ê & FF | = & & es º ã a Z Z 8 <s | eE a E & | ES 8 3 & | S2 88 2 x | E ET RES = bad there FE 3

X 3% s & 2

669/803

[002627] In Table 4, all samples were able to stand alone due to surface tension before measuring “force applied per unit mass-unit area (1)” and “force applied per unit mass-unit area” (2) ”(that is, they did not slip). <Verification of the third modality>

[002628] As will be described below, Experimental Examples were provided according to the third modality (in the <Verification of the third modality> section, simply called “Examples”) and Experimental Examples not according to the third modality (in the section <Verification of the third modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 57 to 62, as appropriate. (1) Electrolytic evaluation (voltage (V), current efficiency (%))

[002629] Electrolytic performance was assessed by the following electrolytic experiment.

[002630] A titanium anode cell with an anode chamber in which an anode (anode cell) was provided and a cathode cell with a nickel cathode chamber in which a cathode (cathode cell) was provided were arranged opposite. A pair of gaskets were arranged between the cells, and an ion exchange membrane was sandwiched between the gaskets. Then, the anode cell, the gasket, the ion exchange membrane, the gasket and the cathode were placed in close contact to obtain an electrolytic cell.

[002631] The anode was produced by applying a mixed solution of ruthenium chloride, iridium chloride and titanium tetrachloride on a titanium substrate subjected to pickling and acid attack treatment as a pre-treatment, followed by drying and cooking. The anode was fixed to the anode chamber by welding. As cathode, one described in each of the

669/803

[002627] In Table 4, all samples were able to stand alone due to surface tension before measuring “force applied per unit mass-unit area (1)” and “force applied per unit mass-unit area” (2) ”(that is, they did not slip). <Verification of the third modality>

[002628] As will be described below, Experimental Examples were provided according to the third modality (in the <Verification of the third modality> section, simply called “Examples”) and Experimental Examples not according to the third modality (in the section <Verification of the third modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 57 to 62, as appropriate. (1) Electrolytic evaluation (voltage (V), current efficiency (%))

[002629] Electrolytic performance was assessed by the following electrolytic experiment.

[002630] A titanium anode cell with an anode chamber in which an anode (anode cell) was provided and a cathode cell with a nickel cathode chamber in which a cathode (cathode cell) was provided were arranged opposite. A pair of gaskets were arranged between the cells, and an ion exchange membrane was sandwiched between the gaskets. Then, the anode cell, the gasket, the ion exchange membrane, the gasket and the cathode were placed in close contact to obtain an electrolytic cell.

[002631] The anode was produced by applying a mixed solution of ruthenium chloride, iridium chloride and titanium tetrachloride on a titanium substrate subjected to pickling and acid attack treatment as a pre-treatment, followed by drying and cooking. The anode was fixed to the anode chamber by welding. As cathode, one described in each of the

670/803 Examples and Comparative Examples. As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. Nickel mesh formed by simple weaving nickel wire with a diameter of 150 µm in a size 40 mesh was placed on top and a rope made of Teflon (R) was used to fix the four corners of the Ni mesh to the collector. This Ni mesh was used as a supply conductor. In this electrolytic cell, the repulsive force of the mattress as the elastic metal body was used in order to achieve a zero interstice structure. Like gaskets, ethylene-propylene-diene rubber (EPDM) gaskets were used. Like the membrane, an ion exchange membrane below was used.

[002632] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarn) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[002633] Next, a dry resin A which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a B resin of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF;) OCF; CF; SO, 7F and had an ion exchange capacity of 1.03 mg equivalent / g.

670/803 Examples and Comparative Examples. As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. Nickel mesh formed by simple weaving nickel wire with a diameter of 150 µm in a size 40 mesh was placed on top and a rope made of Teflon (R) was used to fix the four corners of the Ni mesh to the collector. This Ni mesh was used as a supply conductor. In this electrolytic cell, the repulsive force of the mattress as the elastic metal body was used in order to achieve a zero interstice structure. Like gaskets, ethylene-propylene-diene rubber (EPDM) gaskets were used. Like the membrane, an ion exchange membrane below was used.

[002632] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarn) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[002633] Next, a dry resin A which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a B resin of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF;) OCF; CF; SO, 7F and had an ion exchange capacity of 1.03 mg equivalent / g.

671/803

[002634] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[002635] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[002636] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for 1 hour to replace the ion exchange group counter with Na and then washed with water. In addition, the membrane was dried at 60ºC.

[002637] In addition, 20 wt% zirconium oxide with an average particle size (primary particle size) of 1 µm was added to a 5 wt% ethanol solution of the acid type resin of resin B and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the surfaces of the composite membrane to obtain an ion exchange membrane. The coating density of zirconium oxide measured by X-ray fluorescence measurement was 0.5 mg / em ?. The average particle size was measured by a particle size analyzer (for example,

671/803

[002634] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[002635] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[002636] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for 1 hour to replace the ion exchange group counter with Na and then washed with water. In addition, the membrane was dried at 60ºC.

[002637] In addition, 20 wt% zirconium oxide with an average particle size (primary particle size) of 1 µm was added to a 5 wt% ethanol solution of the acid type resin of resin B and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the surfaces of the composite membrane to obtain an ion exchange membrane. The coating density of zirconium oxide measured by X-ray fluorescence measurement was 0.5 mg / em ?. The average particle size was measured by a particle size analyzer (for example,

672/803 manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[002638] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and the cathodic chamber was adjusted so that the temperature in each electrolytic cell reached 90ºC. Was common salt electrolysis performed at a current density of 6 kA / m? to measure voltage and current density. The current efficiency here is the ratio of the amount of caustic soda produced to the past stream, and when impurity fons and hydroxide fons instead of sodium fons move across the ion exchange membrane due to the passed current, the current efficiency decreases. The current efficiency was obtained by dividing the number of moles of caustic soda produced for a certain period of time by the number of moles of electrons in the current that passed during that period of time. The number of moles of caustic soda was obtained by recovering the caustic soda produced by electrolysis in a plastic container and measuring its mass. (2) Handling property (response assessment)

[002639] (A) The ion exchange membrane (membrane) mentioned above was cut into a 170 mm square, and the electrode obtained in each of the Examples and Comparative Examples mentioned below was cut to a size of 95 x 110 mm. The ion exchange membrane and the electrode were laminated and placed on a Teflon plate. The interval between the anodic cell and the cathodic cell used in the electrolytic evaluation was established at about 3 cm. The laminate placed immobile was lifted and an insertion and retention operation of the laminate was carried out between them. This operation was performed while the electrode was checked for displacement and fall.

[002640] (B) The laminate was placed on a Teflon plate from

672/803 manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[002638] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and the cathodic chamber was adjusted so that the temperature in each electrolytic cell reached 90ºC. Was common salt electrolysis performed at a current density of 6 kA / m? to measure voltage and current density. The current efficiency here is the ratio of the amount of caustic soda produced to the past stream, and when impurity fons and hydroxide fons instead of sodium fons move across the ion exchange membrane due to the passed current, the current efficiency decreases. The current efficiency was obtained by dividing the number of moles of caustic soda produced for a certain period of time by the number of moles of electrons in the current that passed during that period of time. The number of moles of caustic soda was obtained by recovering the caustic soda produced by electrolysis in a plastic container and measuring its mass. (2) Handling property (response assessment)

[002639] (A) The ion exchange membrane (membrane) mentioned above was cut into a 170 mm square, and the electrode obtained in each of the Examples and Comparative Examples mentioned below was cut to a size of 95 x 110 mm. The ion exchange membrane and the electrode were laminated and placed on a Teflon plate. The interval between the anodic cell and the cathodic cell used in the electrolytic evaluation was established at about 3 cm. The laminate placed immobile was lifted and an insertion and retention operation of the laminate was carried out between them. This operation was performed while the electrode was checked for displacement and fall.

[002640] (B) The laminate was placed on a Teflon plate from

673/803 the same way as in (A) above. The two adjacent corners of the membrane portion of the laminate were held by hands to lift the laminate so that it was vertical. The two corners held by the hands were moved from this state to be close to each other, so that the membrane was designed or embedded. This operation was repeated again to verify the conformability of the electrode to the membrane. The results were evaluated on a four-level scale from 1 to 4, based on the following indices: 1: good manipulation property 2: able to be manipulated 3: difficult to manipulate 4: substantially unable to be manipulated

[002641] Here, in relation to the samples of Examples 3-4 and 3-6, samples with the same size as those of the large electrolytic cell were also subjected to the evaluation of the manipulation property, as mentioned below. The results of the evaluation of Example 3-4 and 3-6 were used as indexes to assess the difference between the evaluation of (A) and (B) above and those of larger size. That is, in the case where the result of the evaluation of a small laminate was "1" or "2", it was considered that the handling property becomes good even if the laminate was provided in a larger size. (3) Proportion of fixed region

[002642] The surface area opposite the electrode for electrolysis on the ion exchange membrane (the total of the portion corresponding to the conductive surface and the portion corresponding to the non-conductive surface) was calculated as an area Sl. Then, the electrode area for electrolysis was calculated as a conductive surface area S2. Areas S1 and S2 were identified with the area of the ion exchange membrane laminate and the electrolysis electrode when viewed from the electrolysis electrode side (see

673/803 the same way as in (A) above. The two adjacent corners of the membrane portion of the laminate were held by hands to lift the laminate so that it was vertical. The two corners held by the hands were moved from this state to be close to each other, so that the membrane was designed or embedded. This operation was repeated again to verify the conformability of the electrode to the membrane. The results were evaluated on a four-level scale from 1 to 4, based on the following indices: 1: good manipulation property 2: able to be manipulated 3: difficult to manipulate 4: substantially unable to be manipulated

[002641] Here, in relation to the samples of Examples 3-4 and 3-6, samples with the same size as those of the large electrolytic cell were also subjected to the evaluation of the manipulation property, as mentioned below. The results of the evaluation of Example 3-4 and 3-6 were used as indexes to assess the difference between the evaluation of (A) and (B) above and those of larger size. That is, in the case where the result of the evaluation of a small laminate was "1" or "2", it was considered that the handling property becomes good even if the laminate was provided in a larger size. (3) Proportion of fixed region

[002642] The surface area opposite the electrode for electrolysis on the ion exchange membrane (the total of the portion corresponding to the conductive surface and the portion corresponding to the non-conductive surface) was calculated as an area Sl. Then, the electrode area for electrolysis was calculated as a conductive surface area S2. Areas S1 and S2 were identified with the area of the ion exchange membrane laminate and the electrolysis electrode when viewed from the electrolysis electrode side (see

674/803 Figure 57). Regarding the shape of the electrolysis electrode, even an electrode with openings had an opening ratio of less than 90%. Thus, the electrolysis electrode was considered to be a flat plate (the opening portion should be included in the area).

[002643] The area of the fixed region S3 was also identified as the area in which the laminate was seen from above, as in Figure 57 (the same applies to the area of the portion that corresponds only to the conductive surface S3º). In the event that the PTFE tape mentioned below was fixed as a fixing member, the overlapping portion of the tape should not be included in the area. Alternatively, in the event that the PTFE wires and an adhesive mentioned below were attached as fixing members, the area present on the back sides of the electrode and membrane was included in the area.

[002644] As described above, 100 x (S3 / S1) was calculated as the ratio of the area of the fixed region to (%) in relation to the surface area opposite the electrode for electrolysis on the ion exchange membrane. Additionally, 100 x S3 ”/ S2 was calculated as the proportion of the portion area that corresponds only to the conductive surface of the fixed region À in relation to the area of the conductive surface. [Example 3-1]

[002645] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 22 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.96 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002646] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 44%.

674/803 Figure 57). Regarding the shape of the electrolysis electrode, even an electrode with openings had an opening ratio of less than 90%. Thus, the electrolysis electrode was considered to be a flat plate (the opening portion should be included in the area).

[002643] The area of the fixed region S3 was also identified as the area in which the laminate was seen from above, as in Figure 57 (the same applies to the area of the portion that corresponds only to the conductive surface S3º). In the event that the PTFE tape mentioned below was fixed as a fixing member, the overlapping portion of the tape should not be included in the area. Alternatively, in the event that the PTFE wires and an adhesive mentioned below were attached as fixing members, the area present on the back sides of the electrode and membrane was included in the area.

[002644] As described above, 100 x (S3 / S1) was calculated as the ratio of the area of the fixed region to (%) in relation to the surface area opposite the electrode for electrolysis on the ion exchange membrane. Additionally, 100 x S3 ”/ S2 was calculated as the proportion of the portion area that corresponds only to the conductive surface of the fixed region À in relation to the area of the conductive surface. [Example 3-1]

[002645] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 22 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.96 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002646] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 44%.

675/803

[002647] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002648] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced in Example 3-1 was 24 µm. The thickness of the catalytic layer containing ruthenium oxide and cerium oxide, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface.

[002649] The electrode produced by the method above was cut in a

675/803

[002647] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002648] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced in Example 3-1 was 24 µm. The thickness of the catalytic layer containing ruthenium oxide and cerium oxide, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface.

[002649] The electrode produced by the method above was cut in a

676/803 size 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was positioned opposite in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm x 160 mm) and equilibrated with an aqueous solution of 0.1 N NaOH. PTFE tape (manufactured by NITTO DENKO CORPORATION) was used to fix the four sides so that the ion exchange membrane and electrode were sandwiched as shown in Figure 57 (it should be noted that Figure 57 illustrates a schematic view only for illustrative purposes and dimensions are not necessarily accurate (the same applies to the figures below). In Example 3-1, the PTFE tape was the fixing member, the ratio a was 60% and the ratio B was 1.0%.

[002650] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002651] The electrode integrated into the membrane above was sandwiched between the anode cell and the cathode cell in such a way that the surface on which the electrode was affixed was left facing the side of the cathode chamber. In the sectional structure, the collector, mattress, nickel mesh feed conductor, electrode, membrane and anode are arranged in that order from the side of the cathode chamber to form a zero-interstice structure.

[002652] The resulting electrode was subjected to evaluation. The results are shown in Table 5.

676/803 size 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was positioned opposite in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm x 160 mm) and equilibrated with an aqueous solution of 0.1 N NaOH. PTFE tape (manufactured by NITTO DENKO CORPORATION) was used to fix the four sides so that the ion exchange membrane and electrode were sandwiched as shown in Figure 57 (it should be noted that Figure 57 illustrates a schematic view only for illustrative purposes and dimensions are not necessarily accurate (the same applies to the figures below). In Example 3-1, the PTFE tape was the fixing member, the ratio a was 60% and the ratio B was 1.0%.

[002650] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002651] The electrode integrated into the membrane above was sandwiched between the anode cell and the cathode cell in such a way that the surface on which the electrode was affixed was left facing the side of the cathode chamber. In the sectional structure, the collector, mattress, nickel mesh feed conductor, electrode, membrane and anode are arranged in that order from the side of the cathode chamber to form a zero-interstice structure.

[002652] The resulting electrode was subjected to evaluation. The results are shown in Table 5.

677/803

[002653] The electrode had low voltage and high current efficiency. The handling property was also relatively good: "2". [Example 3-2]

[002654] The evaluation was carried out in the same way as in Example 3-1, except by increasing the area where the PTFE tape overlapped the electrolytic surface, as shown in Figure 58. That is, in Example 3-2, the the area of the PTFE tape was allowed to increase in the direction of the electrolyte electrode plane, and thus, the area of the electrolytic surface on the electrolysis electrode decreased compared to Example 3-1. In Example 3-2, the ratio a was 69% and the ratio B was 23%. The results of the assessment are shown in Table 5.

[002655] The electrode had low voltage and high current efficiency. The handling property was also good: “1”. [Example 3-3]

[002656] The evaluation was performed in the same way as in Example 3-1, except by increasing the area where the PTFE tape overlapped the electrolytic surface, as shown in Figure 59. That is, in Example 3-3, the the area of the PTFE tape was allowed to increase in the direction of the electrolyte electrode plane, and thus, the area of the electrolytic surface on the electrolysis electrode decreased compared to Example 3-1. In Example 3-3, the ratio a was 87% and the ratio B was 67%. The results of the assessment are shown in Table 5.

[002657] The electrode had low voltage and high current efficiency. The handling property was also good: “1”. [Example 3-4]

[002658] An electrode identical to that of Example 3-1 was provided and cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was placed opposite in a substantial central position on the side of the acid layer

677/803

[002653] The electrode had low voltage and high current efficiency. The handling property was also relatively good: "2". [Example 3-2]

[002654] The evaluation was carried out in the same way as in Example 3-1, except by increasing the area where the PTFE tape overlapped the electrolytic surface, as shown in Figure 58. That is, in Example 3-2, the the area of the PTFE tape was allowed to increase in the direction of the electrolyte electrode plane, and thus, the area of the electrolytic surface on the electrolysis electrode decreased compared to Example 3-1. In Example 3-2, the ratio a was 69% and the ratio B was 23%. The results of the assessment are shown in Table 5.

[002655] The electrode had low voltage and high current efficiency. The handling property was also good: “1”. [Example 3-3]

[002656] The evaluation was performed in the same way as in Example 3-1, except by increasing the area where the PTFE tape overlapped the electrolytic surface, as shown in Figure 59. That is, in Example 3-3, the the area of the PTFE tape was allowed to increase in the direction of the electrolyte electrode plane, and thus, the area of the electrolytic surface on the electrolysis electrode decreased compared to Example 3-1. In Example 3-3, the ratio a was 87% and the ratio B was 67%. The results of the assessment are shown in Table 5.

[002657] The electrode had low voltage and high current efficiency. The handling property was also good: “1”. [Example 3-4]

[002658] An electrode identical to that of Example 3-1 was provided and cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was placed opposite in a substantial central position on the side of the acid layer

678/803 carboxylic ion exchange membrane (size: 160 mm x 160 mm) and balanced with an aqueous solution of NaOH 0.1 N. The PTFE yarn was used to sew the electrode on the left side of it in a vertical direction over the ion exchange membrane, as shown in Figure 60. The PTFE wire was allowed to pass through a portion at a vertical distance of mm and a horizontal distance of 10 mm from a corner of the electrode, on the back side of the Figure sheet 60 to its front side, allowed to pass through a portion at a vertical distance of 35 mm and a horizontal distance of 10 mm, from the front side of the sheet to the rear side, allowed to pass through a portion at a vertical distance of 60 mm and a horizontal distance of 10 mm, again from the back side of the sheet to its front side, and allowed to pass through a portion at a vertical distance of 85 mm and a horizontal distance of 10 mm, from the front side of the sheet to its back side . A solution obtained by dispersing an S-type resin from a resin that was a copolymer of CF; = CF ,; and CF. = CFOCF; CF (CF,) OCF3xCF3SO, xF and had an ion exchange capacity of 1.03 mg equivalent / g with a content by weight of 5% in ethanol was applied in the portions to which the wire passed through the ion exchange membrane.

[002659] As described above, in Example 3-4, the ratio a was 0.35% and the ratio B was 0.86%.

[002660] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the ground, the electrode did not fall. Even when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not fall.

[002661] The resulting electrode was subjected to evaluation. The results

678/803 carboxylic ion exchange membrane (size: 160 mm x 160 mm) and balanced with an aqueous solution of NaOH 0.1 N. The PTFE yarn was used to sew the electrode on the left side of it in a vertical direction over the ion exchange membrane, as shown in Figure 60. The PTFE wire was allowed to pass through a portion at a vertical distance of mm and a horizontal distance of 10 mm from a corner of the electrode, on the back side of the Figure sheet 60 to its front side, allowed to pass through a portion at a vertical distance of 35 mm and a horizontal distance of 10 mm, from the front side of the sheet to the rear side, allowed to pass through a portion at a vertical distance of 60 mm and a horizontal distance of 10 mm, again from the back side of the sheet to its front side, and allowed to pass through a portion at a vertical distance of 85 mm and a horizontal distance of 10 mm, from the front side of the sheet to its back side . A solution obtained by dispersing an S-type resin from a resin that was a copolymer of CF; = CF ,; and CF. = CFOCF; CF (CF,) OCF3xCF3SO, xF and had an ion exchange capacity of 1.03 mg equivalent / g with a content by weight of 5% in ethanol was applied in the portions to which the wire passed through the ion exchange membrane.

[002659] As described above, in Example 3-4, the ratio a was 0.35% and the ratio B was 0.86%.

[002660] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the ground, the electrode did not fall. Even when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not fall.

[002661] The resulting electrode was subjected to evaluation. The results

679/803 are shown in Table 5.

[002662] The electrode had low voltage and high current efficiency. The handling property was also relatively good: "2".

[002663] Additionally, an ion exchange membrane and an electrode, each formed in a larger size, were provided in Example 3-4. An ion exchange membrane with a size of 1.5 m long and 2.5 m wide and four cathodes with a size of 0.3 m long and 24 m wide were provided. The cathodes were arranged without any interstice on the side of the carboxylic acid layer of the ion exchange membrane, and the cathodes were attached to the ion exchange membrane by PTFE wire to produce a laminate. In this Example, the ratio a was 0.013% and the ratio B was 0.017%.

[002664] When a fitting operation of a large electrolyzer with the electrode integrated into the membrane, which was formed by the integration of the membrane with the electrode, was performed, it was possible to obtain a smooth fit. [Example 3-5]

[002665] An electrode identical to that of Example 3-1 was provided and cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was positioned opposite in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm x 160 mm) and equilibrated with a 0.1 N aqueous solution of NaOH. fixing resin made of polypropylene shown in Figure 61 was used to fix the ion exchange membrane and the electrode. That is, the resin was placed in two portions in total: one portion at a vertical distance of 20 mm and a horizontal distance of 20 mm from a corner of the electrode, and additionally, a portion at a vertical distance of 20 mm and a distance 20 mm horizontal from the corner located below. In the portions in which the fixing resin passed through the ion exchange membrane, a similar solution was applied

679/803 are shown in Table 5.

[002662] The electrode had low voltage and high current efficiency. The handling property was also relatively good: "2".

[002663] Additionally, an ion exchange membrane and an electrode, each formed in a larger size, were provided in Example 3-4. An ion exchange membrane with a size of 1.5 m long and 2.5 m wide and four cathodes with a size of 0.3 m long and 24 m wide were provided. The cathodes were arranged without any interstice on the side of the carboxylic acid layer of the ion exchange membrane, and the cathodes were attached to the ion exchange membrane by PTFE wire to produce a laminate. In this Example, the ratio a was 0.013% and the ratio B was 0.017%.

[002664] When a fitting operation of a large electrolyzer with the electrode integrated into the membrane, which was formed by the integration of the membrane with the electrode, was performed, it was possible to obtain a smooth fit. [Example 3-5]

[002665] An electrode identical to that of Example 3-1 was provided and cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was positioned opposite in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm x 160 mm) and equilibrated with a 0.1 N aqueous solution of NaOH. fixing resin made of polypropylene shown in Figure 61 was used to fix the ion exchange membrane and the electrode. That is, the resin was placed in two portions in total: one portion at a vertical distance of 20 mm and a horizontal distance of 20 mm from a corner of the electrode, and additionally, a portion at a vertical distance of 20 mm and a distance 20 mm horizontal from the corner located below. In the portions in which the fixing resin passed through the ion exchange membrane, a similar solution was applied

680/803 to that of Example 3-4.

[002666] As described above, in Example 3-5, the fixing resin and S resin served as fixing members, the a ratio was 0.47% and the B ratio was 1.1%.

[002667] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the ground, the electrode did not fall. Even when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not fall.

[002668] The resulting electrode was subjected to evaluation. The results are shown in Table 5.

[002669] The electrode had low voltage and high current efficiency. The handling property was also relatively good: "2". [Example 3-6]

[002670] An electrode identical to that of Example 3-1 was provided and cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was positioned opposite in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm x 160 mm) and balanced with an aqueous solution of NaOH 0.1 N. As shown in Figure 62, a cyanoacrylate adhesive (trade name: Aron Alpha, TOAGOSEI CO., LTD.) was used to fix the ion exchange membrane and the electrode. That is, the membrane and electrode were fixed with the adhesive at five points on one vertical side of the electrode (the points were equally spaced) and eight points on a horizontal side of the electrode (the points were equally spaced).

680/803 to that of Example 3-4.

[002666] As described above, in Example 3-5, the fixing resin and S resin served as fixing members, the a ratio was 0.47% and the B ratio was 1.1%.

[002667] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the ground, the electrode did not fall. Even when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not fall.

[002668] The resulting electrode was subjected to evaluation. The results are shown in Table 5.

[002669] The electrode had low voltage and high current efficiency. The handling property was also relatively good: "2". [Example 3-6]

[002670] An electrode identical to that of Example 3-1 was provided and cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was positioned opposite in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm x 160 mm) and balanced with an aqueous solution of NaOH 0.1 N. As shown in Figure 62, a cyanoacrylate adhesive (trade name: Aron Alpha, TOAGOSEI CO., LTD.) was used to fix the ion exchange membrane and the electrode. That is, the membrane and electrode were fixed with the adhesive at five points on one vertical side of the electrode (the points were equally spaced) and eight points on a horizontal side of the electrode (the points were equally spaced).

681/803

[002671] As described above, in Example 3-6, the adhesive served as fixing members, the ratio a was 0.78% and the ratio B was 1.9%.

[002672] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the ground, the electrode did not fall. Even when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not fall.

[002673] The resulting electrode was subjected to evaluation. The results are shown in Table 5.

[002674] The electrode showed low voltage and high current efficiency. The handling property was also relatively good: "1".

[002675] Additionally, an ion exchange membrane and an electrode, each formed in a larger size, were provided in Example 3-6. An ion exchange membrane with a size of 1.5 m in length and 2.5 m in width and four cathodes with a size of 0.3 m in length and 2.4 m in width were provided. The edge of a horizontal side of each four cathodes was connected to each other with the adhesive above to form a large cathode (1.2 m long and 2.4 m wide). This large cathode was attached to the central portion on the carboxylic acid layer side of the ion exchange membrane with Aron Alpha to produce a laminate. That is, the membrane and the electrode were fixed with the adhesive at five points on a vertical side of the electrode (the points were equally spaced) and eight points on a horizontal side of the electrode (the points were equally spaced), in the same way as in Figure 62. In this example, the o. was 0.019% and the proportion B was 0.024%.

[002676] When fitting a large electrolyzer

681/803

[002671] As described above, in Example 3-6, the adhesive served as fixing members, the ratio a was 0.78% and the ratio B was 1.9%.

[002672] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the ground, the electrode did not fall. Even when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not fall.

[002673] The resulting electrode was subjected to evaluation. The results are shown in Table 5.

[002674] The electrode showed low voltage and high current efficiency. The handling property was also relatively good: "1".

[002675] Additionally, an ion exchange membrane and an electrode, each formed in a larger size, were provided in Example 3-6. An ion exchange membrane with a size of 1.5 m in length and 2.5 m in width and four cathodes with a size of 0.3 m in length and 2.4 m in width were provided. The edge of a horizontal side of each four cathodes was connected to each other with the adhesive above to form a large cathode (1.2 m long and 2.4 m wide). This large cathode was attached to the central portion on the carboxylic acid layer side of the ion exchange membrane with Aron Alpha to produce a laminate. That is, the membrane and the electrode were fixed with the adhesive at five points on a vertical side of the electrode (the points were equally spaced) and eight points on a horizontal side of the electrode (the points were equally spaced), in the same way as in Figure 62. In this example, the o. was 0.019% and the proportion B was 0.024%.

[002676] When fitting a large electrolyzer

682/803 with the electrode integrated into the membrane, which was formed by integrating the membrane with the electrode, it was possible to achieve a smooth fit. [Example 3-7]

[002677] An electrode identical to that of Example 3-1 was provided and cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was positioned opposite in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm x 160 mm) and equilibrated with a 0.1 N aqueous solution of NaOH. A solution similar to Example 3-4 was applied to fix the ion exchange membrane and the electrode. That is, the resin was placed in two portions in total: one portion at a vertical distance of 20 mm and a horizontal distance of 20 mm from a corner of the electrode, and additionally, a portion at a vertical distance of 20 mm and a distance horizontal distance of 20 mm from the corner located below (see Figure 61).

[002678] As described above, in Example 3-7, resin S served as fixing members, the ratio a was 2.0% and the ratio B was 4.8%.

[002679] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the ground, the electrode did not fall. Even when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not fall.

[002680] The resulting electrode was subjected to evaluation. The results are shown in Table 5.

[002681] The electrode had low voltage and high current efficiency. The handling property was also relatively good: "2".

682/803 with the electrode integrated into the membrane, which was formed by integrating the membrane with the electrode, it was possible to achieve a smooth fit. [Example 3-7]

[002677] An electrode identical to that of Example 3-1 was provided and cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was positioned opposite in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane (size: 160 mm x 160 mm) and equilibrated with a 0.1 N aqueous solution of NaOH. A solution similar to Example 3-4 was applied to fix the ion exchange membrane and the electrode. That is, the resin was placed in two portions in total: one portion at a vertical distance of 20 mm and a horizontal distance of 20 mm from a corner of the electrode, and additionally, a portion at a vertical distance of 20 mm and a distance horizontal distance of 20 mm from the corner located below (see Figure 61).

[002678] As described above, in Example 3-7, resin S served as fixing members, the ratio a was 2.0% and the ratio B was 4.8%.

[002679] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the ground, the electrode did not fall. Even when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not fall.

[002680] The resulting electrode was subjected to evaluation. The results are shown in Table 5.

[002681] The electrode had low voltage and high current efficiency. The handling property was also relatively good: "2".

683/803 [Comparative Example 3-1]

[002682] The evaluation was carried out in the same way as in Example 3-1, except for increasing the area where the PTFE tape overlapped the electrolytic surface. That is, in Comparative Example 3-1, the area of the PTFE tape was allowed to increase in the direction of the electrolyte electrode plane, and thus, the area of the electrolytic surface on the electrolysis electrode decreased compared to Example 3-1. In Comparative Example 3-1, the a ratio is 93% and the a ratio is 83%. The results of the assessment are shown in Table 5.

[002683] The voltage was high, and the current efficiency was also low. The handling property was good: “1”. [Comparative Example 3-2]

[002684] The evaluation was performed in the same way as in Example 3-1, except for increasing the area where the PTFE tape overlapped the electrolytic surface. The results of the evaluation are shown in Table 5. That is, in Comparative Example 3-2, the area of the PTFE tape was allowed to increase in the direction of the electrode plane for electrolysis.

[002685] In Comparative Example 3-2, the proportion a. and the B ratio was 100%, and the entire electrolytic surface was a fixed region covered with PTFE. Thus, it was not possible to provide an electrolyte solution and, therefore, it was not possible to perform electrolysis. The handling property was good: “1”. [Comparative Example 3-3]

[002686] The evaluation was carried out in the same way as in Example 3-1, except that PTFE tape was not used, that is, the proportion 0 and the proportion f8 were 0%. The results of the assessment are shown in Table 5.

[002687] The electrode had low voltage and high current efficiency. However, as there was no fixed region of the membrane and electrode,

683/803 [Comparative Example 3-1]

[002682] The evaluation was carried out in the same way as in Example 3-1, except for increasing the area where the PTFE tape overlapped the electrolytic surface. That is, in Comparative Example 3-1, the area of the PTFE tape was allowed to increase in the direction of the electrolyte electrode plane, and thus, the area of the electrolytic surface on the electrolysis electrode decreased compared to Example 3-1. In Comparative Example 3-1, the a ratio is 93% and the a ratio is 83%. The results of the assessment are shown in Table 5.

[002683] The voltage was high, and the current efficiency was also low. The handling property was good: “1”. [Comparative Example 3-2]

[002684] The evaluation was performed in the same way as in Example 3-1, except for increasing the area where the PTFE tape overlapped the electrolytic surface. The results of the evaluation are shown in Table 5. That is, in Comparative Example 3-2, the area of the PTFE tape was allowed to increase in the direction of the electrode plane for electrolysis.

[002685] In Comparative Example 3-2, the proportion a. and the B ratio was 100%, and the entire electrolytic surface was a fixed region covered with PTFE. Thus, it was not possible to provide an electrolyte solution and, therefore, it was not possible to perform electrolysis. The handling property was good: “1”. [Comparative Example 3-3]

[002686] The evaluation was carried out in the same way as in Example 3-1, except that PTFE tape was not used, that is, the proportion 0 and the proportion f8 were 0%. The results of the assessment are shown in Table 5.

[002687] The electrode had low voltage and high current efficiency. However, as there was no fixed region of the membrane and electrode,

684/803 it was not possible to manipulate the membrane and electrode as a laminate (integrated part) and, therefore, the manipulation property was “4”.

[002688] The results of the evaluation of Examples 3-1 to 7 and Comparative Examples 3-1 to 3 were also shown in Table 5 below. [Table 5] Area of the region | of the substrat pa Area of the eleiódo Isa - corresponding to Prop- Prop- | property- Embarrassed evaluation PER oo the fixed epion only to the electrolytic CFãoB action for electrolysis Á e and the wavy nanipulation surface ko (evaluation efficiency 2 3 3 o0 * s3 / oo * s3 sensorial) mensã He PP pP? ? 61 (%) | 1H2 (%) o (V) torrent o) Eepernb - fm BB Eb & R E br | Example 3: 3 see —— children ——— hbo ho b kb | Bs bsi | Example 34 ps6 —oss ——— boo bo hph35 bes bp boo br | Example 3: 5 bs6 ——hoss - = -> —— = - h2 ha hp hi b Boobrs | Example 3: 7 ps6 ——hoss ——bo bo bo hg bp boo bro | Comparative example P56 104.5 b3o B7 b3 bb kh 6.50 B B-1 [Example level of comparison b56 [104.5 56 [104.5 hoo hoo | Etrolizing | bo letrolisar [Comparative example P56 104.5 o o p o 2.97 B7.5 Bs <Verification of the fourth modality>

[002689] As will be described below, Experimental Examples were provided in accordance with the fourth modality (in the <Verification of the fourth modality> section, simply called “Examples”) and Experimental Examples not in accordance with the fourth modality (in the section <Verification of the fourth modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 79 to 90, as appropriate. [Valuation method] (1) Opening reason

684/803 it was not possible to manipulate the membrane and electrode as a laminate (integrated part) and, therefore, the manipulation property was “4”.

[002688] The results of the evaluation of Examples 3-1 to 7 and Comparative Examples 3-1 to 3 were also shown in Table 5 below. [Table 5] Area of the region | of the substrat pa Area of the eleiódo Isa - corresponding to Prop- Prop- | property- Embarrassed evaluation PER oo the fixed epion only to the electrolytic CFãoB action for electrolysis Á e and the wavy nanipulation surface ko (evaluation efficiency 2 3 3 o0 * s3 / oo * s3 sensorial) mensã He PP pP? ? 61 (%) | 1H2 (%) o (V) torrent o) Eepernb - fm BB Eb & R E br | Example 3: 3 see —— children ——— hbo ho b kb | Bs bsi | Example 34 ps6 —oss ——— boo bo hph35 bes bp boo br | Example 3: 5 bs6 ——hoss - = -> —— = - h2 ha hp hi b Boobrs | Example 3: 7 ps6 ——hoss ——bo bo bo hg bp boo bro | Comparative example P56 104.5 b3o B7 b3 bb kh 6.50 B B-1 [Example level of comparison b56 [104.5 56 [104.5 hoo hoo | Etrolizing | bo letrolisar [Comparative example P56 104.5 o o p o 2.97 B7.5 Bs <Verification of the fourth modality>

[002689] As will be described below, Experimental Examples were provided in accordance with the fourth modality (in the <Verification of the fourth modality> section, simply called “Examples”) and Experimental Examples not in accordance with the fourth modality (in the section <Verification of the fourth modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 79 to 90, as appropriate. [Valuation method] (1) Opening reason

685/803

[002690] An electrode was cut to a size of 130 mm x 100 mm. A digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale of 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the electrode thickness (gauge thickness) to calculate the volume. Subsequently, an electronic scale was used to measure the mass. From the specific gravity of each metal (specific gravity of nickel = 8.908 glem ?, specific gravity of titanium = 4.506 g / emi), the opening ratio or vacuum ratio was calculated. Opening ratio (Vacuum ratio) (%) = (1 - (electrode mass) / (electrode volume x specific gravity of the nickel)) x 100 (2) Mass per unit area (mg / cm?)

[002691] An electrode was cut to a size of 130 mm x 100 mm, and the mass was measured by an electronic scale. The value was divided by the area (130 mm x 100 mm) to calculate the mass per unit area. (3) Force applied per unit mass-unit area (1) (adhesive force) (N / mg: cm?)) [Method (i)]

[002692] A tensile and compression testing machine was used for measurement (Imada-SS Corporation, main testing machine: SDT-52NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[002693] A 200 mm square nickel plate with a thickness of 1.2 mm was subjected to stripping processing with 320 grain size alumina. The arithmetic mean roughness of the surface (Ra) of the nickel plate after treatment by pickling was 0.7 µm. To measure the surface roughness, an instrument for measuring surface roughness of the SJ-310 type probe (Mitutoyo Corporation) was used. A measurement sample was placed on the surface plate parallel to the

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[002690] An electrode was cut to a size of 130 mm x 100 mm. A digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale of 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the electrode thickness (gauge thickness) to calculate the volume. Subsequently, an electronic scale was used to measure the mass. From the specific gravity of each metal (specific gravity of nickel = 8.908 glem ?, specific gravity of titanium = 4.506 g / emi), the opening ratio or vacuum ratio was calculated. Opening ratio (Vacuum ratio) (%) = (1 - (electrode mass) / (electrode volume x specific gravity of the nickel)) x 100 (2) Mass per unit area (mg / cm?)

[002691] An electrode was cut to a size of 130 mm x 100 mm, and the mass was measured by an electronic scale. The value was divided by the area (130 mm x 100 mm) to calculate the mass per unit area. (3) Force applied per unit mass-unit area (1) (adhesive force) (N / mg: cm?)) [Method (i)]

[002692] A tensile and compression testing machine was used for measurement (Imada-SS Corporation, main testing machine: SDT-52NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[002693] A 200 mm square nickel plate with a thickness of 1.2 mm was subjected to stripping processing with 320 grain size alumina. The arithmetic mean roughness of the surface (Ra) of the nickel plate after treatment by pickling was 0.7 µm. To measure the surface roughness, an instrument for measuring surface roughness of the SJ-310 type probe (Mitutoyo Corporation) was used. A measurement sample was placed on the surface plate parallel to the

686/803 soil surface to measure the average arithmetic roughness Ra under measurement conditions as described below. The measurement was repeated 6 times and the average value was listed.

<Probe shape> conical tapering angle = 60º, tip radius = 2 um, static measuring force = 0.75 mN <Roughness pattern> JIS2001 <Evaluation curve> R <Filter> GAUSS <Ac cut value> 0.8 mm <As cut value> 2.5 um <Number of sections> 5 <Pre-run, post-run> available

[002694] This nickel plate was fixed vertically to the lower shim of the tensile and compression testing machine.

[002695] As the membrane, an ion exchange membrane À below was used.

[002696] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarn) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[002697] Then, a resin A of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ability to exchange

686/803 soil surface to measure the average arithmetic roughness Ra under measurement conditions as described below. The measurement was repeated 6 times and the average value was listed.

<Probe shape> conical tapering angle = 60º, tip radius = 2 um, static measuring force = 0.75 mN <Roughness pattern> JIS2001 <Evaluation curve> R <Filter> GAUSS <Ac cut value> 0.8 mm <As cut value> 2.5 um <Number of sections> 5 <Pre-run, post-run> available

[002694] This nickel plate was fixed vertically to the lower shim of the tensile and compression testing machine.

[002695] As the membrane, an ion exchange membrane À below was used.

[002696] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarn) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[002697] Then, a resin A of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ability to exchange

687/803 ionic 0.85 mg equivalent / g, and a resin B of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.03 mg equivalent / g.

[002698] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[002699] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[002700] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[002701] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of the acid type B resin resin and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the surfaces of the composite membrane to obtain an ion exchange membrane A.

687/803 ionic 0.85 mg equivalent / g, and a resin B of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.03 mg equivalent / g.

[002698] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[002699] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[002700] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[002701] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of the acid type B resin resin and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the surfaces of the composite membrane to obtain an ion exchange membrane A.

688/803 zirconium oxide coating density measured by X-ray fluorescence measurement was 0.5 mg / em ?. The average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[002702] The ion exchange membrane (membrane) obtained above was immersed in pure water for 12 hours or more and then used for the test. The membrane was placed in contact with the nickel plate above sufficiently moistened with pure water and allowed to adhere to the plate by the water tension. At that time, the nickel plate and the ion exchange membrane were placed in order to align their upper ends.

[002703] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The ion exchange membrane A was cut into a 170 mm square. One side of the electrode was sandwiched by two stainless steel plates (thickness: 1 mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[002704] The upper shim of the traction and compression test machine was lowered, and the electrode sample for electrolysis was allowed to adhere to the surface of the ion exchange membrane by the surface tension of pure water.

688/803 zirconium oxide coating density measured by X-ray fluorescence measurement was 0.5 mg / em ?. The average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[002702] The ion exchange membrane (membrane) obtained above was immersed in pure water for 12 hours or more and then used for the test. The membrane was placed in contact with the nickel plate above sufficiently moistened with pure water and allowed to adhere to the plate by the water tension. At that time, the nickel plate and the ion exchange membrane were placed in order to align their upper ends.

[002703] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The ion exchange membrane A was cut into a 170 mm square. One side of the electrode was sandwiched by two stainless steel plates (thickness: 1 mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[002704] The upper shim of the traction and compression test machine was lowered, and the electrode sample for electrolysis was allowed to adhere to the surface of the ion exchange membrane by the surface tension of pure water.

689/803 The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and ion exchange membrane entirely in order to sufficiently moisten the membrane and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess pure water. The roll was laminated only once.

[002705] The electrode was raised at a rate of 10 mm / minute to start the charge measurement, and the charge when the size of the overlapped portion of the electrode and the membrane reached 130 mm in width and 100 mm in length was recorded. This measurement was repeated three times and the average value was calculated.

[002706] This average value was divided by the area of the overlapping portion of the electrode and the ion exchange membrane and the mass of the electrode of the portion overlapping the ion exchange membrane to calculate the force applied per unit mass-unit area (1) . The electrode mass of the portion superimposed on the ion exchange membrane was determined through proportional calculation from the value obtained in (2) Mass per unit area (mg / cm?) Described above.

[002707] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[002708] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to the ion exchange membrane that adhered to a nickel plate fixed vertically through the surface tension.

[002709] A schematic view of a method for evaluating the applied force (1) is shown in Figure 79.

689/803 The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and ion exchange membrane entirely in order to sufficiently moisten the membrane and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess pure water. The roll was laminated only once.

[002705] The electrode was raised at a rate of 10 mm / minute to start the charge measurement, and the charge when the size of the overlapped portion of the electrode and the membrane reached 130 mm in width and 100 mm in length was recorded. This measurement was repeated three times and the average value was calculated.

[002706] This average value was divided by the area of the overlapping portion of the electrode and the ion exchange membrane and the mass of the electrode of the portion overlapping the ion exchange membrane to calculate the force applied per unit mass-unit area (1) . The electrode mass of the portion superimposed on the ion exchange membrane was determined through proportional calculation from the value obtained in (2) Mass per unit area (mg / cm?) Described above.

[002707] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[002708] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to the ion exchange membrane that adhered to a nickel plate fixed vertically through the surface tension.

[002709] A schematic view of a method for evaluating the applied force (1) is shown in Figure 79.

690/803

[002710] The lower limit of measurement of the tensile testing machine was 0.01 (N). (4) Force applied per unit mass-unit area (2) (adhesive force) (N / mg: cm?)) [Method (ii)]

[002711] A tensile and compression test machine was used for measurement (Imada-SS Corporation, main test machine: SDT-52NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[002712] A nickel plate identical to that of Method (1) was fixed vertically to the lower shim of the tensile and compression testing machine.

[002713] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The ion exchange membrane A was cut into a 170 mm square. One side of the electrode was sandwiched by two stainless steel plates (thickness: 1 mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[002714] The upper shim of the traction and compression testing machine was lowered, and the electrode sample for electrolysis was allowed to adhere to the

690/803

[002710] The lower limit of measurement of the tensile testing machine was 0.01 (N). (4) Force applied per unit mass-unit area (2) (adhesive force) (N / mg: cm?)) [Method (ii)]

[002711] A tensile and compression test machine was used for measurement (Imada-SS Corporation, main test machine: SDT-52NA type tensile and compression test machine, load cell: load cell type SL-6001 ).

[002712] A nickel plate identical to that of Method (1) was fixed vertically to the lower shim of the tensile and compression testing machine.

[002713] A sample of electrolysis electrode (electrode) to be used for measurement was cut into a 130 mm square. The ion exchange membrane A was cut into a 170 mm square. One side of the electrode was sandwiched by two stainless steel plates (thickness: 1 mm, length: 9 mm, width: 170 mm). After positioning in order to align the center of the stainless steel plates with the center of the electrode, four clips were used to uniformly fix the electrode and plates. The center of the stainless steel plates was fixed by the upper shim of the tensile and compression testing machine to hang the electrode. The load applied to the test machine at that time was set to O N. The integrated part of the stainless steel plates, electrode and clamps was removed once from the tensile and compression test machine, and immersed in a vat containing pure water, the in order to moisten the electrode sufficiently with pure water. Subsequently, the center of the stainless steel plates was fixed again by the upper shim of the tensile and compression testing machine to hang the electrode.

[002714] The upper shim of the traction and compression testing machine was lowered, and the electrode sample for electrolysis was allowed to adhere to the

691/803 surface of the nickel plate through the surface tension of a solution. The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and the nickel plate entirely in order to sufficiently moisten the nickel plate and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess solution. The roll was laminated only once.

[002715] The electrode was raised at a rate of 10 mm / minute to start the charge measurement, and the charge when the size of the overlapping portion of the electrode and the nickel plate in the longitudinal direction reached 100 mm was recorded. This measurement was repeated three times and the average value was calculated.

[002716] This average value was divided by the area of the overlapping portion of the electrode and the nickel plate and the mass of the electrode of the portion overlapping the nickel plate to calculate the force applied per unit mass-unit area (2). The electrode mass of the portion superimposed on the membrane was determined through proportional calculation from the value obtained in (2) Mass per unit area (mg / cm?) Described above.

[002717] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[002718] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to a nickel plate fixed vertically through the surface tension.

[002719] The lower limit of measurement of the tensile testing machine was 0.01 (N). (5) Method for evaluating the winding around the 280 mm column

691/803 surface of the nickel plate through the surface tension of a solution. The size of the adhesive surface at that time was 130 mm wide and 110 mm long. Pure water in a wash bottle was sprayed onto the electrode and the nickel plate entirely in order to sufficiently moisten the nickel plate and electrode again. After that, a roll formed by wrapping a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was rolled down from the top with light pressure over the electrode to remove excess solution. The roll was laminated only once.

[002715] The electrode was raised at a rate of 10 mm / minute to start the charge measurement, and the charge when the size of the overlapping portion of the electrode and the nickel plate in the longitudinal direction reached 100 mm was recorded. This measurement was repeated three times and the average value was calculated.

[002716] This average value was divided by the area of the overlapping portion of the electrode and the nickel plate and the mass of the electrode of the portion overlapping the nickel plate to calculate the force applied per unit mass-unit area (2). The electrode mass of the portion superimposed on the membrane was determined through proportional calculation from the value obtained in (2) Mass per unit area (mg / cm?) Described above.

[002717] As for the measurement chamber environment, the temperature was 23 + 2ºC and the relative humidity was 30 + 5%.

[002718] The electrode used in the Examples and Comparative Examples was able to stand on its own and adhere without slipping or loosening when allowed to adhere to a nickel plate fixed vertically through the surface tension.

[002719] The lower limit of measurement of the tensile testing machine was 0.01 (N). (5) Method for evaluating the winding around the 280 mm column

692/803 diameter (1) (%) (Membrane and column)

[002720] The evaluation method (1) was conducted by the following procedure.

[002721] The ion exchange membrane A (membrane) produced in [Method (1)] was cut into a 170 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In Examples 33 and 34, the electrode was integrated with the ion exchange membrane by thermal pressing, and thus an integrated part of an ion exchange membrane and an electrode (130 mm square electrode) was provided. After the ion exchange membrane was sufficiently immersed in pure water, the membrane was placed on the curved surface of a plastic (polyethylene) tube with an outer diameter of 280 mm. Subsequently, the excess solution was removed with a roller formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (external diameter: 38 mm). The roll was laminated over the ion exchange membrane from left to right from the schematic view shown in Figure 80. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the plastic tube electrode with an external diameter of 280 mm was measured. (6) Method for evaluating the winding around the 280 mm diameter column (2) (%) (Membrane and electrode)

[002722] The evaluation method (2) was conducted by the following procedure.

[002723] The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in water

692/803 diameter (1) (%) (Membrane and column)

[002720] The evaluation method (1) was conducted by the following procedure.

[002721] The ion exchange membrane A (membrane) produced in [Method (1)] was cut into a 170 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In Examples 33 and 34, the electrode was integrated with the ion exchange membrane by thermal pressing, and thus an integrated part of an ion exchange membrane and an electrode (130 mm square electrode) was provided. After the ion exchange membrane was sufficiently immersed in pure water, the membrane was placed on the curved surface of a plastic (polyethylene) tube with an outer diameter of 280 mm. Subsequently, the excess solution was removed with a roller formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (external diameter: 38 mm). The roll was laminated over the ion exchange membrane from left to right from the schematic view shown in Figure 80. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the plastic tube electrode with an external diameter of 280 mm was measured. (6) Method for evaluating the winding around the 280 mm diameter column (2) (%) (Membrane and electrode)

[002722] The evaluation method (2) was conducted by the following procedure.

[002723] The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in water

693/803 pure for 12 hours or more and then used for testing. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 280 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was laminated from left to right in the schematic view shown in Figure 81 with light pressure on the electrode to remove excess solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured. (7) Method for assessing the winding around the 145 mm diameter column (3) (%) (Membrane and electrode)

[002724] The evaluation method (3) was conducted by the following procedure.

[002725] The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 145 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was laminated from left to right in the schematic view shown in Figure 82 with light pressure on the electrode to remove the

693/803 pure for 12 hours or more and then used for testing. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 280 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was laminated from left to right in the schematic view shown in Figure 81 with light pressure on the electrode to remove excess solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured. (7) Method for assessing the winding around the 145 mm diameter column (3) (%) (Membrane and electrode)

[002724] The evaluation method (3) was conducted by the following procedure.

[002725] The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square, and the electrode was cut into a 130 mm square. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. The ion exchange membrane and the electrode were sufficiently immersed in pure water and then laminated. This laminate was placed on the curved surface of a plastic (polyethylene) tube with an external diameter of 145 mm, so that the electrode was located outside. After that, a roll formed by winding a closed cell EPDM sponge rubber with a thickness of 5 mm around a vinyl chloride tube (outside diameter: 38 mm) was laminated from left to right in the schematic view shown in Figure 82 with light pressure on the electrode to remove the

694/803 excess of solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured. (8) Handling property (response assessment)

[002726] (A) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: aqueous sodium bicarbonate solution, aqueous 0.1 N NaOH solution and pure water, then laminated and placed immobile on a Teflon plate. The interval between the anodic cell and the cathodic cell used in the electrolytic evaluation was established at about 3 cm. The laminate placed immobile was lifted and an insertion and retention operation of the laminate was carried out between them. This operation was performed while the electrode was checked for displacement and fall.

[002727] (B) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: an aqueous solution of sodium bicarbonate, an aqueous solution of NaOH 0.1 N and pure water, then laminated and placed immobile on a Teflon plate . The two adjacent corners of the membrane portion of the laminate were held by hands to lift the laminate so that it was vertical. The two corners held by the hands were moved from this state to be close to each other, so that the membrane was designed or embedded. This movement was repeated again to check the conformability of the electrode to the membrane. The

694/803 excess of solution. The roll was laminated only once. One minute later, the proportion of a portion in which the ion exchange membrane was placed in close contact with the electrode was measured. (8) Handling property (response assessment)

[002726] (A) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: aqueous sodium bicarbonate solution, aqueous 0.1 N NaOH solution and pure water, then laminated and placed immobile on a Teflon plate. The interval between the anodic cell and the cathodic cell used in the electrolytic evaluation was established at about 3 cm. The laminate placed immobile was lifted and an insertion and retention operation of the laminate was carried out between them. This operation was performed while the electrode was checked for displacement and fall.

[002727] (B) The ion exchange membrane A (membrane) produced in [Method (i)] was cut into a 170 mm square and the electrode was cut to a size of 95 x 110 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In each Example, the ion exchange membrane and the electrode were sufficiently immersed in three solutions: an aqueous solution of sodium bicarbonate, an aqueous solution of NaOH 0.1 N and pure water, then laminated and placed immobile on a Teflon plate . The two adjacent corners of the membrane portion of the laminate were held by hands to lift the laminate so that it was vertical. The two corners held by the hands were moved from this state to be close to each other, so that the membrane was designed or embedded. This movement was repeated again to check the conformability of the electrode to the membrane. The

695/803 results were evaluated on a four-level scale from 1 to 4, based on the following indices: 1: good manipulation property 2: able to be manipulated 3: difficult to manipulate 4: substantially unable to be manipulated

[002728] Here, the sample from Example 4-28, provided in a size equivalent to that of a large electrolytic cell including an electrode in a size of 1.3 mx 2.5 m and an ion exchange membrane in a size of 1, 5 mx 2.8 m, was subjected to manipulation. The result of the evaluation of Example 28 (“3” as described below) was used as an index to assess the difference between the evaluation of (A) and (B) above and the largest. That is, in the case where the result of the evaluation of a small laminate was "1" or "2", it was considered that there was no problem in the handling property even if the laminate was provided in a larger size. (9) Electrolytic evaluation (voltage (V), current efficiency (%), common saline concentration in caustic soda (ppm, on the basis of 50%))

[002729] Electrolytic performance was evaluated by the following electrolytic experiment.

[002730] A titanium anode cell with an anode chamber in which an anode (anode cell) was provided and a cathode cell with a nickel cathode chamber in which a cathode (cell of the cathode terminal) was provided were arranged opposite. A pair of gaskets were arranged between the cells, and a laminate (an I-exchange membrane laminate and an electrolysis electrode) was sandwiched between the gaskets. Here, both the À ion exchange membrane and the electrolysis electrode were placed directly between the gaskets. Then, the anodic cell, gasket, laminate, gasket and cathode were placed in

695/803 results were evaluated on a four-level scale from 1 to 4, based on the following indices: 1: good manipulation property 2: able to be manipulated 3: difficult to manipulate 4: substantially unable to be manipulated

[002728] Here, the sample from Example 4-28, provided in a size equivalent to that of a large electrolytic cell including an electrode in a size of 1.3 mx 2.5 m and an ion exchange membrane in a size of 1, 5 mx 2.8 m, was subjected to manipulation. The result of the evaluation of Example 28 (“3” as described below) was used as an index to assess the difference between the evaluation of (A) and (B) above and the largest. That is, in the case where the result of the evaluation of a small laminate was "1" or "2", it was considered that there was no problem in the handling property even if the laminate was provided in a larger size. (9) Electrolytic evaluation (voltage (V), current efficiency (%), common saline concentration in caustic soda (ppm, on the basis of 50%))

[002729] Electrolytic performance was evaluated by the following electrolytic experiment.

[002730] A titanium anode cell with an anode chamber in which an anode (anode cell) was provided and a cathode cell with a nickel cathode chamber in which a cathode (cell of the cathode terminal) was provided were arranged opposite. A pair of gaskets were arranged between the cells, and a laminate (an I-exchange membrane laminate and an electrolysis electrode) was sandwiched between the gaskets. Here, both the À ion exchange membrane and the electrolysis electrode were placed directly between the gaskets. Then, the anodic cell, gasket, laminate, gasket and cathode were placed in

696/803 close contact to obtain an electrolytic cell, and an electrolyzer including the cell was provided.

[002731] The anode was produced by applying a mixed solution of ruthenium chloride, iridium chloride and titanium tetrachloride on a titanium substrate subjected to pickling and acid attack treatment as a pre-treatment, followed by drying and cooking. The anode was fixed to the anode chamber by welding. As a cathode, one described in each of the Examples and Comparative Examples was used. As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. Nickel mesh formed by simple weaving nickel wire with a diameter of 150 µm in a size 40 mesh was placed on top and a rope made of Teflon (R) was used to fix the four corners of the Ni mesh to the collector. This Ni mesh was used as a supply conductor. This electrolytic cell has a zero interstice structure using the repulsive force of the mattress like the elastic metal body. Like gaskets, ethylene-propylene-diene rubber (EPDM) gaskets were used. As a membrane, the ion exchange membrane A (160 mm square) produced in [Method (i)] was used.

[002732] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and in the cathodic chamber was adjusted to allow the temperature in each electrolytic cell to reach 90ºC. Was common salt electrolysis performed at a current density of 6 kA / m? to measure voltage, current efficiency and common salt concentration in caustic soda. The current efficiency here is the proportion of the amount of soda

696/803 close contact to obtain an electrolytic cell, and an electrolyzer including the cell was provided.

[002731] The anode was produced by applying a mixed solution of ruthenium chloride, iridium chloride and titanium tetrachloride on a titanium substrate subjected to pickling and acid attack treatment as a pre-treatment, followed by drying and cooking. The anode was fixed to the anode chamber by welding. As a cathode, one described in each of the Examples and Comparative Examples was used. As a collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. Nickel mesh formed by simple weaving nickel wire with a diameter of 150 µm in a size 40 mesh was placed on top and a rope made of Teflon (R) was used to fix the four corners of the Ni mesh to the collector. This Ni mesh was used as a supply conductor. This electrolytic cell has a zero interstice structure using the repulsive force of the mattress like the elastic metal body. Like gaskets, ethylene-propylene-diene rubber (EPDM) gaskets were used. As a membrane, the ion exchange membrane A (160 mm square) produced in [Method (i)] was used.

[002732] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and in the cathodic chamber was adjusted to allow the temperature in each electrolytic cell to reach 90ºC. Was common salt electrolysis performed at a current density of 6 kA / m? to measure voltage, current efficiency and common salt concentration in caustic soda. The current efficiency here is the proportion of the amount of soda

697/803 caustic produced for the passed current, and when impurity fons and hydroxide fons instead of sodium ions move through the ion exchange membrane due to the passed current, the current efficiency decreases. The current efficiency was obtained by dividing the number of moles of caustic soda produced for a certain time by the number of moles of electrons in the current that passed during that time. The number of moles of caustic soda was obtained by recovering the caustic soda produced by electrolysis in a plastic container and measuring its mass. As the concentration of common salt in caustic soda, a value obtained by converting the concentration of caustic soda to the base of 50% was shown.

[002733] The specification of the electrode and the supply conductor used in each of the Examples and Comparative Examples is shown in Table 6. (11) Measurement of the thickness of the catalytic layer, electrode substrate for electrolysis and electrode thickness

[002734] For the thickness of the electrode substrate for electrolysis, a digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the substrate thickness for the electrolysis electrode (gauge thickness). For the electrode thickness, a digital thickness gauge was used to calculate an average value of 10 points obtained by measuring uniformly in the plane, in the same way as for the electrode substrate. The value was used as the electrode thickness (gauge thickness). The thickness of the catalytic layer was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness. (12) Test of elastic deformation of the electrode

[002735] The ion exchange membrane A (membrane) and the electrode produced in [Method (i)] were cut, each, in a square of 110

697/803 caustic produced for the passed current, and when impurity fons and hydroxide fons instead of sodium ions move through the ion exchange membrane due to the passed current, the current efficiency decreases. The current efficiency was obtained by dividing the number of moles of caustic soda produced for a certain time by the number of moles of electrons in the current that passed during that time. The number of moles of caustic soda was obtained by recovering the caustic soda produced by electrolysis in a plastic container and measuring its mass. As the concentration of common salt in caustic soda, a value obtained by converting the concentration of caustic soda to the base of 50% was shown.

[002733] The specification of the electrode and the supply conductor used in each of the Examples and Comparative Examples is shown in Table 6. (11) Measurement of the thickness of the catalytic layer, electrode substrate for electrolysis and electrode thickness

[002734] For the thickness of the electrode substrate for electrolysis, a digital thickness gauge (manufactured by Mitutoyo Corporation, minimum scale 0.001 mm) was used to calculate an average value of 10 points obtained by measuring uniformly in the plane. The value was used as the substrate thickness for the electrolysis electrode (gauge thickness). For the electrode thickness, a digital thickness gauge was used to calculate an average value of 10 points obtained by measuring uniformly in the plane, in the same way as for the electrode substrate. The value was used as the electrode thickness (gauge thickness). The thickness of the catalytic layer was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness. (12) Test of elastic deformation of the electrode

[002735] The ion exchange membrane A (membrane) and the electrode produced in [Method (i)] were cut, each, in a square of 110

698/803 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. After the ion exchange membrane and the electrode were laminated to produce a laminate under conditions of a temperature: 23 + 2ºC and a relative humidity: 30 + 5%, the laminate was wrapped around a PVC tube with an outside diameter of 632 mm and a length of 20 cm without any interstice, as shown in Figure 83. The laminate was fixed using a polyethylene clamp so that the laminated roll did not come out of the PVC tube or come loose. The laminate was retained in this state for 6 hours. Subsequently, the cable tie was removed and the laminate was unrolled from the PVC tube. Only the electrode was placed on a surface plate, and the heights L, 1 and L7 of a raised portion of the surface plate were measured to determine an average value. This value was used as the electrode strain index. In other words, a lower value means that the laminate is unlikely to deform.

[002736] When an expanded metal is used, there are two winding directions: the SW direction and the LW direction. In this test, the laminate was rolled in the SW direction.

[002737] Deformed electrodes (electrodes that did not return to their original flat state) were evaluated for smoothness after plastic deformation according to a method shown in Figure 84. That is, a deformed electrode was placed in a membrane sufficiently immersed in water. pure. One end of the electrode was attached, and the other raised end was pressed into the membrane to release a force, and an assessment was made as to whether the deformed electrode matched the membrane. (13) Assessment of membrane damage

[002738] As the membrane, an ion exchange membrane B below was used.

[002739] As reinforcement core materials, those obtained were used

698/803 mm. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. After the ion exchange membrane and the electrode were laminated to produce a laminate under conditions of a temperature: 23 + 2ºC and a relative humidity: 30 + 5%, the laminate was wrapped around a PVC tube with an outside diameter of 632 mm and a length of 20 cm without any interstice, as shown in Figure 83. The laminate was fixed using a polyethylene clamp so that the laminated roll did not come out of the PVC tube or come loose. The laminate was retained in this state for 6 hours. Subsequently, the cable tie was removed and the laminate was unrolled from the PVC tube. Only the electrode was placed on a surface plate, and the heights L, 1 and L7 of a raised portion of the surface plate were measured to determine an average value. This value was used as the electrode strain index. In other words, a lower value means that the laminate is unlikely to deform.

[002736] When an expanded metal is used, there are two winding directions: the SW direction and the LW direction. In this test, the laminate was rolled in the SW direction.

[002737] Deformed electrodes (electrodes that did not return to their original flat state) were evaluated for smoothness after plastic deformation according to a method shown in Figure 84. That is, a deformed electrode was placed in a membrane sufficiently immersed in water. pure. One end of the electrode was attached, and the other raised end was pressed into the membrane to release a force, and an assessment was made as to whether the deformed electrode matched the membrane. (13) Assessment of membrane damage

[002738] As the membrane, an ion exchange membrane B below was used.

[002739] As reinforcement core materials, those obtained were used

699/803 by twisting strands of 100 denier polytetrafluoroethylene (PTFE) tape 900 times / m in a thread form (hereinafter referred to as PTFE threads). As warp sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. As weft sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m were used. First, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric with a thickness of 100 µm.

[002740] Next, a polymer (Al) of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.92 mg equivalent / g, and a polymer (B1) of a dry resin that was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF; SO, F and had an ion exchange capacity of 1.10 mg equivalent / g. Using these polymers (Al) and (B1), a two-layer film X in which the thickness of a polymer layer (Al) was 25 µm and the thickness of a polymer layer (B1) was 89 µm was obtained by a coextrusion matrix method T. As the ion exchange capacity of each polymer, the ion exchange capacity was shown in the case of hydrolysis of the precursors of the ion exchange group of each polymer for conversion into ion exchange groups.

[002741] Separately, a polymer (B2) of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF3SO, F and had an ion exchange capacity of 1 , 10 mg equivalent / g. This polymer was extruded in a single layer to obtain a Y film with a thickness of 20 µm.

[002742] Subsequently, the release paper, film Y, a

699/803 by twisting strands of 100 denier polytetrafluoroethylene (PTFE) tape 900 times / m in a thread form (hereinafter referred to as PTFE threads). As warp sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. As weft sacrifice yarns, yarns obtained by twisting eight strands of 35 denier polyethylene terephthalate (PET) 200 times / m were used. First, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric with a thickness of 100 µm.

[002740] Next, a polymer (Al) of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.92 mg equivalent / g, and a polymer (B1) of a dry resin that was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF; SO, F and had an ion exchange capacity of 1.10 mg equivalent / g. Using these polymers (Al) and (B1), a two-layer film X in which the thickness of a polymer layer (Al) was 25 µm and the thickness of a polymer layer (B1) was 89 µm was obtained by a coextrusion matrix method T. As the ion exchange capacity of each polymer, the ion exchange capacity was shown in the case of hydrolysis of the precursors of the ion exchange group of each polymer for conversion into ion exchange groups.

[002741] Separately, a polymer (B2) of a dry resin was provided which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF; CF3SO, F and had an ion exchange capacity of 1 , 10 mg equivalent / g. This polymer was extruded in a single layer to obtain a Y film with a thickness of 20 µm.

[002742] Subsequently, the release paper, film Y, a

700/803 reinforcement material and film X were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate temperature of 225ºC and a reduced pressure degree of 0.022 MPa for two minutes, and then the release paper was removed to obtain a composite membrane. The resulting composite membrane was immersed in an aqueous solution comprising dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) for one hour for saponification. Then, the membrane was immersed in 0.5SN NaOH for one hour to replace the fons attached to the ion exchange groups with Na and then washed with water. In addition, the membrane was dried at 60ºC.

[002743] Additionally, a polymer (B3) of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.05 mg equivalent / g was hydrolyzed and then transformed into an acid type with hydrochloric acid. Zirconium oxide particles with an average particle size of primary particles of 0.02 µm were added to a mixed solution of water and ethanol 50/50 (mass ratio) in which the polymer (B3 ') of this acid type was dissolved in a proportion of 5% by mass so that the mass ratio of the polymer (B3 ') to the zirconium oxide particles was 20/80. Subsequently, the polymer (B3 ') was dispersed in a suspension of the zirconium oxide particles with a ball mill to obtain a suspension.

[002744] This suspension was applied by a spray method on both surfaces of the ion exchange and dry membrane to obtain an ion exchange membrane B with a coating layer containing the polymer (B3 ') and the oxide particles of zirconium. The coating density of zirconium oxide measured by X-ray fluorescence measurement was 0.35 mg / em ?.

[002745] The anode used was the same as for (9) Electrolytic evaluation.

700/803 reinforcement material and film X were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate temperature of 225ºC and a reduced pressure degree of 0.022 MPa for two minutes, and then the release paper was removed to obtain a composite membrane. The resulting composite membrane was immersed in an aqueous solution comprising dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) for one hour for saponification. Then, the membrane was immersed in 0.5SN NaOH for one hour to replace the fons attached to the ion exchange groups with Na and then washed with water. In addition, the membrane was dried at 60ºC.

[002743] Additionally, a polymer (B3) of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.05 mg equivalent / g was hydrolyzed and then transformed into an acid type with hydrochloric acid. Zirconium oxide particles with an average particle size of primary particles of 0.02 µm were added to a mixed solution of water and ethanol 50/50 (mass ratio) in which the polymer (B3 ') of this acid type was dissolved in a proportion of 5% by mass so that the mass ratio of the polymer (B3 ') to the zirconium oxide particles was 20/80. Subsequently, the polymer (B3 ') was dispersed in a suspension of the zirconium oxide particles with a ball mill to obtain a suspension.

[002744] This suspension was applied by a spray method on both surfaces of the ion exchange and dry membrane to obtain an ion exchange membrane B with a coating layer containing the polymer (B3 ') and the oxide particles of zirconium. The coating density of zirconium oxide measured by X-ray fluorescence measurement was 0.35 mg / em ?.

[002745] The anode used was the same as for (9) Electrolytic evaluation.

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[002746] The cathode used was one described in each of the Examples and Comparative Examples. The collector, mattress and feeding conductor of the cathodic chamber used were the same as in (9) Electrolytic evaluation. That is, a zero interstice structure was provided by the use of Ni mesh as the feed conductor and the repulsive force of the mattress as the elastic metal body. The gaskets used were the same as for (9) Electrolytic evaluation. As a membrane, ion exchange membrane B produced by the method mentioned above was used. That is, an electrolyzer equivalent to that of (9) was provided, except that the laminate of the ion exchange membrane B and the electrolysis electrode were sandwiched between a pair of gaskets.

[002747] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and the cathodic chamber was adjusted so that the temperature in each electrolytic cell reached 70ºC. Common salt electrolysis was carried out at a current density of 8 kKA / m ?. Electrolysis was interrupted 12 hours after the start of electrolysis, and the ion exchange membrane B was removed and observed for its damage condition.

[002748] "o" means no damage. "X" means that damage was present on the substantially entire surface of the ion exchange membrane. (14) Electrode ventilation resistance

[002749] The ventilation resistance of the electrode was measured using a KES-F8 air permeability tester (trade name, KATO TECH CO., LTD.). The unit for the ventilation resistance value is kKPa-s / m. The measurement was repeated 5 times and the average value was listed in Table 7. The measurement was conducted following two conditions. The temperature of the measuring chamber was 24ºC and the relative humidity was 32%.

701/803

[002746] The cathode used was one described in each of the Examples and Comparative Examples. The collector, mattress and feeding conductor of the cathodic chamber used were the same as in (9) Electrolytic evaluation. That is, a zero interstice structure was provided by the use of Ni mesh as the feed conductor and the repulsive force of the mattress as the elastic metal body. The gaskets used were the same as for (9) Electrolytic evaluation. As a membrane, ion exchange membrane B produced by the method mentioned above was used. That is, an electrolyzer equivalent to that of (9) was provided, except that the laminate of the ion exchange membrane B and the electrolysis electrode were sandwiched between a pair of gaskets.

[002747] The electrolytic cell above was used to perform the electrolysis of common salt. The brine concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The concentration of sodium hydroxide in the cathodic chamber was adjusted to 32% by mass. The temperature in the anodic chamber and the cathodic chamber was adjusted so that the temperature in each electrolytic cell reached 70ºC. Common salt electrolysis was carried out at a current density of 8 kKA / m ?. Electrolysis was interrupted 12 hours after the start of electrolysis, and the ion exchange membrane B was removed and observed for its damage condition.

[002748] "o" means no damage. "X" means that damage was present on the substantially entire surface of the ion exchange membrane. (14) Electrode ventilation resistance

[002749] The ventilation resistance of the electrode was measured using a KES-F8 air permeability tester (trade name, KATO TECH CO., LTD.). The unit for the ventilation resistance value is kKPa-s / m. The measurement was repeated 5 times and the average value was listed in Table 7. The measurement was conducted following two conditions. The temperature of the measuring chamber was 24ºC and the relative humidity was 32%.

702/803 “Measuring condition 1 (ventilation resistance 1) Piston speed: 0.2 cm / s Ventilation volume: 0.4 cc / in? / S Measuring range: SENSE L (low) Sample size: 50 mm x 50 mm “Measuring condition 2 (ventilation resistance 2) Piston speed: 2 cm / s Ventilation volume: 4 cc / in? / S Measuring range: SENSE M (high) or H (high) Size sample size: 50 mm x 50 mm [Example 4-1]

[002750] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 16 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002751] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 49%.

[002752] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002753] A vat containing the above coating liquid was

702/803 “Measuring condition 1 (ventilation resistance 1) Piston speed: 0.2 cm / s Ventilation volume: 0.4 cc / in? / S Measuring range: SENSE L (low) Sample size: 50 mm x 50 mm “Measuring condition 2 (ventilation resistance 2) Piston speed: 2 cm / s Ventilation volume: 4 cc / in? / S Measuring range: SENSE M (high) or H (high) Size sample size: 50 mm x 50 mm [Example 4-1]

[002750] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 16 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002751] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 49%.

[002752] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002753] A vat containing the above coating liquid was

703/803 placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced in Example 4-1 was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface. The thickness was the total thickness of ruthenium oxide and cerium oxide.

[002754] The results of measuring the adhesive force of the electrode produced by the method above are shown in Table 7. A sufficient adhesive force was observed.

[002755] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002756] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

703/803 placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced in Example 4-1 was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface. The thickness was the total thickness of ruthenium oxide and cerium oxide.

[002754] The results of measuring the adhesive force of the electrode produced by the method above are shown in Table 7. A sufficient adhesive force was observed.

[002755] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002756] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

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[002757] The electrode produced by the above method was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was placed in an opposite position in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane A (size: 160 mm x 160 mm), produced in [Method (1)] and balanced with a aqueous solution of 0.1 N NaOH and allowed to adhere to it through the surface tension of the aqueous solution.

[002758] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002759] The electrode integrated into the above membrane was sandwiched between the anode cell and the cathode cell in such a way that the surface on which the electrode was affixed was left facing the side of the cathode chamber. In the sectional structure, the collector, mattress, nickel mesh feed conductor, electrode, membrane and anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure.

[002760] The resulting electrode was subjected to electrolytic evaluation. The results are shown in Table 7.

[002761] The electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "o".

[002762] When the amount of coating after electrolysis has been

704/803

[002757] The electrode produced by the above method was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The rough surface of the electrode was placed in an opposite position in a substantial central position on the side of the carboxylic acid layer of the ion exchange membrane A (size: 160 mm x 160 mm), produced in [Method (1)] and balanced with a aqueous solution of 0.1 N NaOH and allowed to adhere to it through the surface tension of the aqueous solution.

[002758] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the electrode, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002759] The electrode integrated into the above membrane was sandwiched between the anode cell and the cathode cell in such a way that the surface on which the electrode was affixed was left facing the side of the cathode chamber. In the sectional structure, the collector, mattress, nickel mesh feed conductor, electrode, membrane and anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure.

[002760] The resulting electrode was subjected to electrolytic evaluation. The results are shown in Table 7.

[002761] The electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "o".

[002762] When the amount of coating after electrolysis has been

705/803 measured by X-ray fluorescence analysis (XRF), substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4-2]

[002763] In Example 4-2, an electrolytic nickel blade with a gauge thickness of 22 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 0.96 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002764] The thickness of the electrode was 29 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[002765] Sufficient adhesive strength has been observed.

[002766] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002767] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0033 (kPa-s / m) in the condition of measurement 2.

705/803 measured by X-ray fluorescence analysis (XRF), substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4-2]

[002763] In Example 4-2, an electrolytic nickel blade with a gauge thickness of 22 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 0.96 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002764] The thickness of the electrode was 29 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[002765] Sufficient adhesive strength has been observed.

[002766] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002767] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0033 (kPa-s / m) in the condition of measurement 2.

706/803

[002768] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". The damage to the membrane was also rated as good: "0".

[002769] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4-3]

[002770] In Example 4-3, an electrolytic nickel blade with a gauge thickness of 30 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 1.38 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002771] The thickness of the electrode was 38 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface.

[002772] Sufficient adhesive strength has been observed.

[002773] When an electrode deformation test was performed, the average value of L, and L, was O mm. The electrode was found to have a

706/803

[002768] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". The damage to the membrane was also rated as good: "0".

[002769] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4-3]

[002770] In Example 4-3, an electrolytic nickel blade with a gauge thickness of 30 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to roughness treatment by electroplating with electrolytic nickel. The average arithmetic roughness Ra of the rough surface was 1.38 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 44%. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002771] The thickness of the electrode was 38 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm. The coating was also formed on the non-roughened surface.

[002772] Sufficient adhesive strength has been observed.

[002773] When an electrode deformation test was performed, the average value of L, and L, was O mm. The electrode was found to have a

707/803 wide region of elastic deformation.

[002774] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002775] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002776] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4-4]

[002777] In Example 4-4, an electrolytic nickel blade with a gauge thickness of 16 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 75%. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002778] The thickness of the electrode was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

707/803 wide region of elastic deformation.

[002774] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002775] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002776] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4-4]

[002777] In Example 4-4, an electrolytic nickel blade with a gauge thickness of 16 µm was used as a substrate for the electrode for cathode electrolysis. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 75%. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002778] The thickness of the electrode was 24 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

708/803

[002779] Sufficient adhesive strength has been observed.

[002780] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002781] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002782] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002783] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4-5]

[002784] In Example 4-5, an electrolytic nickel blade with a gauge thickness of 20 µm was provided as a substrate for the electrode for cathode electrolysis. Both surfaces of this nickel blade were subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.96 µm. Both surfaces had the same roughness. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 49%. Except as described above, the evaluation was carried out in the same manner as in Example 4-1, and

708/803

[002779] Sufficient adhesive strength has been observed.

[002780] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002781] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002782] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002783] When the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on the rough surface, and the coating on the non-rough surface was reduced. This indicates that the surface opposite the membrane (rough surface) contributes to electrolysis and the other surface not opposite the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4-5]

[002784] In Example 4-5, an electrolytic nickel blade with a gauge thickness of 20 µm was provided as a substrate for the electrode for cathode electrolysis. Both surfaces of this nickel blade were subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.96 µm. Both surfaces had the same roughness. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The opening ratio was 49%. Except as described above, the evaluation was carried out in the same manner as in Example 4-1, and

709/803 results are shown in Table 7.

[002785] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm. The coating was also formed on the non-roughened surface.

[002786] Sufficient adhesive strength has been observed.

[002787] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002788] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002789] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002790] Additionally, when the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on both surfaces. In consideration of the comparison with Examples 4-1 to 4-4, this indicates that the other surface not opposed to the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4-6]

[002791] In Example 4-6, the evaluation was carried out in the same way as in Example 4-1, except that the coating of the substrate for the electrode for electrode cathode was carried out by ion galvanization, and the results are shown in Table 7 In ion galvanizing, the film formation was carried out using a heating temperature of 200ºC and Ru metal target under an argon / oxygen atmosphere at a pressure of formation

709/803 results are shown in Table 7.

[002785] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm. The coating was also formed on the non-roughened surface.

[002786] Sufficient adhesive strength has been observed.

[002787] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002788] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0023 (kPa-s / m) in the condition of measurement 2.

[002789] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0".

[002790] Additionally, when the amount of coating after electrolysis was measured by XRF, substantially 100% of the coating remained on both surfaces. In consideration of the comparison with Examples 4-1 to 4-4, this indicates that the other surface not opposed to the membrane can achieve satisfactory electrolytic performance when the amount of coating is small or no coating is present. [Example 4-6]

[002791] In Example 4-6, the evaluation was carried out in the same way as in Example 4-1, except that the coating of the substrate for the electrode for electrode cathode was carried out by ion galvanization, and the results are shown in Table 7 In ion galvanizing, the film formation was carried out using a heating temperature of 200ºC and Ru metal target under an argon / oxygen atmosphere at a film formation pressure of 7 x 10? Pa. The coating formed was ruthenium oxide.

[002792] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002793] Sufficient adhesive strength has been observed.

[002794] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002795] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

[002796] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-7]

[002797] In Example 4-7, the electrode substrate for cathode electrolysis was produced by an electroforming method. The photomask had a shape formed by a vertical and horizontal arrangement of 0.485 mm x 0.485 mm square in a range of 0.15 mm. Exposure, development and electroplating were performed sequentially to obtain a porous nickel film with a gauge thickness of 20 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002798] The thickness of the electrode was 37 µm. The film layer thickness of 7 x 10? Pa. The coating formed was ruthenium oxide.

[002792] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002793] Sufficient adhesive strength has been observed.

[002794] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002795] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2.

[002796] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-7]

[002797] In Example 4-7, the electrode substrate for cathode electrolysis was produced by an electroforming method. The photomask had a shape formed by a vertical and horizontal arrangement of 0.485 mm x 0.485 mm square in a range of 0.15 mm. Exposure, development and electroplating were performed sequentially to obtain a porous nickel film with a gauge thickness of 20 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.71 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002798] The thickness of the electrode was 37 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 17 µm.

[002799] Sufficient adhesive strength has been observed.

[002800] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002801] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002802] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-8]

[002803] In Example 4-8, the electrode substrate for cathode electrolysis was produced by an electroforming method. The substrate had a gauge thickness of 50 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.73 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002804] The thickness of the electrode was 60 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002805] Sufficient adhesive strength has been observed.

[002806] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

catalytic, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 17 µm.

[002799] Sufficient adhesive strength has been observed.

[002800] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002801] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002802] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-8]

[002803] In Example 4-8, the electrode substrate for cathode electrolysis was produced by an electroforming method. The substrate had a gauge thickness of 50 µm and an opening ratio of 56%. The arithmetic mean roughness Ra of the surface was 0.73 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002804] The thickness of the electrode was 60 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002805] Sufficient adhesive strength has been observed.

[002806] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002807] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002808] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-9]

[002809] In Example 4-9, a non-woven nickel fabric with a gauge thickness of 150 µm and a void ratio of 76% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrolyte electrode cathode. The nonwoven fabric had a nickel fiber diameter of about 40 µm and a base weight of 300 g / m2. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002810] The thickness of the electrode was 165 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 15 µm.

[002811] Sufficient adhesive strength has been observed.

[002812] When an electrode deformation test was performed, the average value of L, and L, was 29 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002813] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0612 (kPa-s / m) in the condition of measurement 2.

[002807] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0032 (kPa-s / m) in the condition of measurement 2.

[002808] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-9]

[002809] In Example 4-9, a non-woven nickel fabric with a gauge thickness of 150 µm and a void ratio of 76% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrolyte electrode cathode. The nonwoven fabric had a nickel fiber diameter of about 40 µm and a base weight of 300 g / m2. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002810] The thickness of the electrode was 165 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 15 µm.

[002811] Sufficient adhesive strength has been observed.

[002812] When an electrode deformation test was performed, the average value of L, and L, was 29 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002813] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0612 (kPa-s / m) in the condition of measurement 2.

[002814] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 4-10]

[002815] In Example 4-10, a nickel nonwoven fabric with a gauge thickness of 200 µm and a void ratio of 72% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrolyte electrode cathode. The non-woven fabric had a nickel fiber diameter of about 40 µm and a base weight of 500 g / m2. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002816] The thickness of the electrode was 215 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 15 µm.

[002817] Sufficient adhesive strength has been observed.

[002818] When an electrode deformation test was performed, the average value of L, and L, was 40 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002819] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0164 (kPa-s / m) in the condition of measurement 2.

[002820] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode

[002814] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0". [Example 4-10]

[002815] In Example 4-10, a nickel nonwoven fabric with a gauge thickness of 200 µm and a void ratio of 72% (manufactured by NIKKO TECHNO, Ltd.) was used as a substrate for the electrolyte electrode cathode. The non-woven fabric had a nickel fiber diameter of about 40 µm and a base weight of 500 g / m2. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002816] The thickness of the electrode was 215 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 15 µm.

[002817] Sufficient adhesive strength has been observed.

[002818] When an electrode deformation test was performed, the average value of L, and L, was 40 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002819] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0164 (kPa-s / m) in the condition of measurement 2.

[002820] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode

714/803 had a “2” handling property and was determined to be manipulable as a large laminate. The damage to the membrane was rated as good: "0". [Example 4-11]

[002821] In Example 4-11, a foamed nickel with a gauge thickness of 200 µm and a void ratio of 72% (manufactured by Mitsubishi Materials Corporation) was used as the substrate for the electrode for cathode electrolysis. Except as described above, the evaluation was performed in the same way as in Example 4-1, and the results are shown in Table

7.

[002822] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002823] Sufficient adhesive strength has been observed.

[002824] When an electrode deformation test was performed, the average value of L, and L, was 17 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002825] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0402 (kPa-s / m) in the condition of measurement 2.

[002826] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0".

714/803 had a “2” handling property and was determined to be manipulable as a large laminate. The damage to the membrane was rated as good: "0". [Example 4-11]

[002821] In Example 4-11, a foamed nickel with a gauge thickness of 200 µm and a void ratio of 72% (manufactured by Mitsubishi Materials Corporation) was used as the substrate for the electrode for cathode electrolysis. Except as described above, the evaluation was performed in the same way as in Example 4-1, and the results are shown in Table

7.

[002822] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002823] Sufficient adhesive strength has been observed.

[002824] When an electrode deformation test was performed, the average value of L, and L, was 17 mm, and the electrode did not return to the original flat state. Then, when the smoothness after the plastic deformation was evaluated, the electrode conformed to the membrane due to the surface tension. Thus, it was observed that the electrode was able to contact the membrane by a small force, even if the electrode was plastically deformed and that electrode had a satisfactory handling property.

[002825] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0402 (kPa-s / m) in the condition of measurement 2.

[002826] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode had a “2” manipulation property and was determined to be manipulable like a large laminate. The damage to the membrane was rated as good: "0".

715/803 [Example 4-12]

[002827] In Example 4-12, a 200 mesh nickel mesh with a line diameter of 50 µm, a gauge thickness of 100 µm and an opening ratio of 37% was used as a substrate for the electrolyte of the electrode. cathode. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 4-12, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The average arithmetic roughness Ra of a piece of wire of the wire mesh was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002828] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002829] Sufficient adhesive strength has been observed.

[002830] When an electrode deformation test was performed, the average value of L, and L, was 0.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002831] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0154 (kPa-s / m) in the condition of measurement 2.

[002832] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". Membrane damage

715/803 [Example 4-12]

[002827] In Example 4-12, a 200 mesh nickel mesh with a line diameter of 50 µm, a gauge thickness of 100 µm and an opening ratio of 37% was used as a substrate for the electrolyte of the electrode. cathode. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 4-12, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The average arithmetic roughness Ra of a piece of wire of the wire mesh was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002828] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002829] Sufficient adhesive strength has been observed.

[002830] When an electrode deformation test was performed, the average value of L, and L, was 0.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002831] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0154 (kPa-s / m) in the condition of measurement 2.

[002832] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good as "1". Membrane damage

716/803 was also rated as good: “0”. [Example 4-13]

[002833] In Example 4-13, a 150 mesh nickel mesh with a line diameter of 65 µm, a gauge thickness of 130 µm and an opening ratio of 38% was used as a substrate for the electrolyte of the electrode. cathode. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 4-13, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.66 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the above assessment was performed in the same manner as in Example 4- 1, and the results are shown in Table 7.

[002834] The thickness of the electrode was 133 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 3 µm.

[002835] Sufficient adhesive strength has been observed.

[002836] When an electrode deformation test was performed, the average value of L, and L, was 6.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002837] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0124 (kPa-s / m) in the condition of measurement 2.

[002838] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode

716/803 was also rated as good: “0”. [Example 4-13]

[002833] In Example 4-13, a 150 mesh nickel mesh with a line diameter of 65 µm, a gauge thickness of 130 µm and an opening ratio of 38% was used as a substrate for the electrolyte of the electrode. cathode. A pickling treatment was carried out with grain size alumina number 320. The pickling treatment did not change the opening ratio. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 4-13, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.66 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the above assessment was performed in the same manner as in Example 4- 1, and the results are shown in Table 7.

[002834] The thickness of the electrode was 133 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 3 µm.

[002835] Sufficient adhesive strength has been observed.

[002836] When an electrode deformation test was performed, the average value of L, and L, was 6.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002837] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0124 (kPa-s / m) in the condition of measurement 2.

[002838] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The electrode

717/803 had a “2” handling property and was determined to be manipulable as a large laminate. The damage to the membrane was also rated as good: "0". [Example 4-14]

[002839] In Example 4-14, a substrate identical to that of Example 4-3 (gauge thickness of 30 µm and an opening ratio of 44%) was used as the substrate for the electrode for cathode electrolysis. The electrolytic evaluation was carried out with a structure identical to that of Example 4-1, except that no nickel mesh feed conductor was included. That is, in the sectional structure of the cell, the collector, the mattress, the electrode integrated into the membrane and the anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the mattress serves as the conductor feed. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002840] Sufficient adhesive strength has been observed.

[002841] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002842] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002843] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-15]

[002844] In Example 4-15, a substrate identical to that of Example 4-3 (gauge thickness of 30 µm and an opening ratio of 44%) was used

717/803 had a “2” handling property and was determined to be manipulable as a large laminate. The damage to the membrane was also rated as good: "0". [Example 4-14]

[002839] In Example 4-14, a substrate identical to that of Example 4-3 (gauge thickness of 30 µm and an opening ratio of 44%) was used as the substrate for the electrode for cathode electrolysis. The electrolytic evaluation was carried out with a structure identical to that of Example 4-1, except that no nickel mesh feed conductor was included. That is, in the sectional structure of the cell, the collector, the mattress, the electrode integrated into the membrane and the anode are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the mattress serves as the conductor feed. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002840] Sufficient adhesive strength has been observed.

[002841] When an electrode deformation test was performed, the average value of L, and L, was 0 mm. It was found that the electrode had a wide region of elastic deformation.

[002842] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002843] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-15]

[002844] In Example 4-15, a substrate identical to that of Example 4-3 (gauge thickness of 30 µm and an opening ratio of 44%) was used

718/803 as a substrate for the electrode for electrolysis of the cathode. The cathode used in Reference Example 1, which was degraded and had an intensified electrolytic voltage, was placed instead of the nickel mesh feed conductor. With the exception of that described above, the electrolyte evaluation was carried out with a structure identical to that of Example 4-1. That is, in the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage (serves as a supply conductor), the cathode, the membrane and the anode are arranged in the order mentioned from the side of the cathodic chamber to form a zero-interstice structure, and the cathode that is degraded and has an intensified electrolytic voltage serves as the supply conductor. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002845] Sufficient adhesive strength has been observed.

[002846] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002847] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002848] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-16]

[002849] A titanium blade with a gauge thickness of 20 µm was provided as a substrate for the electrode for electrolysis of the anode. Both surfaces of the titanium sheet were subjected to a roughness treatment. A porous sheet was formed by perforating that sheet

718/803 as a substrate for the electrode for electrolysis of the cathode. The cathode used in Reference Example 1, which was degraded and had an intensified electrolytic voltage, was placed instead of the nickel mesh feed conductor. With the exception of that described above, the electrolyte evaluation was carried out with a structure identical to that of Example 4-1. That is, in the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage (serves as a supply conductor), the cathode, the membrane and the anode are arranged in the order mentioned from the side of the cathodic chamber to form a zero-interstice structure, and the cathode that is degraded and has an intensified electrolytic voltage serves as the supply conductor. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002845] Sufficient adhesive strength has been observed.

[002846] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002847] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2.

[002848] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-16]

[002849] A titanium blade with a gauge thickness of 20 µm was provided as a substrate for the electrode for electrolysis of the anode. Both surfaces of the titanium sheet were subjected to a roughness treatment. A porous sheet was formed by perforating that sheet

719/803 titanium with circular perforation holes. The diameter of the hole was 1 mm, and the opening ratio was 14%. The arithmetic mean roughness Ra of the surface was 0.37 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002850] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anodic coating liquid.

[002851] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, baking operations

719/803 titanium with circular perforation holes. The diameter of the hole was 1 mm, and the opening ratio was 14%. The arithmetic mean roughness Ra of the surface was 0.37 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[002850] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anodic coating liquid.

[002851] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, baking operations

720/803 preliminary and cooking was performed repeatedly, and then cooking at 520ºC was performed for one hour.

[002852] The electrode produced by the above method was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The cut electrode was allowed to adhere through the surface tension of the aqueous solution to a substantial central position on the side of the sulfonic acid layer of the ion exchange membrane A (size: 160 mm x 160 mm) produced in [Method (1)] and balanced with a 0.1 N aqueous solution of NaOH.

[002853] The cathode was prepared in the following procedure. First, a 40 mesh nickel wire mesh with a line diameter of 150 µm was provided as a substrate. After stripping with alumina as a pretreatment, the wire mesh was immersed in 6 N hydrochloric acid for 5 minutes, washed sufficiently with pure, dry water.

[002854] Then a solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and cerium chloride (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the ruthenium element and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002855] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on top of it, and a roll of PVC was additionally

720/803 preliminary and cooking was performed repeatedly, and then cooking at 520ºC was performed for one hour.

[002852] The electrode produced by the above method was cut to a size of 95 mm long and 110 mm wide for electrolytic evaluation. The cut electrode was allowed to adhere through the surface tension of the aqueous solution to a substantial central position on the side of the sulfonic acid layer of the ion exchange membrane A (size: 160 mm x 160 mm) produced in [Method (1)] and balanced with a 0.1 N aqueous solution of NaOH.

[002853] The cathode was prepared in the following procedure. First, a 40 mesh nickel wire mesh with a line diameter of 150 µm was provided as a substrate. After stripping with alumina as a pretreatment, the wire mesh was immersed in 6 N hydrochloric acid for 5 minutes, washed sufficiently with pure, dry water.

[002854] Then a solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and cerium chloride (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the ruthenium element and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002855] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on top of it, and a roll of PVC was additionally

721/803 placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was performed at 300ºC for 3 minutes and cooking at 550ºC for 10 minutes. Then, cooking was carried out at 550ºC for one hour. A series of these coating, drying, preliminary cooking and cooking operations were repeated.

[002856] As collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. The cathode produced by the above method was placed on it, and a rope made of Teflon (R) was used to fix the four corners of the mesh to the collector.

[002857] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the anodes, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002858] The anode used in Reference Example 3, which was degraded and had an intensified electrolytic voltage, was attached to the anode cell by welding, and the electrode integrated into the above membrane was placed between the anode cell and the cathode cell so that the surface on which the electrode was attached was left facing the side of the anodic chamber. That is, in the sectional structure of the cell, the collector, the mattress, the cathode, the membrane, the porous titanium sheet anode and the anode that has been degraded and

721/803 placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was performed at 300ºC for 3 minutes and cooking at 550ºC for 10 minutes. Then, cooking was carried out at 550ºC for one hour. A series of these coating, drying, preliminary cooking and cooking operations were repeated.

[002856] As collector of the cathodic chamber, an expanded nickel metal was used. The collector was 95 mm long x 110 mm wide. As an elastic metal body, a mattress formed by a fine knitted nickel wire was used. The mattress as the elastic metal body was placed in the collector. The cathode produced by the above method was placed on it, and a rope made of Teflon (R) was used to fix the four corners of the mesh to the collector.

[002857] Even when the four corners of the membrane portion of the electrode integrated into the membrane, formed by the integration of the membrane with the anodes, were clamped and suspended so that the electrode integrated into the membrane was in parallel with the ground, allowing the electrode if it returned to the side of the ground, the electrode did not come loose or was not moved. In addition, when both ends of one side were clamped and suspended so that the electrode integrated into the membrane was vertical in relation to the ground, the electrode did not come loose or was not moved.

[002858] The anode used in Reference Example 3, which was degraded and had an intensified electrolytic voltage, was attached to the anode cell by welding, and the electrode integrated into the above membrane was placed between the anode cell and the cathode cell so that the surface on which the electrode was attached was left facing the side of the anodic chamber. That is, in the sectional structure of the cell, the collector, the mattress, the cathode, the membrane, the anode of the porous titanium foil and the anode that was degraded and had an intensified electrolytic voltage were arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure. The anode that was degraded and had an intensified electrolytic voltage served as the supply conductor. The porous titanium blade anode and the anode that was degraded and had an intensified electrolytic voltage were only in physical contact with each other and were not fixed to each other by welding.

[002859] The evaluation in this structure was performed in the same way as in Example 4-1, and the results are shown in Table 7.

[002860] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 6 µm.

[002861] Sufficient adhesive strength has been observed.

[002862] When an electrode deformation test was performed, the average value of L, and L, was 4 mm. It was found that the electrode had a wide region of elastic deformation.

[002863] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0060 (kPa-s / m) in the condition of measurement 2.

[002864] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-17]

[002865] In Example 4-17, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 30% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.37 µm. The measurement of the surface roughness was carried out under the same conditions as the measurement of the roughness had an intensified electrolytic voltage were arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure. The anode that was degraded and had an intensified electrolytic voltage served as the supply conductor. The porous titanium blade anode and the anode that was degraded and had an intensified electrolytic voltage were only in physical contact with each other and were not fixed to each other by welding.

[002859] The evaluation in this structure was performed in the same way as in Example 4-1, and the results are shown in Table 7.

[002860] The thickness of the electrode was 26 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 6 µm.

[002861] Sufficient adhesive strength has been observed.

[002862] When an electrode deformation test was performed, the average value of L, and L, was 4 mm. It was found that the electrode had a wide region of elastic deformation.

[002863] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0060 (kPa-s / m) in the condition of measurement 2.

[002864] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-17]

[002865] In Example 4-17, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 30% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.37 µm. The surface roughness measurement was performed under the same conditions as the roughness measurement

723/803 of the nickel plate surface submitted to pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002866] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002867] Sufficient adhesive strength has been observed.

[002868] When an electrode deformation test was performed, the average value of L, and L, was 5 mm. It was found that the electrode had a wide region of elastic deformation.

[002869] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2.

[002870] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-18]

[002871] In Example 4-18, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 42% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.38 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002872] The thickness of the electrode was 32 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 12 µm.

723/803 of the nickel plate surface submitted to pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002866] The thickness of the electrode was 30 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002867] Sufficient adhesive strength has been observed.

[002868] When an electrode deformation test was performed, the average value of L, and L, was 5 mm. It was found that the electrode had a wide region of elastic deformation.

[002869] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2.

[002870] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-18]

[002871] In Example 4-18, a titanium blade with a gauge thickness of 20 µm and an opening ratio of 42% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.38 µm. The surface roughness measurement was performed under the same conditions as the surface roughness measurement of the nickel plate subjected to pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002872] The thickness of the electrode was 32 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 12 µm.

724/803

[002873] Sufficient adhesive strength has been observed.

[002874] When an electrode deformation test was performed, the average value of L, and L, was 2.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002875] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0022 (kPa: s / m) in the condition of measurement 2.

[002876] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-19]

[002877] In Example 4-19, a titanium blade with a caliber thickness of 50 µm and an opening ratio of 47% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.40 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002878] The thickness of the electrode was 69 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 19 µm.

[002879] Sufficient adhesive strength has been observed.

[002880] When an electrode deformation test was performed, the average value of L, and L, was 8 mm. It was found that the electrode had a wide region of elastic deformation.

[002881] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in the condition of

724/803

[002873] Sufficient adhesive strength has been observed.

[002874] When an electrode deformation test was performed, the average value of L, and L, was 2.5 mm. It was found that the electrode had a wide region of elastic deformation.

[002875] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0022 (kPa: s / m) in the condition of measurement 2.

[002876] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-19]

[002877] In Example 4-19, a titanium blade with a caliber thickness of 50 µm and an opening ratio of 47% was used as a substrate for the electrode for anode electrolysis. The arithmetic mean roughness Ra of the surface was 0.40 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002878] The thickness of the electrode was 69 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 19 µm.

[002879] Sufficient adhesive strength has been observed.

[002880] When an electrode deformation test was performed, the average value of L, and L, was 8 mm. It was found that the electrode had a wide region of elastic deformation.

[002881] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in the condition of

725/803 measurement 1 and 0.0024 (kPa: s / m) in measurement condition 2.

[002882] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-20]

[002883] In Example 4-20, a titanium nonwoven fabric with a gauge thickness of 100 µm, a titanium fiber diameter of one, a base weight of 100 g / m? Was used, and an opening ratio 78% as a substrate for the electrode for electrolysis of the anode. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002884] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002885] Sufficient adhesive strength has been observed.

[002886] When an electrode deformation test was performed, the average value of L, and L, was 2 mm. It was found that the electrode had a wide region of elastic deformation.

[002887] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0228 (kPa-s / m) in the condition of measurement 2.

[002888] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-21]

[002889] In Example 4-21, a 150 mesh titanium wire mesh with a gauge thickness of 120 µm and a fiber diameter of

725/803 measurement 1 and 0.0024 (kPa: s / m) in measurement condition 2.

[002882] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-20]

[002883] In Example 4-20, a titanium nonwoven fabric with a gauge thickness of 100 µm, a titanium fiber diameter of one, a base weight of 100 g / m? Was used, and an opening ratio 78% as a substrate for the electrode for electrolysis of the anode. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002884] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002885] Sufficient adhesive strength has been observed.

[002886] When an electrode deformation test was performed, the average value of L, and L, was 2 mm. It was found that the electrode had a wide region of elastic deformation.

[002887] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0228 (kPa-s / m) in the condition of measurement 2.

[002888] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-21]

[002889] In Example 4-21, a 150 mesh titanium wire mesh with a gauge thickness of 120 µm and a fiber diameter of

726/803 titanium of about 60 µm as a substrate for the electrode for anode electrolysis. The opening ratio was 42%. A pickling treatment was carried out with grain size alumina number 320. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 4-21, a titanium plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. . The average arithmetic roughness Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002890] The thickness of the electrode was 140 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 20 µm.

[002891] Sufficient adhesive strength has been observed.

[002892] When an electrode deformation test was performed, the average value of L, and L, was 10 mm. It was found that the electrode had a wide region of elastic deformation.

[002893] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0132 (kPa-s / m) in the condition of measurement 2.

[002894] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-22]

[002895] In Example 4-22, an anode was used which was degraded and

726/803 titanium of about 60 µm as a substrate for the electrode for anode electrolysis. The opening ratio was 42%. A pickling treatment was carried out with grain size alumina number 320. It is difficult to measure the roughness of the metal mesh surface. Thus, in Example 4-21, a titanium plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. . The average arithmetic roughness Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002890] The thickness of the electrode was 140 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 20 µm.

[002891] Sufficient adhesive strength has been observed.

[002892] When an electrode deformation test was performed, the average value of L, and L, was 10 mm. It was found that the electrode had a wide region of elastic deformation.

[002893] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0132 (kPa-s / m) in the condition of measurement 2.

[002894] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: "0". [Example 4-22]

[002895] In Example 4-22, an anode was used which was degraded and had an intensified electrolytic voltage in the same manner as in Example 4-16 as the anode feed conductor, and a titanium non-woven fabric identical to that of Example 4-20 as an anode. A cathode that was degraded and had an intensified electrolytic voltage was used in the same way as in Example 4-15 as the cathode supply conductor, and a nickel-plated electrode identical to Example 4-3 was used as the cathode. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified tension, the cathode of the porous nickel blade, the membrane, the anode of the titanium non-woven fabric, and the anode that was degraded and had an intensified electrolytic voltage are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the cathode and anode which is degraded and has an intensified electrolytic voltage serve as the supply conductor. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002896] The thickness of the electrode (anode) was 114 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode (anode) thickness, was 14 µm. The thickness of the electrode (cathode) was 38 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the substrate for the electrode from the electrode thickness (cathode), was 8 µm.

[002897] Sufficient adhesive force was observed both on the anode and on the cathode.

[002898] When a deformation test of the electrode (anode) was performed, the average value of L, and L7 was 2 mm. When an electrode deformation test (cathode) was performed, the average value of L, and L, was 0 mm.

[002899] When the ventilation resistance of the electrode (anode) was had an electrolytic voltage intensified in the same way as in Example 4-16 as the anode supply conductor, and a titanium non-woven fabric identical to Example 4-20 as anode. A cathode that was degraded and had an intensified electrolytic voltage was used in the same way as in Example 4-15 as the cathode supply conductor, and a nickel-plated electrode identical to Example 4-3 was used as the cathode. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified tension, the cathode of the porous nickel blade, the membrane, the anode of the titanium non-woven fabric, and the anode that was degraded and had an intensified electrolytic voltage are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure, and the cathode and anode which is degraded and has an intensified electrolytic voltage serve as the supply conductor. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002896] The thickness of the electrode (anode) was 114 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode (anode) thickness, was 14 µm. The thickness of the electrode (cathode) was 38 µm, and the thickness of the catalytic layer, which was determined by subtracting the thickness of the substrate for the electrode from the electrode thickness (cathode), was 8 µm.

[002897] Sufficient adhesive force was observed both on the anode and on the cathode.

[002898] When a deformation test of the electrode (anode) was performed, the average value of L, and L7 was 2 mm. When an electrode deformation test (cathode) was performed, the average value of L, and L, was 0 mm.

[002899] When the ventilation resistance of the electrode (anode) was

728/803 measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0228 (kPa-s / m) in measurement condition 2. When the ventilation resistance of the electrode (cathode) was measured, the ventilation resistance was 0.07 (kPa-s / m) or less in measurement condition 1 and 0.0027 (kKPa-s / m) in measurement condition 2.

[002900] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: “0” at both the anode and the cathode. In Example 4-22, the cathode and anodes were combined by affixing the cathode to one surface of the membrane and the anode to the other surface and subjecting them to membrane damage assessment. [Example 4-23]

[002901] In Example 4-23, a microporous membrane "Zirfon Perl UTP 500" manufactured by Agfa was used.

[002902] The Zirfon membrane was immersed in pure water for 12 hours or more and used for the test. Except as described above, the above assessment was performed in the same manner as in Example 4-3, and the results are shown in Table 7.

[002903] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002904] Similar to the case where an ion exchange membrane was used as a membrane, sufficient adhesive strength was observed. The microporous membrane was placed in close contact with the electrode through surface tension, and the manipulation property was good: “1”. [Reference example 1]

[002905] In Reference Example 1, a cathode was used as a cathode in a large electrolyzer for eight years, degraded and with a

728/803 measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0228 (kPa-s / m) in measurement condition 2. When the ventilation resistance of the electrode (cathode) was measured, the ventilation resistance was 0.07 (kPa-s / m) or less in measurement condition 1 and 0.0027 (kKPa-s / m) in measurement condition 2.

[002900] Additionally, the electrode had low voltage, high current efficiency and low salt concentration in caustic soda. The handling property was also good: “1”. The damage to the membrane was also rated as good: “0” at both the anode and the cathode. In Example 4-22, the cathode and anodes were combined by affixing the cathode to one surface of the membrane and the anode to the other surface and subjecting them to membrane damage assessment. [Example 4-23]

[002901] In Example 4-23, a microporous membrane "Zirfon Perl UTP 500" manufactured by Agfa was used.

[002902] The Zirfon membrane was immersed in pure water for 12 hours or more and used for the test. Except as described above, the above assessment was performed in the same manner as in Example 4-3, and the results are shown in Table 7.

[002903] When an electrode deformation test was performed, the average value of L, and L, was O mm. It was found that the electrode had a wide region of elastic deformation.

[002904] Similar to the case where an ion exchange membrane was used as a membrane, sufficient adhesive strength was observed. The microporous membrane was placed in close contact with the electrode through surface tension, and the manipulation property was good: “1”. [Reference example 1]

[002905] In Reference Example 1, a cathode was used as a cathode in a large electrolyzer for eight years, degraded and with a

729/803 intensified electrolytic voltage. The above cathode was placed instead of the nickel mesh feed conductor on the cathode chamber mattress, and the ion exchange membrane A produced in [Method (1)] was sandwiched between them. Then, electrolytic evaluation was performed. In Reference Example 1, no electrodes integrated into the membrane were used. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage, the ion exchange membrane A and the anodes were arranged in the order mentioned from the side of the cathode chamber to form a structure of zero interstice.

[002906] As a result of the electrolytic evaluation with this structure, the voltage was 3.04 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) 20 ppm. Consequently, due to the cathode degradation, the voltage was high. [Reference example 2]

[002907] In Reference Example 2, a nickel mesh feed conductor was used as the cathode. In other words, electrolysis was performed on a nickel mesh without a catalyst coating.

[002908] The nickel mesh cathode was placed on the mattress of the cathodic chamber, and the ion exchange membrane A produced in [Method (i)] was sandwiched between them. Then, electrolytic evaluation was performed. In the sectional structure of the electrical cell of Reference Example 2, the collector, mattress, nickel mesh, ion exchange membrane A and anodes were arranged in the order mentioned from the side of the cathode chamber to form an interstitial structure zero.

[002909] As a result of the electrolytic evaluation with this structure, the voltage was 3.38 V, the current efficiency was 97.7%, the concentration of common salt in the caustic soda (value converted into the base of 50%) 24 ppm. Consequently, the tension was high because the cathode catalyst was uncoated.

729/803 intensified electrolytic voltage. The above cathode was placed instead of the nickel mesh feed conductor on the cathode chamber mattress, and the ion exchange membrane A produced in [Method (1)] was sandwiched between them. Then, electrolytic evaluation was performed. In Reference Example 1, no electrodes integrated into the membrane were used. In the sectional structure of the cell, the collector, the mattress, the cathode that was degraded and had an intensified electrolytic voltage, the ion exchange membrane A and the anodes were arranged in the order mentioned from the side of the cathode chamber to form a structure of zero interstice.

[002906] As a result of the electrolytic evaluation with this structure, the voltage was 3.04 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) 20 ppm. Consequently, due to the cathode degradation, the voltage was high. [Reference example 2]

[002907] In Reference Example 2, a nickel mesh feed conductor was used as the cathode. In other words, electrolysis was performed on a nickel mesh without a catalyst coating.

[002908] The nickel mesh cathode was placed on the mattress of the cathodic chamber, and the ion exchange membrane A produced in [Method (i)] was sandwiched between them. Then, electrolytic evaluation was performed. In the sectional structure of the electrical cell of Reference Example 2, the collector, mattress, nickel mesh, ion exchange membrane A and anodes were arranged in the order mentioned from the side of the cathode chamber to form an interstitial structure zero.

[002909] As a result of the electrolytic evaluation with this structure, the voltage was 3.38 V, the current efficiency was 97.7%, the concentration of common salt in the caustic soda (value converted into the base of 50%) 24 ppm. Consequently, the tension was high because the cathode catalyst was uncoated.

730/803 [Reference example 3]

[002910] In Reference Example 3, an anode used as an anode in a large electrolyzer for about eight years was used, degraded and with an intensified electrolytic voltage.

[002911] In the sectional structure of the electrolytic cell of Reference Example 3, the collector, the mattress, the cathode, the ion exchange membrane À produced in [Method (1i)], and the anode that was degraded and had an electrolytic voltage intensified were arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure.

[002912] As a result of the electrolytic evaluation with this structure, the voltage was 3.18 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) of 22 ppm. Consequently, due to degradation of the anode, the voltage was high. [Example 4-24]

[002913] In Example 4-24, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 33% was used as substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-24, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.68 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

730/803 [Reference example 3]

[002910] In Reference Example 3, an anode used as an anode in a large electrolyzer for about eight years was used, degraded and with an intensified electrolytic voltage.

[002911] In the sectional structure of the electrolytic cell of Reference Example 3, the collector, the mattress, the cathode, the ion exchange membrane À produced in [Method (1i)], and the anode that was degraded and had an electrolytic voltage intensified were arranged in the order mentioned from the side of the cathodic chamber to form a zero interstice structure.

[002912] As a result of the electrolytic evaluation with this structure, the voltage was 3.18 V, the current efficiency was 97.0%, the concentration of common salt in the caustic soda (value converted into the base of 50%) of 22 ppm. Consequently, due to degradation of the anode, the voltage was high. [Example 4-24]

[002913] In Example 4-24, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 33% was used as substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-24, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.68 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

731/803

[002914] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002915] The mass per unit area was 67.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.05 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 64%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 22%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002916] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002917] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Example 4-25]

[002918] In Example 4-25, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 16% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-25, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the

731/803

[002914] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002915] The mass per unit area was 67.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.05 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 64%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 22%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002916] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002917] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Example 4-25]

[002918] In Example 4-25, a fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 16% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-25, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the

732/803 surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.604 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002919] The thickness of the electrode was 107 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm.

[002920] The mass per unit area was 78.1 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.04 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 37%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 25%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002921] When an electrode deformation test was performed, the average value of L, and L> was 18.5 mm.

[002922] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0176 (kPa-s / m) in the condition of measurement 2. [Example 4-26]

[002923] In Example 4-26, a fully laminated nickel expanded metal with a 100 µm gauge thickness and a 40% opening ratio was used as a substrate for the electrode for cathode electrolysis. a

732/803 surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.604 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002919] The thickness of the electrode was 107 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 7 µm.

[002920] The mass per unit area was 78.1 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.04 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 37%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 25%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002921] When an electrode deformation test was performed, the average value of L, and L> was 18.5 mm.

[002922] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0176 (kPa-s / m) in the condition of measurement 2. [Example 4-26]

[002923] In Example 4-26, a fully laminated nickel expanded metal with a 100 µm gauge thickness and a 40% opening ratio was used as a substrate for the electrode for cathode electrolysis. a

733/803 pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-26, a nickel plate with a thickness of 1 mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.70 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The substrate coating for the electrolysis electrode was carried out by ion plating in the same manner as in Example 4-6. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002924] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002925] The force applied per unit mass-unit area (1) was a small value like 0.07 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 80%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 32%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "3", which was also problematic. The membrane damage was rated “0”.

[002926] When an electrode deformation test was performed, the average value of L, and L> was 11 mm.

733/803 pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-26, a nickel plate with a thickness of 1 mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.70 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. The substrate coating for the electrolysis electrode was carried out by ion plating in the same manner as in Example 4-6. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002924] The thickness of the electrode was 110 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002925] The force applied per unit mass-unit area (1) was a small value like 0.07 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 80%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 32%. The portions in which the electrode came off the membrane increased. This is because there were problems where it was likely that the electrode would come off when the electrode integrated with the membrane was manipulated and that the electrode would come loose and fall off the membrane during manipulation. The handling property was "3", which was also problematic. The membrane damage was rated “0”.

[002926] When an electrode deformation test was performed, the average value of L, and L> was 11 mm.

734/803

[002927] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2. [Example 4-27]

[002928] In Example 4-27, a fully laminated nickel expanded metal with a 100 µm gauge thickness and an opening ratio of 58% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-27, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002929] The thickness of the electrode was 109 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 9 µm.

[002930] The force applied per unit mass-unit area (1) was a small value such as 0.06 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 69%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 39%. The portions in which the electrode came off the membrane increased. This is because there were problems where the electrode was likely to come off when the electrode integrated into the membrane was

734/803

[002927] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0030 (kPa-s / m) in the condition of measurement 2. [Example 4-27]

[002928] In Example 4-27, a fully laminated nickel expanded metal with a 100 µm gauge thickness and an opening ratio of 58% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-27, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002929] The thickness of the electrode was 109 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 9 µm.

[002930] The force applied per unit mass-unit area (1) was a small value such as 0.06 (N / mg: cm?). Thus, the result of the evaluation of the winding around the 280 mm diameter column (2) was 69%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 39%. The portions in which the electrode came off the membrane increased. This is because there were problems where the electrode was likely to come off when the electrode integrated into the membrane was

735/803 manipulated and that the electrode came loose and fell from the membrane during manipulation. The handling property was "3", which was also problematic. The membrane damage was rated “0”.

[002931] When an electrode deformation test was performed, the average value of L, and L> was 11.5 mm.

[002932] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2. [Example 4-28]

[002933] In Example 4-28, a nickel wire mesh with a gauge thickness of 300 µm and an opening ratio of 56% was used as a substrate for the electrode for cathode electrolysis. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 4-28, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. The arithmetic mean roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002934] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002935] The mass per unit area was 49.2 (mg / cm?). Thus, the result of the evaluation of the winding around the 280 mm column

735/803 manipulated and that the electrode came loose and fell from the membrane during manipulation. The handling property was "3", which was also problematic. The membrane damage was rated “0”.

[002931] When an electrode deformation test was performed, the average value of L, and L> was 11.5 mm.

[002932] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0028 (kPa-s / m) in the condition of measurement 2. [Example 4-28]

[002933] In Example 4-28, a nickel wire mesh with a gauge thickness of 300 µm and an opening ratio of 56% was used as a substrate for the electrode for cathode electrolysis. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 4-28, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. The arithmetic mean roughness Ra of the surface was 0.64 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-1, and the results are shown in Table 7.

[002934] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002935] The mass per unit area was 49.2 (mg / cm?). Thus, the result of the evaluation of the winding around the 280 mm column

736/803 diameter (2) was 88%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 42%. The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. When the large size electrode was actually operated, it was possible to evaluate the handling property as “3”. The membrane damage was rated “0”.

[002936] When an electrode deformation test was performed, the average value of L, and L> was 23 mm.

[002937] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in the condition of measurement 2. [Example 4-29]

[002938] In Example 4-29, a nickel wire mesh with a gauge thickness of 200 µm and an opening ratio of 37% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 4-29, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.65 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. With the exception of the above, the assessment of electrode electrolysis, the measurement results

736/803 diameter (2) was 88%, and the result of the evaluation of the winding around the 145 mm diameter column (3) was 42%. The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. When the large size electrode was actually operated, it was possible to evaluate the handling property as “3”. The membrane damage was rated “0”.

[002936] When an electrode deformation test was performed, the average value of L, and L> was 23 mm.

[002937] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in the condition of measurement 2. [Example 4-29]

[002938] In Example 4-29, a nickel wire mesh with a gauge thickness of 200 µm and an opening ratio of 37% was used as a substrate for the electrode for cathode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the wire mesh. Thus, in Example 4-29, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling treatment during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. . The arithmetic mean roughness Ra of the surface was 0.65 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. With the exception of the above, the assessment of electrode electrolysis, the measurement results

737/803 of the adhesive strength and adhesiveness were performed in the same manner as in Example 4-1. The results are shown in Table 7.

[002939] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002940] The mass per unit area was 56.4 (mg / cm?). Thus, the result of the method of assessing the winding around the 145 mm diameter column (3) was 63%, and the adhesion between the electrode and the membrane was poor. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. The membrane damage was rated “0”.

[002941] When an electrode deformation test was performed, the average value of L, and L> was 19 mm.

[002942] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0096 (kPa-s / m) in the condition of measurement 2. [Example 4-30]

[002943] In Example 4-30, a fully laminated titanium expanded metal with a gauge thickness of 500 µm and an opening ratio of 17% was used as a substrate for the electrode for electrolysis of the anode. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-30, a titanium plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness

737/803 of the adhesive strength and adhesiveness were performed in the same manner as in Example 4-1. The results are shown in Table 7.

[002939] The thickness of the electrode was 210 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 10 µm.

[002940] The mass per unit area was 56.4 (mg / cm?). Thus, the result of the method of assessing the winding around the 145 mm diameter column (3) was 63%, and the adhesion between the electrode and the membrane was poor. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated and because the electrode could come loose and fall off the membrane during manipulation. There was a problem with the handling property, which was rated “3”. The membrane damage was rated “0”.

[002941] When an electrode deformation test was performed, the average value of L, and L> was 19 mm.

[002942] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0096 (kPa-s / m) in the condition of measurement 2. [Example 4-30]

[002943] In Example 4-30, a fully laminated titanium expanded metal with a gauge thickness of 500 µm and an opening ratio of 17% was used as a substrate for the electrode for electrolysis of the anode. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-30, a titanium plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness

738/803 Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002944] The thickness of the electrode was 508 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002945] The mass per unit area was 152.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002946] When an electrode deformation test was carried out, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002947] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0072 (kPa-s / m) in the condition of measurement 2. [Example 4-31]

[002948] In Example 4-31, a fully rolled titanium expanded metal with a caliber thickness of 800 µm and an opening ratio of 8% was used as a substrate for the anode electrolysis electrode. a

738/803 Ra of the surface was 0.60 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the evaluation was carried out in the same way as in Example 4-16, and the results are shown in Table 7.

[002944] The thickness of the electrode was 508 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002945] The mass per unit area was 152.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002946] When an electrode deformation test was carried out, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002947] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0072 (kPa-s / m) in the condition of measurement 2. [Example 4-31]

[002948] In Example 4-31, a fully rolled titanium expanded metal with a caliber thickness of 800 µm and an opening ratio of 8% was used as a substrate for the anode electrolysis electrode. a

739/803 pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-31, a titanium plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.61 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the above assessment was performed in the same manner as in Example 4-16, and the results are shown in Table 7.

[002949] The thickness of the electrode was 808 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002950] The mass per unit area was 251.3 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002951] When an electrode deformation test was carried out, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

739/803 pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-31, a titanium plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The average arithmetic roughness Ra of the surface was 0.61 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the above assessment was performed in the same manner as in Example 4-16, and the results are shown in Table 7.

[002949] The thickness of the electrode was 808 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002950] The mass per unit area was 251.3 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because it was likely that the electrode would come off when the electrode integrated into the membrane was manipulated, the electrode would come loose and fall off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002951] When an electrode deformation test was carried out, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

740/803

[002952] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0172 (kPa-s / m) in the condition of measurement 2. [Example 4-32]

[002953] In Example 4-32, a fully laminated titanium expanded metal with a gauge thickness of 1000 µm and an opening ratio of 46% was used as a substrate for the electrode for anode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-32, a titanium plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.59 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the above assessment was performed in the same manner as in Example 4-16, and the results are shown in Table 7.

[002954] The thickness of the electrode was 1011 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 11 µm.

[002955] The mass per unit area was 245.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because the electrode was likely to come off

740/803

[002952] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0172 (kPa-s / m) in the condition of measurement 2. [Example 4-32]

[002953] In Example 4-32, a fully laminated titanium expanded metal with a gauge thickness of 1000 µm and an opening ratio of 46% was used as a substrate for the electrode for anode electrolysis. A pickling treatment was carried out with grain size alumina number 320. The opening ratio was not changed after the pickling treatment. It is difficult to measure the surface roughness of the expanded metal. Thus, in Example 4-32, a titanium plate with a thickness of | mm was subjected simultaneously to the pickling treatment during pickling, and the surface roughness of the titanium plate was taken as the surface roughness of the wire mesh. The arithmetic mean roughness Ra of the surface was 0.59 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment. Except as described above, the above assessment was performed in the same manner as in Example 4-16, and the results are shown in Table 7.

[002954] The thickness of the electrode was 1011 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 11 µm.

[002955] The mass per unit area was 245.5 (mg / in?). The force applied per unit mass-unit area (1) was a small value such as 0.01 (N / mg: cm?). Thus, the result of the evaluation of the winding around the column of 280 mm in diameter (2) was less than 5%, and the result of the evaluation of the winding around the column of 145 mm in diameter (3) was less than 5% . The portions in which the electrode came off the membrane increased. This is because the electrode was likely to come off

741/803 when the electrode integrated into the membrane was manipulated, the electrode came loose and fell off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002956] When a deformation test of the electrode was performed, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002957] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2. [Example 4-33]

[002958] In Example 4-33, a set of membrane electrodes was produced by thermal compression of an electrode on a membrane with reference to a prior art document (Examples of Japanese Patent Open to the Public No. 58-48686).

[002959] A fully laminated nickel expanded metal with a gauge thickness of 100 μm and an opening ratio of 33% was used as a substrate for the electrode for cathode electrolysis to perform electrode coating in the same manner as in Example 4- 1. Subsequently, an electrode surface was subjected to an inactivation treatment in the following procedure. Polyimide adhesive tape (Chukoh Chemical Industries, Ltd.) was affixed to an electrode surface. A dispersion of PTFE (Dupont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was applied to the other surface and dried in a muffle at 120ºC for 10 minutes. The polyimide tape was peeled and a sintering treatment was carried out in a muffle at 380ºC for 10 minutes. This operation was repeated twice to inactivate the electrode surface.

[002960] A membrane formed by two layers of a perfluorocarbon polymer whose terminal functional group is "-COOCH; 3"

741/803 when the electrode integrated into the membrane was manipulated, the electrode came loose and fell off the membrane during manipulation, and so on. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002956] When a deformation test of the electrode was performed, the electrode did not recover and remained wrapped in the form of a PVC tube. Thus, it was not possible to measure the values of L, and Lo.

[002957] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0027 (kPa-s / m) in the condition of measurement 2. [Example 4-33]

[002958] In Example 4-33, a set of membrane electrodes was produced by thermal compression of an electrode on a membrane with reference to a prior art document (Examples of Japanese Patent Open to the Public No. 58-48686).

[002959] A fully laminated nickel expanded metal with a gauge thickness of 100 μm and an opening ratio of 33% was used as a substrate for the electrode for cathode electrolysis to perform electrode coating in the same manner as in Example 4- 1. Subsequently, an electrode surface was subjected to an inactivation treatment in the following procedure. Polyimide adhesive tape (Chukoh Chemical Industries, Ltd.) was affixed to an electrode surface. A dispersion of PTFE (Dupont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was applied to the other surface and dried in a muffle at 120ºC for 10 minutes. The polyimide tape was peeled and a sintering treatment was carried out in a muffle at 380ºC for 10 minutes. This operation was repeated twice to inactivate the electrode surface.

[002960] A membrane formed by two layers of a perfluorocarbon polymer whose terminal functional group is "-COOCH; 3"

742/803 (polymer C) and a perfluorocarbon polymer whose terminal functional group is "-SOzF" (polymer S). The thickness of polymer layer C was 3 mils and the thickness of polymer layer S was 4 mils. This two-layer membrane was subjected to a saponification treatment to introduce ion exchange groups at the polymer terminals by hydrolysis. The polymer C terminals were hydrolyzed in carboxylic acid groups and the polymer S terminals in sulfo groups. The ion exchange capacity, like the sulfonic acid group, was 1.0 meq / g, and the ion exchange capacity, like the carboxylic acid group, was 0.9 meq / g.

[002961] The inactivated electrode surface was arranged in the opposite way and thermally pressed on the surface with carboxylic acid groups such as ion exchange groups to integrate the ion exchange membrane and the electrode. The electrode surface was exposed even after thermal compression, and the electrode passed through no portion of the membrane.

[002962] Subsequently, in order to suppress the affixing of bubbles to be generated during electrolysis to the membrane, a mixture of zirconium oxide and a perfluorocarbon polymer in which sulfo groups were introduced was applied to both surfaces. Thus, the membrane electrode set of Example 4-33 was produced.

[002963] When the force applied per unit mass-unit area (1) was measured using this membrane electrode assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression . Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.50 (N / mg: in?) Was applied, a portion of the membrane was broken. The membrane electrode set of Example 4-33 had a force applied per unit mass-unit area (1) of at least 1.50 (N / mg: cm?) And was strongly bonded.

742/803 (polymer C) and a perfluorocarbon polymer whose terminal functional group is "-SOzF" (polymer S). The thickness of polymer layer C was 3 mils and the thickness of polymer layer S was 4 mils. This two-layer membrane was subjected to a saponification treatment to introduce ion exchange groups at the polymer terminals by hydrolysis. The polymer C terminals were hydrolyzed in carboxylic acid groups and the polymer S terminals in sulfo groups. The ion exchange capacity, like the sulfonic acid group, was 1.0 meq / g, and the ion exchange capacity, like the carboxylic acid group, was 0.9 meq / g.

[002961] The inactivated electrode surface was arranged in the opposite way and thermally pressed on the surface with carboxylic acid groups such as ion exchange groups to integrate the ion exchange membrane and the electrode. The electrode surface was exposed even after thermal compression, and the electrode passed through no portion of the membrane.

[002962] Subsequently, in order to suppress the affixing of bubbles to be generated during electrolysis to the membrane, a mixture of zirconium oxide and a perfluorocarbon polymer in which sulfo groups were introduced was applied to both surfaces. Thus, the membrane electrode set of Example 4-33 was produced.

[002963] When the force applied per unit mass-unit area (1) was measured using this membrane electrode assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression . Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.50 (N / mg: in?) Was applied, a portion of the membrane was broken. The membrane electrode set of Example 4-33 had a force applied per unit mass-unit area (1) of at least 1.50 (N / mg: cm?) And was strongly bonded.

743/803

[002964] When the winding was evaluated around the 280 mm diameter column (1), the area in contact with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and the membrane were 100% connected to each other, but the membrane was not wound around the column in the first place. The result of the evaluation of the winding around the 145 mm column (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The handling property was "3", which was problematic. The membrane damage was rated “0”. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda (value converted to the base of 50%) was increased and the electrolytic performance deteriorated.

[002965] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002966] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002967] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Example 4-34]

[002968] In Example 4-34, a 40 mesh nickel mesh with a line diameter of 150 µm, a gauge thickness of 300 µm and an opening ratio of 58% was used as substrate for the electrolyte of the electrode. cathode. Except for the above, a set of membrane electrodes was produced in the same manner as in Example 4-33.

743/803

[002964] When the winding was evaluated around the 280 mm diameter column (1), the area in contact with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and the membrane were 100% connected to each other, but the membrane was not wound around the column in the first place. The result of the evaluation of the winding around the 145 mm column (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The handling property was "3", which was problematic. The membrane damage was rated “0”. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda (value converted to the base of 50%) was increased and the electrolytic performance deteriorated.

[002965] The thickness of the electrode was 114 µm. The thickness of the catalytic layer, which was determined by subtracting the thickness of the electrode substrate for electrolysis from the electrode thickness, was 14 µm.

[002966] When an electrode deformation test was performed, the average value of L, and L> was 13 mm.

[002967] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0168 (kPa-s / m) in the condition of measurement 2. [Example 4-34]

[002968] In Example 4-34, a 40 mesh nickel mesh with a line diameter of 150 µm, a gauge thickness of 300 µm and an opening ratio of 58% was used as substrate for the electrolyte of the electrode. cathode. Except for the above, a set of membrane electrodes was produced in the same manner as in Example 4-33.

744/803

[002969] When the force applied per unit mass-unit area (1) was measured using this membrane electrode assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression . Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.60 (N / mg: ecm?) Was applied, a portion of the membrane was broken. The membrane electrode set of Example 4-34 had a force applied per unit mass-unit area (1) of at least 1.60 (N / mg: cm?) And was strongly bonded.

[002970] When the winding was evaluated around the 280 mm diameter column (1) using this membrane electrode set, the contact area with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and the membrane were 100% connected to each other, but the membrane was not wound around the column in the first place. The result of the evaluation of the winding around the 145 mm column (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The handling property was "3", which was problematic. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda was increased and the electrolytic performance deteriorated.

[002971] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002972] When an electrode deformation test was performed, the average value of L, and L, was 23 mm.

744/803

[002969] When the force applied per unit mass-unit area (1) was measured using this membrane electrode assembly, the electrode did not move upwards because the electrode and the membrane were firmly connected to each other by thermal compression . Then, the ion exchange membrane and the nickel plate were fixed so as not to move, and the electrode was pulled up by a stronger force. When a force of 1.60 (N / mg: ecm?) Was applied, a portion of the membrane was broken. The membrane electrode set of Example 4-34 had a force applied per unit mass-unit area (1) of at least 1.60 (N / mg: cm?) And was strongly bonded.

[002970] When the winding was evaluated around the 280 mm diameter column (1) using this membrane electrode set, the contact area with the plastic tube was less than 5%. However, when the winding was evaluated around the 280 mm diameter column (2), the electrode and the membrane were 100% connected to each other, but the membrane was not wound around the column in the first place. The result of the evaluation of the winding around the 145 mm column (3) was the same. The result meant that the integrated electrode impaired the membrane's handling property, thereby making it difficult to roll the membrane in a roll and bend the membrane. The handling property was "3", which was problematic. In addition, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the concentration of common salt in the caustic soda was increased and the electrolytic performance deteriorated.

[002971] The thickness of the electrode was 308 µm. The thickness of the catalytic layer, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 8 µm.

[002972] When an electrode deformation test was performed, the average value of L, and L, was 23 mm.

745/803

[002973] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in the condition of measurement 2. [Example 4-35]

[002974] A nickel line with a thickness of 150 µm was provided as a substrate for the electrode for electrolysis of the cathode. A roughness treatment by this nickel line was carried out. It is difficult to measure the surface roughness of the nickel line. Thus, in Example 4-35, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the nickel line. . A pickling treatment was carried out with grain size alumina number 320. The arithmetic mean roughness Ra was 0.64 µm.

[002975] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002976] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088 (trade name), thickness 10 mm) in around a polyvinyl chloride (PVC) cylinder was always in contact with the above coating liquid. A coating roll around which the same EPDM had been

745/803

[002973] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.07 (kKPa-s / m) or less in measurement condition 1 and 0.0034 (kPa-s / m) in the condition of measurement 2. [Example 4-35]

[002974] A nickel line with a thickness of 150 µm was provided as a substrate for the electrode for electrolysis of the cathode. A roughness treatment by this nickel line was carried out. It is difficult to measure the surface roughness of the nickel line. Thus, in Example 4-35, a nickel plate with a thickness of 1 mm was simultaneously subjected to pickling during pickling, and the surface roughness of the nickel plate was taken as the surface roughness of the nickel line. . A pickling treatment was carried out with grain size alumina number 320. The arithmetic mean roughness Ra was 0.64 µm.

[002975] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[002976] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088 (trade name), thickness 10 mm) in around a polyvinyl chloride (PVC) cylinder was always in contact with the above coating liquid. A coating roll around which the same EPDM had been

746/803 rolled up was placed in the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the nickel line produced in Example 4-35 was 158 µm.

[002977] The nickel line produced by the above method was cut to a length of 110 mm and a length of 95 mm. As shown in Figure 85, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with Aron Alpha to produce an electrode. The electrode was evaluated, and the results are shown in Table 7.

[002978] The portion of the electrode in which the nickel lines were superimposed was of the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.7%.

[002979] The mass per unit area of the electrode was 0.5 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002980] When an electrode deformation test was performed, the

746/803 rolled up was placed in the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the nickel line produced in Example 4-35 was 158 µm.

[002977] The nickel line produced by the above method was cut to a length of 110 mm and a length of 95 mm. As shown in Figure 85, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with Aron Alpha to produce an electrode. The electrode was evaluated, and the results are shown in Table 7.

[002978] The portion of the electrode in which the nickel lines were superimposed was of the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.7%.

[002979] The mass per unit area of the electrode was 0.5 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002980] When an electrode deformation test was performed, the

747/803 mean value of L, and L> was 15 mm.

[002981] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance value was 0.0002 (kPa-s / m).

[002982] In addition, the structure shown in Figure 86 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.16 V. [Example 4-36]

[002983] In Example 4-36, the electrode produced in Example 4-35 was used. As shown in Figure 87, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with Aron Alpha to produce an electrode. The electrode was evaluated, and the results are shown in Table 7.

[002984] The portion of the electrode in which the nickel lines were superimposed was of the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.4%.

[002985] The mass per unit area of the electrode was 0.9 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002986] When an electrode deformation test was performed, the

747/803 mean value of L, and L> was 15 mm.

[002981] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance value was 0.0002 (kPa-s / m).

[002982] In addition, the structure shown in Figure 86 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.16 V. [Example 4-36]

[002983] In Example 4-36, the electrode produced in Example 4-35 was used. As shown in Figure 87, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with Aron Alpha to produce an electrode. The electrode was evaluated, and the results are shown in Table 7.

[002984] The portion of the electrode in which the nickel lines were superimposed was of the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 99.4%.

[002985] The mass per unit area of the electrode was 0.9 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002986] When an electrode deformation test was performed, the

748/803 mean value of L, and L> was 16 mm.

[002987] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0004 (kPa-s / m).

[002988] In addition, the structure shown in Figure 88 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Example 4-37]

[002989] In Example 4-37, the electrode produced in Example 4-35 was used. As shown in Figure 89, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with Aron Alpha to produce an electrode. The electrode was evaluated, and the results are shown in Table 7.

[002990] The portion of the electrode in which the nickel lines were superimposed had the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 98.8%.

[002991] The mass per unit area of the electrode was 1.9 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002992] When an electrode deformation test was performed, the

748/803 mean value of L, and L> was 16 mm.

[002987] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0004 (kPa-s / m).

[002988] In addition, the structure shown in Figure 88 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Example 4-37]

[002989] In Example 4-37, the electrode produced in Example 4-35 was used. As shown in Figure 89, the 110 mm nickel line and the 95 mm nickel line were placed so that the nickel lines were superimposed vertically in the center of each of the nickel lines and joined together at the intersection with Aron Alpha to produce an electrode. The electrode was evaluated, and the results are shown in Table 7.

[002990] The portion of the electrode in which the nickel lines were superimposed had the greatest thickness, and the thickness of the electrode was 306 µm. The thickness of the catalytic layer was 6 µm. The opening ratio was 98.8%.

[002991] The mass per unit area of the electrode was 1.9 (mg / cm?). The forces applied per unit mass-unit area (1) and (2) were equal to or less than the lower measurement limit of the tensile testing machine. Thus, the result of the evaluation of the winding around the 280 mm diameter column (1) was less than 5%, and the portions in which the electrode came loose from the membrane increased. The handling property was "4", which was also problematic. The membrane damage was rated “0”.

[002992] When an electrode deformation test was performed, the

749/803 mean value of L, and L> was 14 mm.

[002993] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0005 (kPa-s / m).

[002994] In addition, the structure shown in Figure 90 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Comparative example 4-1] (Preparation of the catalyst)

[002995] An aqueous solution of metal salt was produced by adding 0.728 g of silver nitrate (Wako Pure Chemical Industries, Ltd.) and 1.86 g of cerium nitrate hexahydrate (Wako Pure Chemical Industries, Ltd .) to 150 ml of pure water. An alkaline solution was produced by adding 240 g of pure water to 100 g of a 15% aqueous solution of tetramethylammonium hydroxide (Wako Pure Chemical Industries, Ltd.). While the alkaline solution was stirred using a magnetic stirrer, the aqueous metal salt solution was added dropwise at 5 ml / minute using a burette. A suspension containing the resulting metal hydroxide particles was filtered with suction and then washed with water to remove the alkali content. Then, the residue was transferred to 200 ml of 2-propanol (KISHIDA CHEMICAL Co. Ltd.) and redispersed by an ultrasonic dispersion apparatus (US-600T, NISSEI Corporation) for 10 minutes to obtain a uniform suspension.

[002996] A carbon black suspension was obtained by dispersing 0.36 g of hydrophobic carbon black (DENKA BLACK (R) AB-7 (trade name), Denka Company Limited) and 0.84 g of black hydrophilic smoke

749/803 mean value of L, and L> was 14 mm.

[002993] When the ventilation resistance of the electrode was measured, the ventilation resistance was 0.001 (kPa-s / m) or less in measurement condition 2. When measured under measurement condition 2 with SENSE (measurement range) set to H (high) of the ventilation resistance measuring device, the ventilation resistance was 0.0005 (kPa-s / m).

[002994] In addition, the structure shown in Figure 90 was used to position the electrode (cathode) in the Ni mesh feed conductor and the electrolyte evaluation of the electrode was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18 V. [Comparative example 4-1] (Preparation of the catalyst)

[002995] An aqueous solution of metal salt was produced by adding 0.728 g of silver nitrate (Wako Pure Chemical Industries, Ltd.) and 1.86 g of cerium nitrate hexahydrate (Wako Pure Chemical Industries, Ltd .) to 150 ml of pure water. An alkaline solution was produced by adding 240 g of pure water to 100 g of a 15% aqueous solution of tetramethylammonium hydroxide (Wako Pure Chemical Industries, Ltd.). While the alkaline solution was stirred using a magnetic stirrer, the aqueous metal salt solution was added dropwise at 5 ml / minute using a burette. A suspension containing the resulting metal hydroxide particles was filtered with suction and then washed with water to remove the alkali content. Then, the residue was transferred to 200 ml of 2-propanol (KISHIDA CHEMICAL Co. Ltd.) and redispersed by an ultrasonic dispersion apparatus (US-600T, NISSEI Corporation) for 10 minutes to obtain a uniform suspension.

[002996] A carbon black suspension was obtained by dispersing 0.36 g of hydrophobic carbon black (DENKA BLACK (R) AB-7 (trade name), Denka Company Limited) and 0.84 g of black hydrophilic smoke

750/803 (Ketjenblack (R) EC-600JD (trade name), Mitsubishi Chemical Corporation) in 100 ml of 2-propanol and dispersion of the mixture by the ultrasonic dispersion apparatus for 10 minutes. The suspension of the metal hydroxide precursor and the carbon black suspension were mixed and dispersed by the ultrasonic dispersion apparatus for 10 minutes. This suspension was suction filtered and dried at room temperature for half a day to obtain carbon black containing the dispersed and fixed metal hydroxide precursor. Subsequently, an inert gas cooking oven (type VMFI65, YAMADA DENKI CO ,, LTD.) Was used to cook in an atmosphere of nitrogen at 400ºC for one hour to obtain carbon black A containing a fixed and dispersed electrode catalyst. (Powder production for reaction layer)

[002997] To 1.6 g of carbon black A containing a dispersed and fixed electrode catalyst, 0.84 ml of a Triton (R) X-100 surfactant (trade name, ICN Biomedicals) was added diluted to 20% by weight with pure water and 15 ml of pure water, and the mixture was dispersed by an ultrasonic dispersion apparatus for 10 minutes. To that dispersion, 0.664 g of a polytetrafluoroethylene (PTFE) dispersion (PTFE30J (tradename), Dupont-Mitsui Fluorochemicals Co., Ltd.) was added. After the mixture had been stirred for five minutes, suction filtration was performed. In addition, the residue was dried in a dryer at 80ºC for one hour and the spraying was carried out by a mill to obtain a powder for reaction layer A. (Powder production for gas diffusion layer)

[002998] 20 g of hydrophobic carbon black (DENKA BLACK (R) AB-7 (trade name)), SO ml of a Triton (R) X-100 (trade name) surfactant diluted to 20% by weight with pure water and 360 ml of pure water by an ultrasonic dispersion device for 10 minutes. To the resulting dispersion, 22.32 g of the PTFE dispersion was added. The mixture

750/803 (Ketjenblack (R) EC-600JD (trade name), Mitsubishi Chemical Corporation) in 100 ml of 2-propanol and dispersion of the mixture by the ultrasonic dispersion apparatus for 10 minutes. The suspension of the metal hydroxide precursor and the carbon black suspension were mixed and dispersed by the ultrasonic dispersion apparatus for 10 minutes. This suspension was suction filtered and dried at room temperature for half a day to obtain carbon black containing the dispersed and fixed metal hydroxide precursor. Subsequently, an inert gas cooking oven (type VMFI65, YAMADA DENKI CO ,, LTD.) Was used to cook in an atmosphere of nitrogen at 400ºC for one hour to obtain carbon black A containing a fixed and dispersed electrode catalyst. (Powder production for reaction layer)

[002997] To 1.6 g of carbon black A containing a dispersed and fixed electrode catalyst, 0.84 ml of a Triton (R) X-100 surfactant (trade name, ICN Biomedicals) was added diluted to 20% by weight with pure water and 15 ml of pure water, and the mixture was dispersed by an ultrasonic dispersion apparatus for 10 minutes. To that dispersion, 0.664 g of a polytetrafluoroethylene (PTFE) dispersion (PTFE30J (tradename), Dupont-Mitsui Fluorochemicals Co., Ltd.) was added. After the mixture had been stirred for five minutes, suction filtration was performed. In addition, the residue was dried in a dryer at 80ºC for one hour and the spraying was carried out by a mill to obtain a powder for reaction layer A. (Powder production for gas diffusion layer)

[002998] 20 g of hydrophobic carbon black (DENKA BLACK (R) AB-7 (trade name)), SO ml of a Triton (R) X-100 (trade name) surfactant diluted to 20% by weight with pure water and 360 ml of pure water by an ultrasonic dispersion device for 10 minutes. To the resulting dispersion, 22.32 g of the PTFE dispersion was added. The mixture

751/803 was stirred for 5 minutes, and then filtration was performed. In addition, the residue was dried in a dryer at 80ºC for one hour and the spraying was carried out by a mill to obtain a powder for the gas diffusion layer A. (Production of the gas diffusion electrode)

[002999] To 4 g of the powder for the gas diffusion layer A, 8.7 ml of ethanol were added and the mixture was kneaded into a paste. This powder for the gas diffusion layer in the form of paste was formed into a sheet form by a roll former. Silver mesh (SW = 1, LW = 2 and thickness = 0.3 mm) as the collector was embedded in the sheet and finally formed into a sheet shape with a thickness of 1.8 mm. To 1 g of the powder for reaction layer A, 2.2 ml of ethanol was added and the mixture was kneaded into a paste. This powder for the paste reaction layer was formed into a sheet form 0.2 mm thick by a roll former. In addition, the two sheets, that is, the sheet obtained using the powder for the gas diffusion layer A produced and the sheet obtained using the powder for reaction layer A were laminated and formed into a sheet form with a thickness of 1.8 mm by a roll former. This laminated sheet was dried at room temperature for one day and overnight to remove ethanol. In addition, in order to remove the remaining surfactant, the leaf was subjected to an air pyrolysis treatment at 300ºC for one hour. The sheet was wrapped in aluminum foil and subjected to hot pressing by a hot pressing machine (SA303 (trade name), TESTER SANGYO CO ,. LTD) at 360ºC and 50 kgf / cm? for 1 minute to obtain a gas diffusion electrode. The thickness of the gas diffusion electrode was 412 µm.

[003000] The resulting electrode was used to perform electrolytic evaluation. In the sectional structure of the electrolytic cell, the collector, the mattress, the nickel mesh feed conductor, the electrode, the membrane and the

751/803 was stirred for 5 minutes, and then filtration was performed. In addition, the residue was dried in a dryer at 80ºC for one hour and the spraying was carried out by a mill to obtain a powder for the gas diffusion layer A. (Production of the gas diffusion electrode)

[002999] To 4 g of the powder for the gas diffusion layer A, 8.7 ml of ethanol were added and the mixture was kneaded into a paste. This powder for the gas diffusion layer in the form of paste was formed into a sheet form by a roll former. Silver mesh (SW = 1, LW = 2 and thickness = 0.3 mm) as the collector was embedded in the sheet and finally formed into a sheet shape with a thickness of 1.8 mm. To 1 g of the powder for reaction layer A, 2.2 ml of ethanol was added and the mixture was kneaded into a paste. This powder for the paste reaction layer was formed into a sheet form 0.2 mm thick by a roll former. In addition, the two sheets, that is, the sheet obtained using the powder for the gas diffusion layer A produced and the sheet obtained using the powder for reaction layer A were laminated and formed into a sheet form with a thickness of 1.8 mm by a roll former. This laminated sheet was dried at room temperature for one day and overnight to remove ethanol. In addition, in order to remove the remaining surfactant, the leaf was subjected to an air pyrolysis treatment at 300ºC for one hour. The sheet was wrapped in aluminum foil and subjected to hot pressing by a hot pressing machine (SA303 (trade name), TESTER SANGYO CO ,. LTD) at 360ºC and 50 kgf / cm? for 1 minute to obtain a gas diffusion electrode. The thickness of the gas diffusion electrode was 412 µm.

[003000] The resulting electrode was used to perform electrolytic evaluation. In the sectional structure of the electrolytic cell, the collector, the mattress, the nickel mesh feed conductor, the electrode, the membrane and the

752/803 anodes are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure. The results are shown in Table 7.

[003001] When an electrode deformation test was performed, the average value of L, and L> was 19 mm.

[003002] When the ventilation resistance of the electrode was measured, the ventilation resistance was 25.88 (kPa-s / m) in measurement condition 1.

[003003] The handling property was "3", which was problematic. In addition, when the electrolytic evaluation was carried out, the current efficiency was low, the concentration of common salt in the caustic soda was increased and the electrolytic performance deteriorated remarkably. The membrane damage, which was rated "3", also had a problem.

[003004] These results revealed that the gas diffusion electrode obtained in Comparative Example 4-1 had a remarkably weak electrolytic performance. In addition, damage was observed to the substantially entire surface of the ion exchange membrane. It was conceived that this is due to the fact that the NaOH that was generated in the electrode accumulated at the interface between the electrode and the membrane to increase its concentration, due to the remarkably high ventilation resistance of the gas diffusion electrode of Comparative Example 4 -1. [Table 6] ubstrate - x rma of substrate forMethod - del 'ara:' feed electrode coating electrode Example 1 Ni = ——> = —— Drilling - => Pyrolysis - MalhadeNi Example 42 Ni === Drilling - => Pyrolysis = Ni mesh Example 3 Ni => Perfection - >> Pyrolysis - Ni mesh Example 44 Ni == - = - Perfection - => Pyrolysis - Ni mesh Example 5 Ni = -> - = - Perfection - >> Pyrolysis - MalhadeNi 1Ónica Example 4-7 Ni ——— Electroforming ——— Pyrolysis - Ni Mesh Example 4-8 Ni> Electroforming - —— Pyrolysis - Ni Mesh Example 4-9 Ni = TTecidon nonwoven - = Pyrolysis - Ni Mesh [Example 4- 10 Ni> Non-woven fabric - - Pyrolysis - Ni mesh Example -11 Ni >> Foam - == Pyrolysis - Ni mesh Example 4-12 Ni ——— VMaha ——— - Pyrolysis —MalhadeNi Example 4-13 Ni Mana - Pyrolysis MalhadeNi

752/803 anodes are arranged in the order mentioned from the side of the cathode chamber to form a zero interstice structure. The results are shown in Table 7.

[003001] When an electrode deformation test was performed, the average value of L, and L> was 19 mm.

[003002] When the ventilation resistance of the electrode was measured, the ventilation resistance was 25.88 (kPa-s / m) in measurement condition 1.

[003003] The handling property was "3", which was problematic. In addition, when the electrolytic evaluation was carried out, the current efficiency was low, the concentration of common salt in the caustic soda was increased and the electrolytic performance deteriorated remarkably. The membrane damage, which was rated "3", also had a problem.

[003004] These results revealed that the gas diffusion electrode obtained in Comparative Example 4-1 had a remarkably weak electrolytic performance. In addition, damage was observed to the substantially entire surface of the ion exchange membrane. It was conceived that this is due to the fact that the NaOH that was generated in the electrode accumulated at the interface between the electrode and the membrane to increase its concentration, due to the remarkably high ventilation resistance of the gas diffusion electrode of Comparative Example 4 -1. [Table 6] ubstrate - x rma of substrate forMethod - del 'ara:' feed electrode coating electrode Example 1 Ni = ——> = —— Drilling - => Pyrolysis - MalhadeNi Example 42 Ni === Drilling - => Pyrolysis = Ni mesh Example 3 Ni => Perfection - >> Pyrolysis - Ni mesh Example 44 Ni == - = - Perfection - => Pyrolysis - Ni mesh Example 5 Ni = -> - = - Perfection - >> Pyrolysis - MalhadeNi 1Ónica Example 4-7 Ni ——— Electroforming ——— Pyrolysis - Ni Mesh Example 4-8 Ni> Electroforming - —— Pyrolysis - Ni Mesh Example 4-9 Ni = TTecidon nonwoven - = Pyrolysis - Ni Mesh [Example 4- 10 Ni> Non-woven fabric - - Pyrolysis - Ni mesh Example -11 Ni >> Foam - == Pyrolysis - Ni mesh Example 4-12 Ni ——— VMaha ——— - Pyrolysis —MalhadeNi Example 4-13 Ni Mana - Pyrolysis MalhadeNi

753/803 [Example 4-14 Ni Aa E * pyrolysis' oil weights fo E Sinks In example 4-3) tension Example 416 fi - ——Perfirmation - >>> Pyrolysis - JAnode with increased tension | Example 17 fi Perfection -> Pyrolysis - JAnode with increased tension | Example 418 fi Perfection - >> Pyrolysis - JAnode with increased voltage | Example 419 fi Perfection - >> Pyrolysis - JAnode with increased voltage | Example 4:20 laughs - >> TTecidonwoven - = —Pyrolysis - JAnode with increased tension | to price] [Example 4-22 Ni / Ti Example 4-3 and ExamplePyrolysis z 14-20 ha voltage

Example 4:23 fi => Perfection - ———— Pyroise FP | fisheries Hey Fiat | Example 4:27 Ni => lExpandido = = ==> Pyrolysis - MahadeNi ===> Example 4:28 Ni Mana pyrolysis MahadeNi ==> Example 4:29 Niíi Mana> Pyrolysis MahadeNi = ——c = - => = & j Example 4:30 ri => Expanded - ==> Pyrolysis - Janode with increased tension | Example 4:31 [laughs => Expanded - ==> Pyrolysis - Janode with increased tension | Example 4:32 laughs => Expanded - => Pyrolysis - Janode with increased tension | Example 4:33 Ni >> lexpandido = == Pyrolysis - MahadeNi ===> Example 4:34 Ni Manha pyrolytic MahadeNi ==> Example 4:35 Ni Mana pyrolytic MahadeNi ==> Example 4:36 fi Mana pyrolytic MahadeNi == => Example 4:37 Node Mana piróise ManadeNio ===> | comparative 4-1

753/803 [Example 4-14 Ni Aa E * pyrolysis' oil weights fo E Sinks In example 4-3) tension Example 416 fi - ——Perfirmation - >>> Pyrolysis - JAnode with increased tension | Example 17 fi Perfection -> Pyrolysis - JAnode with increased tension | Example 418 fi Perfection - >> Pyrolysis - JAnode with increased voltage | Example 419 fi Perfection - >> Pyrolysis - JAnode with increased voltage | Example 4:20 laughs - >> TTecidonwoven - = —Pyrolysis - JAnode with increased tension | to price] [Example 4-22 Ni / Ti Example 4-3 and ExamplePyrolysis z 14-20 ha voltage

Example 4:23 fi => Perfection - ———— Pyroise FP | fisheries Hey Fiat | Example 4:27 Ni => lExpandido = = ==> Pyrolysis - MahadeNi ===> Example 4:28 Ni Mana pyrolysis MahadeNi ==> Example 4:29 Niíi Mana> Pyrolysis MahadeNi = ——c = - => = & j Example 4:30 ri => Expanded - ==> Pyrolysis - Janode with increased tension | Example 4:31 [laughs => Expanded - ==> Pyrolysis - Janode with increased tension | Example 4:32 laughs => Expanded - => Pyrolysis - Janode with increased tension | Example 4:33 Ni >> lexpandido = == Pyrolysis - MahadeNi ===> Example 4:34 Ni Manha pyrolytic MahadeNi ==> Example 4:35 Ni Mana pyrolytic MahadeNi ==> Example 4:36 fi Mana pyrolytic MahadeNi == => Example 4:37 Node Mana piróise ManadeNio ===> | comparative 4-1

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757/803

[003005] In Table 7, all samples were able to stand alone due to surface tension before measuring “force applied per unit mass-unit area (1)” and “force applied per unit mass-unit area” (2) ”(that is, they did not slip). <Verification of the fifth modality>

[003006] As will be described below, Experimental Examples were provided according to the fifth modality (in the <Verification of the fifth modality> section, simply called “Examples”) and Experimental Examples not according to the fifth modality (in the section <Verification of the fifth modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 93 to 94 and 100 to 102, as appropriate.

[003007] As the membrane, an A ion exchange membrane produced as described below was used.

[003008] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarn) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[003009] Next, a dry resin A which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a dry resin B resin that was

757/803

[003005] In Table 7, all samples were able to stand alone due to surface tension before measuring “force applied per unit mass-unit area (1)” and “force applied per unit mass-unit area” (2) ”(that is, they did not slip). <Verification of the fifth modality>

[003006] As will be described below, Experimental Examples were provided according to the fifth modality (in the <Verification of the fifth modality> section, simply called “Examples”) and Experimental Examples not according to the fifth modality (in the section <Verification of the fifth modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 93 to 94 and 100 to 102, as appropriate.

[003007] As the membrane, an A ion exchange membrane produced as described below was used.

[003008] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarn) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[003009] Next, a dry resin A which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a dry resin B resin that was

758/803 a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.03 mg equivalent / g.

[003010] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[003011] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[003012] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[003013] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of acid type B resin and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the composite membrane surfaces to obtain an ion exchange membrane A. At the zirconium oxide coating density measured by measurement by

758/803 a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.03 mg equivalent / g.

[003010] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[003011] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[003012] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[003013] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of acid type B resin and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the composite membrane surfaces to obtain an ion exchange membrane A. At the zirconium oxide coating density measured by measurement by

759/803 X-ray fluorescence was 0.5 mg / ecm ?. Here, the average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[003014] As the electrode, a cathode and anode below were used.

[003015] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 22 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.95 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[003016] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 44%.

[003017] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[003018] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was

759/803 X-ray fluorescence was 0.5 mg / ecm ?. Here, the average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[003014] As the electrode, a cathode and anode below were used.

[003015] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 22 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.95 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[003016] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 44%.

[003017] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[003018] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was

760/803 placed in the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced was 29 µm. The thickness of the catalytic layer containing ruthenium oxide and cerium oxide, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[003019] A non-woven fabric of titanium with a gauge thickness of 100 µm, a titanium fiber diameter of 20 µm, a base weight of 100 g / m? Was used, and an opening ratio of 78% as a substrate to the electrode for electrolysis of the anode.

[003020] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anodic coating liquid.

[003021] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed by

760/803 placed in the upper portion thereof, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced was 29 µm. The thickness of the catalytic layer containing ruthenium oxide and cerium oxide, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[003019] A non-woven fabric of titanium with a gauge thickness of 100 µm, a titanium fiber diameter of 20 µm, a base weight of 100 g / m? Was used, and an opening ratio of 78% as a substrate to the electrode for electrolysis of the anode.

[003020] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anodic coating liquid.

[003021] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed by

761/803 winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a polyvinyl chloride (PVC) cylinder was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, preliminary cooking and cooking operations were carried out repeatedly, and then cooking at 520ºC was carried out for one hour. [Example 5-1] (Example of using a cathodic membrane laminate)

[003022] A rolled body was produced in advance as follows. First, an ion exchange membrane with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003023] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the cathodes were arranged without any interstice on the carboxylic acid layer side of the ion exchange membrane to produce a laminate of the cathodes and the ion exchange membrane (see Figure 100). When the cathodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the

761/803 winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a polyvinyl chloride (PVC) cylinder was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, preliminary cooking and cooking operations were carried out repeatedly, and then cooking at 520ºC was carried out for one hour. [Example 5-1] (Example of using a cathodic membrane laminate)

[003022] A rolled body was produced in advance as follows. First, an ion exchange membrane with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003023] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the cathodes were arranged without any interstice on the carboxylic acid layer side of the ion exchange membrane to produce a laminate of the cathodes and the ion exchange membrane (see Figure 100). When the cathodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the

762/803 cathodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. The resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m as shown in Figure 101, to produce a rolled body. The rolled body was in a cylindrical shape with an outer diameter of 84 mm and a length of 1.7 m, and it was possible to reduce the size of the laminate.

[003024] Then, in an existing large electrolyzer (electrolyzer with a structure similar to those shown in Figures 93 and 94), a fixed state of the adjacent electrolytic cells and the ion exchange membrane through a pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the cathode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003025] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the renewal of the electrode and the replacement of the membrane can be completed in several tens of minutes per cell, when a rolled body of the laminate is provided in advance during electrolytic operation. [Example 5-2] (Example of using anodic membrane laminate)

[003026] A rolled body was produced in advance as follows. First, an ion exchange membrane with a size

762/803 cathodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. The resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m as shown in Figure 101, to produce a rolled body. The rolled body was in a cylindrical shape with an outer diameter of 84 mm and a length of 1.7 m, and it was possible to reduce the size of the laminate.

[003024] Then, in an existing large electrolyzer (electrolyzer with a structure similar to those shown in Figures 93 and 94), a fixed state of the adjacent electrolytic cells and the ion exchange membrane through a pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the cathode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003025] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the renewal of the electrode and the replacement of the membrane can be completed in several tens of minutes per cell, when a rolled body of the laminate is provided in advance during electrolytic operation. [Example 5-2] (Example of using anodic membrane laminate)

[003026] A rolled body was produced in advance as follows. First, an ion exchange membrane with a size

763/803 1.5 m long and 2.5 m wide according to the method mentioned above. Additionally, four anodes with a size of 0.3 m in length and 2.4 m in width were provided according to the method mentioned above.

[003027] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the anodes were arranged without any interstices on the side of the sulfonic acid layer in the same way as in Example 5 -1 to produce a laminate of the anodes and the ion exchange membrane. When the anodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the anodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. The resulting laminate was wound around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body in the same manner as in Example 5-1. The rolled body was in a cylindrical shape with an outer diameter of 86 mm and a length of 1.7 m, and it was possible to reduce the size of the laminate.

[003028] Then, in an existing large electrolyzer (electrolyzer similar to Example 5-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between the electrolytic cells.

763/803 1.5 m long and 2.5 m wide according to the method mentioned above. Additionally, four anodes with a size of 0.3 m in length and 2.4 m in width were provided according to the method mentioned above.

[003027] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the anodes were arranged without any interstices on the side of the sulfonic acid layer in the same way as in Example 5 -1 to produce a laminate of the anodes and the ion exchange membrane. When the anodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the anodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. The resulting laminate was wound around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body in the same manner as in Example 5-1. The rolled body was in a cylindrical shape with an outer diameter of 86 mm and a length of 1.7 m, and it was possible to reduce the size of the laminate.

[003028] Then, in an existing large electrolyzer (electrolyzer similar to Example 5-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between the electrolytic cells.

764/803 same.

[003029] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the electrode renewal and membrane replacement can be completed in several tens of minutes per cell, when a rolled laminated body is provided in advance during the electrolytic operation. [Example 5-3] (Example of using anodic / cathodic membrane laminate)

[003030] A rolled body was produced in advance as follows. First, an ion exchange membrane with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four anodes and four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003031] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the cathodes were arranged on the side of the carboxylic acid layer and the anodes were arranged on the side of the sulfonic acid without any interstice in the same way as in Example 5-1 to produce a laminate of the cathodes, anodes and ion exchange membrane. When the cathodes and anodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution made the surface tension work, and the cathodes, anodes and membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. The resulting laminate was wound around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body in the same manner as in Example 5-1. The rolled-up body was in a cylindrical shape with an outer diameter of 88 mm and a length of 1.7 m, and it was possible

764/803 same.

[003029] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the electrode renewal and membrane replacement can be completed in several tens of minutes per cell, when a rolled laminated body is provided in advance during the electrolytic operation. [Example 5-3] (Example of using anodic / cathodic membrane laminate)

[003030] A rolled body was produced in advance as follows. First, an ion exchange membrane with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four anodes and four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003031] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the cathodes were arranged on the side of the carboxylic acid layer and the anodes were arranged on the side of the sulfonic acid without any interstice in the same way as in Example 5-1 to produce a laminate of the cathodes, anodes and ion exchange membrane. When the cathodes and anodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution made the surface tension work, and the cathodes, anodes and membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. The resulting laminate was wound around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body in the same manner as in Example 5-1. The rolled-up body was in a cylindrical shape with an outer diameter of 88 mm and a length of 1.7 m, and it was possible

765/803 reduce the size of the laminate.

[003032] Then, in an existing large electrolyzer (electrolyzer similar to that of Example 5-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003033] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the electrode renewal and membrane replacement can be completed in several tens of minutes per cell, when a rolled laminated body is provided in advance during the electrolytic operation. [Example 5-4] (Example of using cathodes)

[003034] A rolled body was produced in advance as follows. First, four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above. The four cathodes were arranged without any interstice in order to reach a size of 1.2 m in length and 2.4 in width. The adjacent cathodes were tied and fixed so that the cathodes were not separated by placing a PTFE string through the openings of each cathode (not shown) as shown in Figure 102. In operation, no pressure was applied and the temperature was 23ºC. Those

765/803 reduce the size of the laminate.

[003032] Then, in an existing large electrolyzer (electrolyzer similar to that of Example 5-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003033] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the electrode renewal and membrane replacement can be completed in several tens of minutes per cell, when a rolled laminated body is provided in advance during the electrolytic operation. [Example 5-4] (Example of using cathodes)

[003034] A rolled body was produced in advance as follows. First, four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above. The four cathodes were arranged without any interstice in order to reach a size of 1.2 m in length and 2.4 in width. The adjacent cathodes were tied and fixed so that the cathodes were not separated by placing a PTFE string through the openings of each cathode (not shown) as shown in Figure 102. In operation, no pressure was applied and the temperature was 23ºC. Those

766/803 cathodes were wound around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body in the same manner as in Example 5-1. The rolled body was in a cylindrical shape with an outside diameter of 78 mm and a length of 1.7 m, and it was possible to reduce the size of the laminate.

[003035] Then, in an existing large electrolyzer (electrolyzer similar to Example 5-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the coiled state was released to remove the coiled cathodes. At that time, the cathodes were held substantially vertically to the ground, but the cathodes did not come loose. Then, after the cathodes were inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003036] It was possible to replace the cathodes more easily than in conventional ones. It was considered that the cathode renewal can be completed in several tens of minutes per cell, when a rolled-up cathode body is provided in advance during the electrolytic operation. [Example 5-5] (Example of using anodes)

[003037] A rolled body was produced in advance as follows. First, four anodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above. The four anodes were arranged without any interstice in order to reach a size of 1.2 m in length and 2.4 in width. Adjacent anodes were tied with a PTFE rope and fixed in such a way

766/803 cathodes were wound around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body in the same manner as in Example 5-1. The rolled body was in a cylindrical shape with an outside diameter of 78 mm and a length of 1.7 m, and it was possible to reduce the size of the laminate.

[003035] Then, in an existing large electrolyzer (electrolyzer similar to Example 5-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the coiled state was released to remove the coiled cathodes. At that time, the cathodes were held substantially vertically to the ground, but the cathodes did not come loose. Then, after the cathodes were inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003036] It was possible to replace the cathodes more easily than in conventional ones. It was considered that the cathode renewal can be completed in several tens of minutes per cell, when a rolled-up cathode body is provided in advance during the electrolytic operation. [Example 5-5] (Example of using anodes)

[003037] A rolled body was produced in advance as follows. First, four anodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above. The four anodes were arranged without any interstice in order to reach a size of 1.2 m in length and 2.4 in width. Adjacent anodes were tied with a PTFE rope and fixed in such a way

767/803 that the anodes were not separated, in the same way as in Example 5-4. In the operation, no pressure was applied and the temperature was 23ºC. These anodes were wound around a polyvinyl chloride (PVC) tube with an external diameter of 76 mm and a length of 1.7 m to produce a coiled body in the same manner as in Example 5-1. The rolled body was in a cylindrical shape with an external diameter of 81 mm and a length of 1.7 m, and it was possible to reduce the size of the laminate.

[003038] Then, in an existing large electrolyzer (electrolyzer similar to that of Example 5-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the coiled state was released to remove the coiled anodes. At that time, the anodes were held substantially vertically to the ground, but the anodes did not come loose. Then, after the anodes were inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003039] It was possible to replace the anodes more easily than conventional ones. It was considered that the renewal of the anodes can be completed in several tens of minutes per cell, when a rolled body of the anode is provided in advance during the electrolytic operation. [Comparative Example 5-1] (Conventional electrode renewal)

[003040] In an existing large electrolyzer (electrolyzer similar to Example 5-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between the

767/803 that the anodes were not separated, in the same way as in Example 5-4. In the operation, no pressure was applied and the temperature was 23ºC. These anodes were wound around a polyvinyl chloride (PVC) tube with an external diameter of 76 mm and a length of 1.7 m to produce a coiled body in the same manner as in Example 5-1. The rolled body was in a cylindrical shape with an external diameter of 81 mm and a length of 1.7 m, and it was possible to reduce the size of the laminate.

[003038] Then, in an existing large electrolyzer (electrolyzer similar to that of Example 5-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the coiled state was released to remove the coiled anodes. At that time, the anodes were held substantially vertically to the ground, but the anodes did not come loose. Then, after the anodes were inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003039] It was possible to replace the anodes more easily than conventional ones. It was considered that the renewal of the anodes can be completed in several tens of minutes per cell, when a rolled body of the anode is provided in advance during the electrolytic operation. [Comparative Example 5-1] (Conventional electrode renewal)

[003040] In an existing large electrolyzer (electrolyzer similar to Example 5-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between the

768/803 electrolytic cells. After that, the electrolytic cells were lifted from the large electrolyser with a winch. The removed electrolytic cells were transported to a plant where welding was available.

[003041] After the anode fixed by welding on the rib of the electrolytic cell was removed, burrs or similar in the portion from which the anode was removed with a grinder and so on to smooth the portion. The cathode was removed by removing the fixed portion by folding the portion in the collector.

[003042] Subsequently, a new anode was placed on the rib of the anodic chamber, and the new anode was fixed to the electrolytic cell by spot welding. Likewise, in the case of the cathode, a new cathode was placed on the side of the cathode and fixed by bending the cathode on the collector.

[003043] The renewed electrolytic cell was transported to the position of the large electrolyzer, and the electrolytic cell was returned to the electrolyzer using a winch.

[003044] The period required from the release of the fixed state of the electrolytic cell and the ion exchange membrane to the refixation of the electrolytic cell was one day or more. <Verification of the sixth modality>

[003045] As will be described below, Experimental Examples according to the sixth modality (in the section <Verification of the sixth modality> below, simply called “Examples”) and Experimental Examples not according to the sixth modality (in the section <Verification of the sixth modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 105 and 106, as appropriate.

[003046] As the membrane, an ion exchange membrane b produced as described below was used.

[003047] As reinforcement core materials, were used

768/803 electrolytic cells. After that, the electrolytic cells were lifted from the large electrolyser with a winch. The removed electrolytic cells were transported to a plant where welding was available.

[003041] After the anode fixed by welding on the rib of the electrolytic cell was removed, burrs or similar in the portion from which the anode was removed with a grinder and so on to smooth the portion. The cathode was removed by removing the fixed portion by folding the portion in the collector.

[003042] Subsequently, a new anode was placed on the rib of the anodic chamber, and the new anode was fixed to the electrolytic cell by spot welding. Likewise, in the case of the cathode, a new cathode was placed on the side of the cathode and fixed by bending the cathode on the collector.

[003043] The renewed electrolytic cell was transported to the position of the large electrolyzer, and the electrolytic cell was returned to the electrolyzer using a winch.

[003044] The period required from the release of the fixed state of the electrolytic cell and the ion exchange membrane to the refixation of the electrolytic cell was one day or more. <Verification of the sixth modality>

[003045] As will be described below, Experimental Examples according to the sixth modality (in the section <Verification of the sixth modality> below, simply called “Examples”) and Experimental Examples not according to the sixth modality (in the section <Verification of the sixth modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 105 and 106, as appropriate.

[003046] As the membrane, an ion exchange membrane b produced as described below was used.

[003047] As reinforcement core materials, were used

769/803 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarns). As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[003048] Next, a dry resin A which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a B resin of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.03 mg equivalent / g.

[003049] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[003050] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[003051] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by weight of dimethyl sulfoxide (DMSO) and

769/803 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarns). As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

[003048] Next, a dry resin A which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a B resin of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.03 mg equivalent / g.

[003049] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[003050] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[003051] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by weight of dimethyl sulfoxide (DMSO) and

770/803 15% by mass of potassium hydroxide (KOH) over 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[003052] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of the acid type B resin resin and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the composite membrane surfaces to obtain an ion exchange membrane A. At the zirconium oxide coating density measured by X-ray fluorescence measurement was 0.5 mg / ecm ?. Here, the average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[003053] As the electrode, a cathode and anode below were used.

[003054] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 22 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.95 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[003055] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 44%.

[003056] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. An

770/803 15% by mass of potassium hydroxide (KOH) over 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[003052] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of the acid type B resin resin and dispersed to prepare a suspension, and the suspension was sprayed on both surfaces of the above composite membrane by a suspension spray method to form zirconium oxide coatings on the composite membrane surfaces to obtain an ion exchange membrane A. At the zirconium oxide coating density measured by X-ray fluorescence measurement was 0.5 mg / ecm ?. Here, the average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[003053] As the electrode, a cathode and anode below were used.

[003054] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 22 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.95 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[003055] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 44%.

[003056] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. An

771/803 ruthenium nitrate solution with 100 g / L ruthenium concentration (FURUYA METAL Co ,, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[003057] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced was 29 µm. The thickness of the catalytic layer containing ruthenium oxide and cerium oxide, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[003058] A titanium non-woven fabric with a gauge thickness of 100 µm, a titanium fiber diameter of 20 µm, a base weight of 100 g / m? Was used, and an opening ratio of 78% as a substrate to the electrode

771/803 ruthenium nitrate solution with 100 g / L ruthenium concentration (FURUYA METAL Co ,, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[003057] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced was 29 µm. The thickness of the catalytic layer containing ruthenium oxide and cerium oxide, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[003058] A titanium non-woven fabric with a gauge thickness of 100 µm, a titanium fiber diameter of 20 µm, a base weight of 100 g / m? Was used, and an opening ratio of 78% as a substrate to the electrode for electrolysis of the anode.

[003059] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anodic coating liquid.

[003060] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, preliminary cooking and cooking operations were carried out repeatedly, and then cooking at 520ºC was carried out for one hour. [Example 6-1] (Example of using a cathodic membrane laminate)

for electrolysis of the anode.

[003059] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anodic coating liquid.

[003060] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, preliminary cooking and cooking operations were carried out repeatedly, and then cooking at 520ºC was carried out for one hour. [Example 6-1] (Example of using a cathodic membrane laminate)

773/803

[003061] A rolled body was produced in advance as follows. First, an ion exchange membrane b with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003062] After immersing the ion exchange membrane b in a 2% sodium bicarbonate solution for a whole day and night, the cathodes were arranged without any interstice on the side of the carboxylic acid layer of the ion exchange membrane to produce a laminate of the cathodes and the ion exchange membrane b. When the cathodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the cathodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body. To fuse the ion exchange membrane b, a temperature of 200ºC or more is required. In the present example, the ion exchange membrane did not fuse during integration.

[003063] Then, in an existing large electrolyzer (electrolyzer with a structure similar to those shown in Figures 105 and 106), a fixed state of the adjacent electrolytic cells and the ion exchange membrane through a pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground,

773/803

[003061] A rolled body was produced in advance as follows. First, an ion exchange membrane b with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003062] After immersing the ion exchange membrane b in a 2% sodium bicarbonate solution for a whole day and night, the cathodes were arranged without any interstice on the side of the carboxylic acid layer of the ion exchange membrane to produce a laminate of the cathodes and the ion exchange membrane b. When the cathodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the cathodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body. To fuse the ion exchange membrane b, a temperature of 200ºC or more is required. In the present example, the ion exchange membrane did not fuse during integration.

[003063] Then, in an existing large electrolyzer (electrolyzer with a structure similar to those shown in Figures 105 and 106), a fixed state of the adjacent electrolytic cells and the ion exchange membrane through a pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground,

774/803 but the cathode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003064] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that electrode renewal and membrane replacement can be completed in several tens of minutes per cell. [Example 6-2] (Example of using anodic membrane laminate)

[003065] A rolled body was produced in advance as follows. First, an ion exchange membrane b with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. Additionally, four anodes with a size of 0.3 m in length and 2.4 m in width were provided according to the method mentioned above.

[003066] After the ion exchange membrane b was immersed in a 2% sodium bicarbonate solution for an entire day and night, the anodes were arranged without any interstice on the sulfonic acid layer side of the ion exchange membrane for produce a laminate of the anodes and the ion exchange membrane. When the anodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the anodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body.

[003067] Then, in an existing large electrolyzer (electrolyzer similar to that of Example 6-1), a fixed state of the cells

774/803 but the cathode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003064] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that electrode renewal and membrane replacement can be completed in several tens of minutes per cell. [Example 6-2] (Example of using anodic membrane laminate)

[003065] A rolled body was produced in advance as follows. First, an ion exchange membrane b with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. Additionally, four anodes with a size of 0.3 m in length and 2.4 m in width were provided according to the method mentioned above.

[003066] After the ion exchange membrane b was immersed in a 2% sodium bicarbonate solution for an entire day and night, the anodes were arranged without any interstice on the sulfonic acid layer side of the ion exchange membrane for produce a laminate of the anodes and the ion exchange membrane. When the anodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the anodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body.

[003067] Then, in an existing large electrolyzer (electrolyzer similar to that of Example 6-1), a fixed state of the cells

775/803 adjacent electrolytes and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003068] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that electrode renewal and membrane replacement can be completed in several tens of minutes per cell. [Example 6-3] (Example of using anodic / cathodic membrane laminate)

[003069] A rolled body was produced in advance as follows. First, an ion exchange membrane b with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four anodes and four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003070] After immersion of the ion exchange membrane b in a 2% sodium bicarbonate solution for an entire day and night, the cathodes were arranged on the side of the carboxylic acid layer of the ion exchange membrane and the anodes were arranged on the side of the sulfonic acid layer of the ion exchange membrane without any interstice to produce a laminate of the cathodes, anodes and the ion exchange membrane b. When the cathodes and anodes were placed on the membrane, contact with

775/803 adjacent electrolytes and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003068] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that electrode renewal and membrane replacement can be completed in several tens of minutes per cell. [Example 6-3] (Example of using anodic / cathodic membrane laminate)

[003069] A rolled body was produced in advance as follows. First, an ion exchange membrane b with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four anodes and four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003070] After immersion of the ion exchange membrane b in a 2% sodium bicarbonate solution for an entire day and night, the cathodes were arranged on the side of the carboxylic acid layer of the ion exchange membrane and the anodes were arranged on the side of the sulfonic acid layer of the ion exchange membrane without any interstice to produce a laminate of the cathodes, anodes and the ion exchange membrane b. When the cathodes and anodes were placed on the membrane, contact with

776/803 the aqueous sodium bicarbonate solution made the surface tension work, and the cathodes, anodes and membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body.

[003071] Then, in an existing large electrolyzer (electrolyzer similar to Example 6-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003072] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that electrode renewal and membrane replacement can be completed in several tens of minutes per cell. [Comparative Example 6-1]

[003073] A laminate of membrane electrodes was produced by thermal compression of an electrode on a membrane as follows, with reference to Japanese Patent Examples Open to the Public No. 58-

48686.

[003074] A fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 33% was used

776/803 the aqueous sodium bicarbonate solution made the surface tension work, and the cathodes, anodes and membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body.

[003071] Then, in an existing large electrolyzer (electrolyzer similar to Example 6-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003072] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that electrode renewal and membrane replacement can be completed in several tens of minutes per cell. [Comparative Example 6-1]

[003073] A laminate of membrane electrodes was produced by thermal compression of an electrode on a membrane as follows, with reference to Japanese Patent Examples Open to the Public No. 58-

48686.

[003074] A fully laminated nickel expanded metal with a gauge thickness of 100 µm and an opening ratio of 33% was used

777/803 as a substrate for the electrode for electrolysis of the cathode to coat the electrode in the same manner as in Example 6-1. The electrode was 200 mm x 200 mm in size, and the number of electrodes was 72. Subsequently, one surface of each electrode was subjected to an inactivation treatment in the following procedure. Polyimide adhesive tape (Chukoh Chemical Industries, Ltd.) was affixed to a surface of the electrodes. A dispersion of PTFE (Dupont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was applied to the other surface and dried in a muffle at 120ºC for 10 minutes. The polyimide tape was peeled and a sintering treatment was carried out in a muffle at 380ºC for 10 minutes. This operation was repeated twice to inactivate the electrode surface.

[003075] A membrane formed by two layers of a perfluorocarbon polymer whose terminal functional group is "-COOCH; 3" (polymer C) and a perfluorocarbon polymer whose terminal group is "- SO3F" (polymer S) was produced. The thickness of polymer layer C was 3 mils and the thickness of polymer layer S was 4 mils. This two-layer membrane was subjected to a saponification treatment to introduce ion exchange groups at the polymer terminals by hydrolysis. The polymer C terminals were hydrolyzed in carboxylic acid groups and the polymer S terminals in sulfo groups. The ion exchange capacity, like the sulfonic acid group, was 1.0 meq / g, and the ion exchange capacity, like the carboxylic acid group, was 0.9 megq / g. The size of the resulting ion exchange membrane was similar to that of Example 6-1.

[003076] The inactivated electrode surface of the above electrode was disposed in an opposite way and thermally pressed (thermally compressed) on the surface with carboxylic acid groups such as ion exchange groups to integrate the ion exchange membrane and the electrodes. That is, under a temperature at which the ion exchange membrane fused, the 72 200 mm square electrodes were integrated into an exchange membrane

777/803 as a substrate for the electrode for electrolysis of the cathode to coat the electrode in the same manner as in Example 6-1. The electrode was 200 mm x 200 mm in size, and the number of electrodes was 72. Subsequently, one surface of each electrode was subjected to an inactivation treatment in the following procedure. Polyimide adhesive tape (Chukoh Chemical Industries, Ltd.) was affixed to a surface of the electrodes. A dispersion of PTFE (Dupont-Mitsui Fluorochemicals Co., Ltd., 31-JR (trade name)) was applied to the other surface and dried in a muffle at 120ºC for 10 minutes. The polyimide tape was peeled and a sintering treatment was carried out in a muffle at 380ºC for 10 minutes. This operation was repeated twice to inactivate the electrode surface.

[003075] A membrane formed by two layers of a perfluorocarbon polymer whose terminal functional group is "-COOCH; 3" (polymer C) and a perfluorocarbon polymer whose terminal group is "- SO3F" (polymer S) was produced. The thickness of polymer layer C was 3 mils and the thickness of polymer layer S was 4 mils. This two-layer membrane was subjected to a saponification treatment to introduce ion exchange groups at the polymer terminals by hydrolysis. The polymer C terminals were hydrolyzed in carboxylic acid groups and the polymer S terminals in sulfo groups. The ion exchange capacity, like the sulfonic acid group, was 1.0 meq / g, and the ion exchange capacity, like the carboxylic acid group, was 0.9 megq / g. The size of the resulting ion exchange membrane was similar to that of Example 6-1.

[003076] The inactivated electrode surface of the above electrode was disposed in an opposite way and thermally pressed (thermally compressed) on the surface with carboxylic acid groups such as ion exchange groups to integrate the ion exchange membrane and the electrodes. That is, under a temperature at which the ion exchange membrane fused, the 72 200 mm square electrodes were integrated into an exchange membrane

778/803 ionic with a size of 1500 mm long and 2500 mm wide. The surface of each electrode was exposed even after thermal compression, and the electrodes passed through no portion of the membrane.

[003077] For the large size of 1500 mm x 2500 mm, a period of one day or more was necessary for the process of integrating the ion exchange membrane and the electrodes via thermal compression. That is, Comparative Example 6-1 was considered to require a longer period to renew the electrode and replace the membrane than in the Examples. <Verification of the seventh modality>

[003078] As will be described below, Experimental Examples were provided according to the seventh modality (in the <Verification of the seventh modality> section, simply called “Examples”) and Experimental Examples not according to the seventh modality (in the section <Verification of the seventh modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 114 and 115, as appropriate.

[003079] Like the membrane, an ion exchange membrane produced as described below was used.

[003080] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarn) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

778/803 ionic with a size of 1500 mm long and 2500 mm wide. The surface of each electrode was exposed even after thermal compression, and the electrodes passed through no portion of the membrane.

[003077] For the large size of 1500 mm x 2500 mm, a period of one day or more was necessary for the process of integrating the ion exchange membrane and the electrodes via thermal compression. That is, Comparative Example 6-1 was considered to require a longer period to renew the electrode and replace the membrane than in the Examples. <Verification of the seventh modality>

[003078] As will be described below, Experimental Examples were provided according to the seventh modality (in the <Verification of the seventh modality> section, simply called “Examples”) and Experimental Examples not according to the seventh modality (in the section <Verification of the seventh modality> below, simply called “Comparative Examples”) were provided and evaluated by the following method. Details will be described with reference to Figures 114 and 115, as appropriate.

[003079] Like the membrane, an ion exchange membrane produced as described below was used.

[003080] As reinforcement core materials, 90 denier monofilaments made of polytetrafluoroethylene (PTFE) (hereinafter called PTFE yarn) were used. As sacrifice yarns, yarns obtained by twisting six strands of 35 denier polyethylene terephthalate (PET) 200 times / m (hereinafter called PET yarns) were used. First, in each of the TD and MD, the PTFE yarns and the sacrificial yarns were woven plain with 24 PTFE yarns / inch so that two sacrificial yarns were arranged between adjacent PTFE yarns, to obtain a woven fabric. The resulting woven fabric was pressed together by a roller to obtain a woven fabric with a thickness of 70 µm.

779/803

[003081] Next, a dry resin A which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a B resin of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.03 mg equivalent / g.

[003082] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[003083] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[003084] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[003085] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of the acid type B resin resin and dispersed to prepare a suspension, and the suspension was sprayed over both

779/803

[003081] Next, a dry resin A which was a copolymer of CF; = CF, and CF; = CFOCF; CF (CF3) OCF,; CF; COOCH; and had an ion exchange capacity of 0.85 mg equivalent / g, and a B resin of a dry resin that was a copolymer of CF; = CF; and CF; = CFOCF; CF (CF3) OCF; CF3SO, zF and had an ion exchange capacity of 1.03 mg equivalent / g.

[003082] Using these resins A and B, a two-layer film X in which the thickness of a layer of resin A was 15 µm and the thickness of a layer of resin B was 104 µm was obtained by a matrix method coextrusion T.

[003083] Subsequently, the release paper (embossed in conical shape 50 µm high), a reinforcement material and the X film were laminated in that order on a hot plate with a heat source and an internal vacuum source and with micropores on its surface, heated and depressurized under the conditions of a hot plate surface temperature of 223ºC and a reduced pressure degree of 0.067 MPa for 2 minutes, and then the release paper was removed to obtain a composite membrane.

[003084] The resulting composite membrane was immersed in an aqueous solution at 80ºC comprising 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes for saponification. Then, the composite membrane was immersed in an aqueous solution at 50ºC comprising 0.5 N sodium hydroxide (NaOH) for one hour to replace the ion exchange group counter with Na and then washed with water. Then, the membrane was dried at 60ºC.

[003085] In addition, 20 wt% zirconium oxide with a primary particle size of 1 µm was added to a 5 wt% ethanol solution of the acid type B resin resin and dispersed to prepare a suspension, and the suspension was sprayed over both

780/803 composite membrane surfaces above by a suspension spray method to form zirconium oxide coatings on the composite membrane surfaces to obtain an ion exchange membrane A. The zirconium oxide coating density measured by fluorescence measurement of X-rays was 0.5 mg / ecm ?. Here, the average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[003086] As the electrode, a cathode and anode below were used.

[003087] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 22 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.95 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[003088] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 44%.

[003089] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[003090] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of ethylene-propylene-diene rubber

780/803 composite membrane surfaces above by a suspension spray method to form zirconium oxide coatings on the composite membrane surfaces to obtain an ion exchange membrane A. The zirconium oxide coating density measured by fluorescence measurement of X-rays was 0.5 mg / ecm ?. Here, the average particle size was measured by a particle size analyzer (manufactured by SHIMADZU CORPORATION, “SALD (R) 2200”).

[003086] As the electrode, a cathode and anode below were used.

[003087] As a substrate for the electrode for cathodic electrolysis, an electrolytic nickel blade with a gauge thickness of 22 µm was provided. A surface of this nickel blade was subjected to a roughness treatment by electroplating with electrolytic nickel. The arithmetic mean roughness Ra of the rough surface was 0.95 µm. The surface roughness measurement was carried out under the same conditions as the surface roughness measurement of the nickel plate submitted to the pickling treatment.

[003088] A porous sheet was formed by drilling this nickel sheet with circular holes for drilling. The opening ratio was 44%.

[003089] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium nitrate with a ruthenium concentration of 100 g / L (FURUYA METAL Co, Ltd.) and cerium nitrate (KISHIDA CHEMICAL Co., Ltd.) was mixed so that the molar ratio between the element ruthenium and the cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode-coated liquid.

[003090] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of ethylene-propylene-diene rubber

781/803 closed cell foam (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a polyvinyl chloride (PVC) cylinder was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced was 29 µm. The thickness of the catalytic layer containing ruthenium oxide and cerium oxide, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[003091] A non-woven fabric of titanium with a gauge thickness of 100 µm, a titanium fiber diameter of 20 µm, a base weight of 100 g / m? Was used, and an opening ratio of 78% as a substrate to the electrode for electrolysis of the anode.

[003092] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as

781/803 closed cell foam (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a polyvinyl chloride (PVC) cylinder was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). Then, after drying at 50ºC for 10 minutes, preliminary cooking was carried out at 150ºC for 3 minutes and cooking at 350ºC for 10 minutes. A series of these coating, drying, preliminary cooking and cooking operations were repeated until a predetermined amount of coating was obtained. The thickness of the electrode produced was 29 µm. The thickness of the catalytic layer containing ruthenium oxide and cerium oxide, which was determined by subtracting the electrode substrate thickness for electrolysis from the electrode thickness, was 7 µm. The coating was also formed on the non-roughened surface.

[003091] A non-woven fabric of titanium with a gauge thickness of 100 µm, a titanium fiber diameter of 20 µm, a base weight of 100 g / m? Was used, and an opening ratio of 78% as a substrate to the electrode for electrolysis of the anode.

[003092] A coating liquid for use in forming an electrode catalyst was prepared by the following procedure. A solution of ruthenium chloride with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK), iridium chloride with an iridium concentration of 100 g / L (Tanaka Kikinzoku Kogyo KK) and titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) were mixed so that the molar ratio between the ruthenium element, the iridium element and the titanium element was 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as

782/803 an anodic coating liquid.

[003093] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, preliminary cooking and cooking operations were carried out repeatedly, and then cooking at 520ºC was carried out for one hour. [Example 7-1] (Example of using a cathodic membrane laminate)

[003094] A rolled body was produced in advance as follows. First, an ion exchange membrane with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003095] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the cathodes were arranged without any gap on the side of the acid layer

782/803 an anodic coating liquid.

[003093] A vat containing the above coating liquid was placed in the lowest portion of a roller coating apparatus. The tub was placed in such a way that a coating roll formed of winding rubber made of foamed closed cell ethylene-propylene-diene rubber (EPDM) (INOAC CORPORATION, E-4088, thickness 10 mm) around a cylinder polyvinyl chloride (PVC) was always in contact with the coating liquid. A coating roll around which the same EPDM had been wrapped was placed on the upper portion of it, and a roll of PVC was additionally placed above. The coating liquid was applied allowing the electrode substrate to pass between the second coating roll and the PVC roll in the upper portion (roll coating method). After applying the above coating liquid to the porous titanium sheet, drying was carried out at 60ºC for 10 minutes and cooking at 475ºC for minutes. A series of these coating, drying, preliminary cooking and cooking operations were carried out repeatedly, and then cooking at 520ºC was carried out for one hour. [Example 7-1] (Example of using a cathodic membrane laminate)

[003094] A rolled body was produced in advance as follows. First, an ion exchange membrane with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003095] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the cathodes were arranged without any gap on the side of the acid layer

783/803 carboxylic ion exchange membrane to produce a laminate of the cathodes and the ion exchange membrane. When the cathodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the cathodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body.

[003096] Then, in an existing large electrolyzer (electrolyzer with a structure similar to those shown in Figures 114 and 115), a fixed state of the adjacent electrolytic cells and the ion exchange membrane through a pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the cathode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003097] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the electrode renewal and membrane replacement can be completed in several tens of minutes per cell, when a rolled laminated body is provided in advance during the electrolytic operation. [Example 7-2] (Example of using anodic membrane laminate)

[003098] A rolled body was produced in advance as follows

783/803 carboxylic ion exchange membrane to produce a laminate of the cathodes and the ion exchange membrane. When the cathodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the cathodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body.

[003096] Then, in an existing large electrolyzer (electrolyzer with a structure similar to those shown in Figures 114 and 115), a fixed state of the adjacent electrolytic cells and the ion exchange membrane through a pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the cathode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003097] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the electrode renewal and membrane replacement can be completed in several tens of minutes per cell, when a rolled laminated body is provided in advance during the electrolytic operation. [Example 7-2] (Example of using anodic membrane laminate)

[003098] A rolled body was produced in advance as follows

784/803 form. First, an ion exchange membrane with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. Additionally, four anodes with a size of 0.3 m in length and 2.4 m in width were provided according to the method mentioned above.

[003099] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the anodes were arranged without any interstice on the sulfonic acid layer side of the ion exchange membrane to produce a laminate of the anodes and the ion exchange membrane. When the anodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the anodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body.

[003100] Then, in an existing large electrolyzer (electrolyzer similar to that of Example 7-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

784/803 form. First, an ion exchange membrane with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. Additionally, four anodes with a size of 0.3 m in length and 2.4 m in width were provided according to the method mentioned above.

[003099] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the anodes were arranged without any interstice on the sulfonic acid layer side of the ion exchange membrane to produce a laminate of the anodes and the ion exchange membrane. When the anodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution caused the surface tension to work, and the anodes and the membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body.

[003100] Then, in an existing large electrolyzer (electrolyzer similar to that of Example 7-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

785/803

[003101] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the renewal of the electrode and the replacement of the membrane can be completed in several tens of minutes per cell, when a rolled body of the laminate is provided in advance during electrolytic operation. [Example 7-3] (Example of using anodic / cathodic membrane laminate)

[003102] A rolled body was produced in advance as follows. First, an ion exchange membrane with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four anodes and four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003103] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the cathodes were arranged on the carboxylic acid layer side of the ion exchange membrane and the anodes were arranged on the sulfonic acid layer side of the ion exchange membrane without any interstitium to produce a laminate of the cathodes, anodes and the ion exchange membrane. When the cathodes and anodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution made the surface tension work, and the cathodes, anodes and membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body.

[003104] Next, in an existing large electrolyzer (electrolyzer similar to that of Example 7-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a

785/803

[003101] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the renewal of the electrode and the replacement of the membrane can be completed in several tens of minutes per cell, when a rolled body of the laminate is provided in advance during electrolytic operation. [Example 7-3] (Example of using anodic / cathodic membrane laminate)

[003102] A rolled body was produced in advance as follows. First, an ion exchange membrane with a size of 1.5 m in length and 2.5 m in width was provided according to the method mentioned above. In addition, four anodes and four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above.

[003103] After the ion exchange membrane was immersed in a 2% sodium bicarbonate solution for an entire day and night, the cathodes were arranged on the carboxylic acid layer side of the ion exchange membrane and the anodes were arranged on the sulfonic acid layer side of the ion exchange membrane without any interstitium to produce a laminate of the cathodes, anodes and the ion exchange membrane. When the cathodes and anodes were placed on the membrane, contact with the aqueous sodium bicarbonate solution made the surface tension work, and the cathodes, anodes and membrane were integrated as if they were joined. No pressure was applied for such integration. The temperature at the integration was 23ºC. This resulting laminate was wrapped around a polyvinyl chloride (PVC) tube with an outside diameter of 76 mm and a length of 1.7 m to produce a rolled body.

[003104] Next, in an existing large electrolyzer (electrolyzer similar to that of Example 7-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a

786/803 pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003105] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the renewal of the electrode and the replacement of the membrane can be completed in several tens of minutes per cell, when a rolled body of the laminate is provided in advance during electrolytic operation. [Example 7-4] (Example of using cathodes)

[003106] A rolled body was produced in advance as follows. First, four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above. The four cathodes were arranged without any interstice in order to reach a size of 1.2 m in length and 2.4 m in width. Adjacent cathodes were tied with a PTFE rope and fixed in such a way that the cathodes were not separated. In the operation, no pressure was applied and the temperature was 23ºC. These cathodes were wrapped around a polyvinyl chloride (PVC) tube with an external diameter of 76 mm and a length of 1.7 m to produce a coiled body.

[003107] Next, in an existing large electrolyzer (electrolyzer similar to that of Example 7-1), a fixed state of the cells

786/803 pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the rolled state was released to remove the rolled laminate. At that time, the laminate was kept substantially vertically to the ground, but the anode did not come loose. Then, after the laminate was inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the laminate between them.

[003105] It was possible to replace the electrode and membrane more easily than conventional ones. It was considered that the renewal of the electrode and the replacement of the membrane can be completed in several tens of minutes per cell, when a rolled body of the laminate is provided in advance during electrolytic operation. [Example 7-4] (Example of using cathodes)

[003106] A rolled body was produced in advance as follows. First, four cathodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above. The four cathodes were arranged without any interstice in order to reach a size of 1.2 m in length and 2.4 m in width. Adjacent cathodes were tied with a PTFE rope and fixed in such a way that the cathodes were not separated. In the operation, no pressure was applied and the temperature was 23ºC. These cathodes were wrapped around a polyvinyl chloride (PVC) tube with an external diameter of 76 mm and a length of 1.7 m to produce a coiled body.

[003107] Next, in an existing large electrolyzer (electrolyzer similar to that of Example 7-1), a fixed state of the cells

787/803 adjacent electrolytes and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the coiled state was released to remove the coiled cathodes. At that time, the cathodes were held substantially vertically to the ground, but the cathodes did not come loose. Then, after the cathodes were inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the cathodes between them.

[003108] It was possible to replace the cathodes more easily than in conventional ones. It was considered that the cathode renewal can be completed in several tens of minutes per cell, when a rolled-up cathode body is provided in advance during the electrolytic operation. [Example 7-5] (Example of using anodes)

[003109] A rolled body was produced in advance as follows. First, four anodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above. The four anodes were arranged without any interstice in order to reach a size of 1.2 m in length and 2.4 m in width. Adjacent anodes were tied with a PTFE rope and fixed in such a way that the anodes were not separated. In the operation, no pressure was applied and the temperature was 23ºC. These anodes were wrapped around a polyvinyl chloride (PVC) tube with an external diameter of 76 mm and a length of 1.7 m to produce a coiled body.

[003110] Then, in an existing large electrolyzer (electrolyzer similar to that of Example 7-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane through a

787/803 adjacent electrolytes and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the coiled state was released to remove the coiled cathodes. At that time, the cathodes were held substantially vertically to the ground, but the cathodes did not come loose. Then, after the cathodes were inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the cathodes between them.

[003108] It was possible to replace the cathodes more easily than in conventional ones. It was considered that the cathode renewal can be completed in several tens of minutes per cell, when a rolled-up cathode body is provided in advance during the electrolytic operation. [Example 7-5] (Example of using anodes)

[003109] A rolled body was produced in advance as follows. First, four anodes with a size of 0.3 m long and 2.4 m wide were provided according to the method mentioned above. The four anodes were arranged without any interstice in order to reach a size of 1.2 m in length and 2.4 m in width. Adjacent anodes were tied with a PTFE rope and fixed in such a way that the anodes were not separated. In the operation, no pressure was applied and the temperature was 23ºC. These anodes were wrapped around a polyvinyl chloride (PVC) tube with an external diameter of 76 mm and a length of 1.7 m to produce a coiled body.

[003110] Then, in an existing large electrolyzer (electrolyzer similar to that of Example 7-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a

788/803 pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the coiled state was released to remove the coiled anodes. At that time, the anodes were held substantially vertically to the ground, but the anodes did not come loose. Then, after the anodes were inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the anodes between them.

[003111] It was possible to replace the anodes more easily than conventional ones. It was considered that the renewal of the anodes can be completed in several tens of minutes per cell, when a rolled body of the anode is provided in advance during the electrolytic operation. [Comparative Example 7-1] (Conventional electrode renewal)

[003112] In an existing large electrolyzer (electrolyzer similar to Example 7-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the electrolytic cells were lifted from the large electrolyser with a winch. The removed electrolytic cells were transported to a plant where welding was available.

[003113] After the anode fixed by welding on the rib of the electrolytic cell, burrs or similar were removed in the portion from which the anode was removed with a grinder to smooth the portion. The cathode was removed by removing the fixed portion by folding the portion in the collector. [0031 14] Subsequently, a new anode was placed on the rib of the anodic chamber, and the new anode was fixed to the electrolytic cell by spot welding. Likewise, in the case of the cathode, a new cathode was

788/803 pressure device was released, and the existing membrane was removed to provide an interstice between the electrolytic cells. After that, the rolled-up body was transported to the large electrolyser. In the large electrolyzer, while the PVC pipe was in an upright position, the coiled state was released to remove the coiled anodes. At that time, the anodes were held substantially vertically to the ground, but the anodes did not come loose. Then, after the anodes were inserted between the electrolytic cells, the electrolytic cells were moved to sandwich the anodes between them.

[003111] It was possible to replace the anodes more easily than conventional ones. It was considered that the renewal of the anodes can be completed in several tens of minutes per cell, when a rolled body of the anode is provided in advance during the electrolytic operation. [Comparative Example 7-1] (Conventional electrode renewal)

[003112] In an existing large electrolyzer (electrolyzer similar to Example 7-1), a fixed state of the adjacent electrolytic cells and the ion exchange membrane by means of a pressure device was released, and the existing membrane was removed to provide an interstice between electrolytic cells. After that, the electrolytic cells were lifted from the large electrolyser with a winch. The removed electrolytic cells were transported to a plant where welding was available.

[003113] After the anode fixed by welding on the rib of the electrolytic cell, burrs or similar were removed in the portion from which the anode was removed with a grinder to smooth the portion. The cathode was removed by removing the fixed portion by folding the portion in the collector. [0031 14] Subsequently, a new anode was placed on the rib of the anodic chamber, and the new anode was fixed to the electrolytic cell by spot welding. Likewise, in the case of the cathode, a new cathode was

789/803 placed on the cathode side and fixed by bending the cathode on the collector.

[003115] The renewed electrolytic cell was transported to the position of the large electrolyzer, and the electrolytic cell was returned to the electrolyzer using a winch.

[003116] The period required from the release of the fixed state of the electrolytic cell and the ion exchange membrane to the refixation of the electrolytic cell was one day or more.

[003117] This application is based on Japanese Patent Applications filed on March 22, 2017 (Japanese Patent Applications No. 2017- 056524 and No. 2017-056525) and Japanese Patent Applications filed on March 20, 2018 (Applications of Japanese Patent nº 2018-053217, nº 2018- 053146, nº 2018-053144, nº 2018-053231, nº 2018-053145, nº 2018-053149, and nº 2018-053139), whose content is incorporated by reference. List of Reference Signs <Figures for the first modality> List of reference signs for the Figure | 10 ... electrolyte electrode substrate 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 2 to 4 1 ... ion exchange membrane 2 .. carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... reinforcement core material 100 ... electrolyser

789/803 placed on the cathode side and fixed by bending the cathode on the collector.

[003115] The renewed electrolytic cell was transported to the position of the large electrolyzer, and the electrolytic cell was returned to the electrolyzer using a winch.

[003116] The period required from the release of the fixed state of the electrolytic cell and the ion exchange membrane to the refixation of the electrolytic cell was one day or more.

[003117] This application is based on Japanese Patent Applications filed on March 22, 2017 (Japanese Patent Applications No. 2017- 056524 and No. 2017-056525) and Japanese Patent Applications filed on March 20, 2018 (Applications of Japanese Patent nº 2018-053217, nº 2018- 053146, nº 2018-053144, nº 2018-053231, nº 2018-053145, nº 2018-053149, and nº 2018-053139), whose content is incorporated by reference. List of Reference Signs <Figures for the first modality> List of reference signs for the Figure | 10 ... electrolyte electrode substrate 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 2 to 4 1 ... ion exchange membrane 2 .. carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... reinforcement core material 100 ... electrolyser

790/803 200 ... anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous hole List of reference signals for Figures 5 to 9

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode 22 ... metal elastic body 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis List of reference signals for Figure 10 1 ... forceps template (SUS)

790/803 200 ... anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous hole List of reference signals for Figures 5 to 9

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode 22 ... metal elastic body 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis List of reference signals for Figure 10 1 ... forceps template (SUS)

791/803 2 ... electrode 3 ... membrane 4 ... nickel plate (etched with 320 grain size alumina) 100 ... front face 200 ... side face List of reference signs for the Figures 11 to 13

1 ... membrane 2a ... polyethylene tube with an outer diameter of 280 mm 2b ... polyethylene tube with an outer diameter of 145 mm 3 ... delaminated portion 4 ... close contact portion 5 .. electrode List of reference signals for Figure 14 1 ... polyvinyl chloride (PVC) tube 2 ... ion exchange membrane 3 ... electrode 4 ... surface plate List of reference signals for the Figure 15 1 ... surface plate 2 ... deformed electrode 10 ... template for fixing electrode 20 ... direction in which a force is applied List of reference signals for Figures 16 to 21 1 ... line 110 mm 2 nickel ... 950 mm nickel line

3 ... armature <Figures for the second modality> List of reference signs for Figure 22

791/803 2 ... electrode 3 ... membrane 4 ... nickel plate (etched with 320 grain size alumina) 100 ... front face 200 ... side face List of reference signs for the Figures 11 to 13

1 ... membrane 2a ... polyethylene tube with an outer diameter of 280 mm 2b ... polyethylene tube with an outer diameter of 145 mm 3 ... delaminated portion 4 ... close contact portion 5 .. electrode List of reference signals for Figure 14 1 ... polyvinyl chloride (PVC) tube 2 ... ion exchange membrane 3 ... electrode 4 ... surface plate List of reference signals for the Figure 15 1 ... surface plate 2 ... deformed electrode 10 ... template for fixing electrode 20 ... direction in which a force is applied List of reference signals for Figures 16 to 21 1 ... line 110 mm 2 nickel ... 950 mm nickel line

3 ... armature <Figures for the second modality> List of reference signs for Figure 22

792/803 10 ... electrode substrate for electrolysis 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 23 to 25 1 ... ion exchange membrane 2 ... carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... core material reinforcement 100 ... electrolyzer 200 ... anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous hole List of reference signals for Figures 26 to 30

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode

12 ... anodic gasket 13 ... cathodic gasket

792/803 10 ... electrode substrate for electrolysis 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 23 to 25 1 ... ion exchange membrane 2 ... carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... core material reinforcement 100 ... electrolyzer 200 ... anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous hole List of reference signals for Figures 26 to 30

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode

12 ... anodic gasket 13 ... cathodic gasket

793/803 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 ... cathodic chamber 21 ... cathode 22 ... elastic body metal 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis List of reference signals for Figure 31 1 ... clamp template (SUS) 2 ... electrode 3 ... membrane 4 ... nickel plate (etched with 320 grain size alumina) 100 ... front face 200 ... side face List of reference signs for Figures 32 to 34

1 ... membrane 2a ... polyethylene tube with an outer diameter of 280 mm 2b ... polyethylene tube with an outer diameter of 145 mm 3 ... delaminated portion 4 ... close contact portion 5 .. electrode List of reference signals for Figure 35 1 ... polyvinyl chloride (PVC) tube 2 ... ion exchange membrane

793/803 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 ... cathodic chamber 21 ... cathode 22 ... elastic body metal 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis List of reference signals for Figure 31 1 ... clamp template (SUS) 2 ... electrode 3 ... membrane 4 ... nickel plate (etched with 320 grain size alumina) 100 ... front face 200 ... side face List of reference signs for Figures 32 to 34

1 ... membrane 2a ... polyethylene tube with an outer diameter of 280 mm 2b ... polyethylene tube with an outer diameter of 145 mm 3 ... delaminated portion 4 ... close contact portion 5 .. electrode List of reference signals for Figure 35 1 ... polyvinyl chloride (PVC) tube 2 ... ion exchange membrane

794/803 3 ... electrode 4 ... surface plate List of reference signals for Figure 36 1 ... surface plate 2 ... deformed electrode 10 ... template for fixing electrode 20 ... direction where a force is applied List of reference signals for Figures 37 to 42 1 ... 110 mm nickel line 2 ... 950 mm nickel line

3 ... frame <Figures for the third modality> List of reference signals for Figure 43 10 ... substrate for electrolysis electrode 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 44 to 46 1 ... ion exchange membrane 2 ... carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... reinforcement core material 100 ... electrolyzer 200 ... anode 300 ... cathode 52 ... reinforcement wire

794/803 3 ... electrode 4 ... surface plate List of reference signals for Figure 36 1 ... surface plate 2 ... deformed electrode 10 ... template for fixing electrode 20 ... direction where a force is applied List of reference signals for Figures 37 to 42 1 ... 110 mm nickel line 2 ... 950 mm nickel line

3 ... frame <Figures for the third modality> List of reference signals for Figure 43 10 ... substrate for electrolysis electrode 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 44 to 46 1 ... ion exchange membrane 2 ... carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... reinforcement core material 100 ... electrolyzer 200 ... anode 300 ... cathode 52 ... reinforcement wire

795/803 504a ... sacrifice wire 504 ... continuous bore 504 List of reference signals for Figures 47 to 51

1 ... laminate 2 ... electrolysis electrode 2a ... inner surface of electrode for electrolysis 2b ... outer surface of electrode for electrolysis 3 ... membrane 3a ... inner surface of membrane 3b ... surface outer membrane 7 ... fixing member List of reference signs for Figures 52 to 56

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode 22 ... elastic metal body

795/803 504a ... sacrifice wire 504 ... continuous bore 504 List of reference signals for Figures 47 to 51

1 ... laminate 2 ... electrolysis electrode 2a ... inner surface of electrode for electrolysis 2b ... outer surface of electrode for electrolysis 3 ... membrane 3a ... inner surface of membrane 3b ... surface outer membrane 7 ... fixing member List of reference signs for Figures 52 to 56

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode 22 ... elastic metal body

796/803 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis <Figures for the fourth modality> List of reference signals for Figures 63 to 67

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode 22 ... metal elastic body 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis List of reference signals for Figure 68 10 ... electrode substrate for electrolysis

796/803 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis <Figures for the fourth modality> List of reference signals for Figures 63 to 67

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode 22 ... metal elastic body 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis List of reference signals for Figure 68 10 ... electrode substrate for electrolysis

797/803 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 69 to 71 1 ... ion exchange membrane 2 ... carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... reinforcement core material 100 ... electrolyzer 200. .. anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous hole List of reference signals for Figures 72 to 78

1 ... laminate 2 ... electrolysis electrode 2a ... inner surface of electrode for electrolysis 2b ... outer surface of electrode for electrolysis 3 ... membrane 3a ... inner surface of membrane 3b ... surface outer membrane 7 ... fixing member A ... gasket B ... membrane C ... electrode for electrolysis

797/803 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 69 to 71 1 ... ion exchange membrane 2 ... carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... reinforcement core material 100 ... electrolyzer 200. .. anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous hole List of reference signals for Figures 72 to 78

1 ... laminate 2 ... electrolysis electrode 2a ... inner surface of electrode for electrolysis 2b ... outer surface of electrode for electrolysis 3 ... membrane 3a ... inner surface of membrane 3b ... surface outer membrane 7 ... fixing member A ... gasket B ... membrane C ... electrode for electrolysis

798/803 Al ... outermost perimeter of the BI gasket ... outermost perimeter of the CI membrane ... outermost perimeter of the electrode for electrolysis List of reference signals for Figure 79 1 ... clamp template (SUS ) 2 ... electrode 3 ... membrane 4 ... nickel plate (etched with 320 grain size alumina) 100 ... front face 200 ... side face List of reference signs for Figure 80 a 82

1 ... membrane 2a ... polyethylene tube with an outer diameter of 280 mm 2b ... polyethylene tube with an outer diameter of 145 mm 3 ... delaminated portion 4 ... close contact portion 5 .. electrode List of reference signals for Figure 84 1 ... surface plate 2 ... deformed electrode 10 ... template for fixing electrode 20 ... direction in which a force is applied List of reference signals for the Figure 85 to 90 1 ... 110 mm nickel line 2 ... 950 mm nickel line

3 ... armature <Figures for the fifth modality> List of reference signs for Figures 91 to 95

798/803 Al ... outermost perimeter of the BI gasket ... outermost perimeter of the CI membrane ... outermost perimeter of the electrode for electrolysis List of reference signals for Figure 79 1 ... clamp template (SUS ) 2 ... electrode 3 ... membrane 4 ... nickel plate (etched with 320 grain size alumina) 100 ... front face 200 ... side face List of reference signs for Figure 80 a 82

1 ... membrane 2a ... polyethylene tube with an outer diameter of 280 mm 2b ... polyethylene tube with an outer diameter of 145 mm 3 ... delaminated portion 4 ... close contact portion 5 .. electrode List of reference signals for Figure 84 1 ... surface plate 2 ... deformed electrode 10 ... template for fixing electrode 20 ... direction in which a force is applied List of reference signals for the Figure 85 to 90 1 ... 110 mm nickel line 2 ... 950 mm nickel line

3 ... armature <Figures for the fifth modality> List of reference signs for Figures 91 to 95

799/803

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode 22 ... metal elastic body 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis List of reference signals for Figure 96 10 ... electrolyte electrode substrate 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 97 to 99 1 ... ion exchange membrane 2 .. layer of carboxylic acid

799/803

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode 22 ... metal elastic body 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis List of reference signals for Figure 96 10 ... electrolyte electrode substrate 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 97 to 99 1 ... ion exchange membrane 2 .. layer of carboxylic acid

800/803 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... reinforcement core material 100 .. electrolyzer 200 ... anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous hole <Figures for the sixth modality> List of reference signals for Figures 103 to 107

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode

800/803 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... reinforcement core material 100 .. electrolyzer 200 ... anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous hole <Figures for the sixth modality> List of reference signals for Figures 103 to 107

1 ... electrolytic cell 2 ... ion exchange membrane 4 ... electrolyzer 5 ... pressure device 6 ... cathode terminal 7 ... anode terminal 10 ... anode chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode

801/803 22 ... elastic metal body 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis List of reference signals for Figure 108 10 ... substrate for electrolysis electrode 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 109 to 111 1 ... ion exchange membrane 2 ... carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... reinforcement core material 100 ... electrolyzer 200 ... anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous hole <Figures for the seventh modality> List of reference signals for Figures 112 to 118

1 ... electrolytic cell 2 ... ion exchange membrane 2a ... new ion exchange membrane

801/803 22 ... elastic metal body 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis List of reference signals for Figure 108 10 ... substrate for electrolysis electrode 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signals for Figures 109 to 111 1 ... ion exchange membrane 2 ... carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21.22 ... reinforcement core material 100 ... electrolyzer 200 ... anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous hole <Figures for the seventh modality> List of reference signals for Figures 112 to 118

1 ... electrolytic cell 2 ... ion exchange membrane 2a ... new ion exchange membrane

802/803 4 ... electrolyzer 5 ... pressure device 6 ... cathodic terminal 7 ... anodic terminal 8 ... electrolyzer frame 9 ... laminated 10 ... anodic chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode 22 ... metal elastic body 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis 100 ... electrode for electrolysis List of reference signs for Figure 119 10 ... electrode substrate for electrolysis 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signs for Figures 120 to 122 1 ... ion exchange membrane

802/803 4 ... electrolyzer 5 ... pressure device 6 ... cathodic terminal 7 ... anodic terminal 8 ... electrolyzer frame 9 ... laminated 10 ... anodic chamber

11 ... anode 12 ... anodic gasket 13 ... cathodic gasket 18 ... reverse current absorber 18a ... substrate 18b ... reverse current absorbent layer 19 ... anodic chamber bottom 20 .. cathodic chamber 21 ... cathode 22 ... metal elastic body 23 ... collector 24 ... support 30 ... partition wall 40 ... cathode structure for electrolysis 100 ... electrode for electrolysis List of reference signs for Figure 119 10 ... electrode substrate for electrolysis 20 ... first layer 30 ... second layer 100 ... electrolysis electrode List of reference signs for Figures 120 to 122 1 ... ion exchange membrane

803/803 2 ... carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21,22 ... reinforcement core material 100 ... electrolyzer 200 ... anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous bore

803/803 2 ... carboxylic acid layer 3 ... sulfonic acid layer 4 ... reinforcement core material 10 ... membrane body 11a, 11b ... coating layer 21,22 ... reinforcement core material 100 ... electrolyzer 200 ... anode 300 ... cathode 52 ... reinforcement wire 504a ... sacrifice wire 504 ... continuous bore

Claims (15)

1. Electrode for electrolysis, characterized by the fact that it has a mass per unit area of 48 mg / cm? or less and a force applied per unit mass-unit area of 0.08 N / mg: cm? or more. 2. Electrolysis electrode according to claim 1, characterized in that the electrolysis electrode comprises a electrolyte electrode substrate and a catalytic layer, and the electrolysis electrode substrate has a thickness of 300 µm or less. 3. Electrolysis electrode according to claim 1 or 2, characterized by the fact that a proportion measured by method (3) below is 75% or more: [Method (3)] An ion exchange membrane (170 mm square), which is obtained by applying particles of inorganic material and a binder on both surfaces of a perfluorocarbon polymer membrane into which an ion exchange group is introduced, and an electrode sample for electrolysis (130 mm square) are rolled in that order; and the laminate is placed on a curved surface of a polyethylene tube (external diameter: 145 mm) so that the electrode sample for electrolysis in that laminate is positioned outside under conditions of 23 + 2ºC and humidity relative to 30 + 5%, the laminate and the tube are sufficiently immersed in pure water, the excess water deposited on a surface of the laminate and the tube is removed, and one minute after this removal, a proportion (% ) of a portion area, in which the electrolyte electrode sample is in close contact with the membrane obtained by applying the particles of inorganic material and the binder on both surfaces of the perfluorocarbon polymer membrane in which the exchange group ionic is introduced. 4. Electrode for electrolysis according to any of the claims | to 3, characterized by the fact that the electrolysis electrode has a porous structure and has an opening ratio of 5 to 90%. 5. Electrolysis electrode according to any of the claims | to 4, characterized by the fact that the electrode has a porous structure and has an opening ratio of 10 to 80%. 6. Electrolysis electrode according to any of the claims | to 5, characterized by the fact that the electrolysis electrode has a thickness of 315 µm or less. 7. Electrolysis electrode according to any of the claims | to 6, characterized by the fact that a value obtained by measuring the electrode for electrolysis by method (A) below is 40 mm or less: [Method (A)] Under conditions of temperature of 23 + 2ºC and relative humidity of 30+ 5%, a sample obtained by laminating the ion exchange membrane and the electrolysis electrode is wound and fixed on a curved surface of a core material made of polyvinyl chloride and with an outside diameter of 32 mm and left to stand for 6 hours; thereafter, when the electrolysis electrode is separated from the sample and placed on a flat plate, heights in a vertical direction on both edges of the electrolysis electrode L, and L7 are measured, and an average value is used as a value of measurement. 8. Electrolysis electrode according to any one of claims 1 to 7, characterized by the fact that a ventilation resistance is 24 kPa-s / m or less when the electrolysis electrode has a size of 50 mm x 50 mm, the ventilation resistance being measured under temperature conditions of 24ºC, the relative humidity of 32%, a piston speed of 0.2 cm / s and a ventilation volume of 0.4 cc / in? / s. 9. Laminate, characterized by the fact that it comprises the electrolysis electrode as defined in any one of claims 1 aê. 10. Coiled body, characterized by the fact that it comprises the electrolysis electrode as defined in any one of claims 1 to 8 or the laminate as defined in claim 9. 11. Laminate, characterized by the fact that it comprises: an electrolysis electrode, and a membrane or supply conductor in contact with the electrolysis electrode, in which a force applied per unit mass-unit area of the electrode for electrolysis in the membrane or in the supply conductor is less than 1.5 N / mg: cm ?. 12. Laminate according to claim 11, characterized by the fact that the force applied per unit mass-unit area of the electrode for electrolysis in the membrane or in the supply conductor is greater than 0.005 N / mg-cm ?. Laminate according to claim 11 or 12, characterized in that the feed conductor is a wire mesh, a non-woven metal fabric, a perforated metal, an expanded metal or a foamy metal. Laminate according to claim 12 or 13, characterized in that it comprises, as at least one membrane surface layer, a layer comprising a mixture of hydrophilic oxide particles and a polymer in which ion exchange groups are introduced . Laminate according to any one of claims 12 to 14, characterized in that a liquid is interposed between the electrolysis electrode and the membrane or the supply conductor.