JP2018159129A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that can improve work efficiency in updating an electrode in an electrolytic cell and can express excellent electrolytic performance even after updating.SOLUTION: A laminate has an electrolysis electrode, and a diaphragm or a power feeder in contact with the electrolysis electrode. An applied force per unit mass/unit area of the electrolysis electrode, with respect to the diaphragm or power feeder, is less than 1.5 N/mg cm. The electrolysis electrode can be readily peeled, to save the time and effort for replacement.SELECTED DRAWING: None

Description

  The present invention relates to a laminate.

In the electrolysis of aqueous alkali metal chloride solutions such as saline and water (hereinafter referred to as “electrolysis”), a diaphragm, more specifically, an electrolytic cell equipped with an ion exchange membrane or a microporous membrane was used. The method is being used. In many cases, the electrolytic cell includes electrolytic cells connected in series inside the electrolytic cell. Electrolysis is performed with a diaphragm interposed between the electrolysis cells. In an electrolysis cell, a cathode chamber having a cathode and an anode chamber having an anode are arranged back to back through a partition wall (back plate) or by pressing by pressing pressure, bolting, or the like.
The anode and cathode currently used in these electrolytic cells are fixed to the anode chamber and cathode chamber of the electrolytic cell by welding, folding, etc., and then stored and transported to customers. On the other hand, the diaphragm itself is stored in a state wrapped around a pipe made of vinyl chloride (vinyl chloride) and transported to a customer. The customer assembles the electrolytic cell by arranging the electrolytic cells on the frame of the electrolytic cell and sandwiching the diaphragm between the electrolytic cells. In this way, the electrolytic cell is manufactured and the electrolytic cell is assembled at the customer site. As a structure applicable to such an electrolytic cell, Patent Documents 1 and 2 disclose a structure in which a diaphragm and an electrode are integrated.

JP 58-048686 JP 55-148775 A

When the electrolysis operation is started and continued, each part deteriorates due to various factors, and the electrolysis performance deteriorates. At a certain point, each part is replaced. The diaphragm can be easily updated by removing it from between the electrolysis cells and inserting a new diaphragm. On the other hand, since the anode and cathode are fixed to the electrolytic cell, when the electrode is renewed, the electrolytic cell is taken out from the electrolytic cell, taken out to the dedicated renewal factory, and the old electrode is peeled off by removing the fixing such as welding, and then the new electrode And fixing by a method such as welding, transporting to an electrolytic factory, and returning to an electrolytic cell. Here, it is conceivable to use a structure in which the diaphragm and the electrode described in Patent Documents 1 and 2 are integrated by thermocompression bonding for the above update, but the structure is relatively easy at the laboratory level. However, it is not easy to manufacture in accordance with an actual commercial size electrolysis cell (for example, 1.5 m in length and 3 m in width). In addition, electrolysis performance (electrolysis voltage, current efficiency, sodium chloride concentration in caustic soda, etc.) and durability are remarkably poor, and chlorine gas and hydrogen gas are generated on the electrode at the diaphragm and interface. Therefore, it cannot be used practically.
The present invention has been made in view of the above-described problems of the prior art, and can improve the working efficiency at the time of electrode renewal in an electrolytic cell, and further exhibits excellent electrolytic performance even after renewal. It aims at providing the laminated body which can be manufactured.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have a laminate including a diaphragm such as an ion exchange membrane and a microporous membrane, a deteriorated existing electrode, and an electrode that adheres with a weak force. It has been found that it is easy to transport and handle, greatly simplify the work when starting a new electrolytic cell or renewing deteriorated parts, and also maintain or improve the electrolytic performance, The present invention has been completed.
That is, this invention includes the following aspects.
[1]
An electrode for electrolysis;
A diaphragm or a power feeder in contact with the electrode for electrolysis;
With
The laminated body whose force per unit mass and unit area of the electrode for electrolysis with respect to the diaphragm or the power feeding body is less than 1.5 N / mg · cm ² .
[2]
The laminated body according to [1], wherein the force per unit mass / unit area of the electrode for electrolysis with respect to the diaphragm or the power feeding body is more than 0.005 N / mg · cm ² .
[3]
The laminated body according to [1] or [2], wherein the power feeding body is a metal mesh, a metal nonwoven fabric, a punching metal, an expanded metal, or a foam metal.
[4]
The laminate according to any one of [1] to [3], which has a layer containing a mixture of hydrophilic oxide particles and a polymer into which an ion exchange group is introduced as at least one surface layer of the diaphragm.
[5]
The laminate according to any one of [1] to [4], wherein a liquid is interposed between the electrode for electrolysis and the diaphragm or the power feeding body.

  According to the laminate of the present invention, it is possible to improve the working efficiency at the time of electrode renewal in an electrolytic cell, and it is possible to develop excellent electrolytic performance even after renewal.

It is a typical sectional view of the electrode for electrolysis in one embodiment of the present invention. It is a cross-sectional schematic diagram which shows one Embodiment of an ion exchange membrane. It is the schematic for demonstrating the aperture ratio of the reinforcing core material which comprises an ion exchange membrane. It is a schematic diagram for demonstrating the method of forming the communicating hole of an ion exchange membrane. It is a typical sectional view of an electrolysis cell. It is a typical sectional view showing the state where two electrolysis cells were connected in series. It is a schematic diagram of an electrolytic cell. It is a typical perspective view which shows the process of assembling an electrolytic cell. It is a typical sectional view of a reverse current absorber with which an electrolysis cell is provided. It is a schematic diagram of the evaluation method of force (1) applied per unit mass and unit area described in the examples. It is a schematic diagram of the 280-mm diameter cylindrical winding evaluation method (1) as described in an Example. It is a schematic diagram of the 280-mm diameter cylindrical winding evaluation method (2) as described in an Example. It is a schematic diagram of the 145 mm diameter cylindrical winding evaluation method (3) described in the Examples. It is a schematic diagram of the elastic deformation test of the electrode as described in an Example. It is a schematic diagram of the evaluation method of the softness after plastic deformation. 6 is a schematic diagram of an electrode produced in Example 34. FIG. It is a schematic diagram of the structure used in order to install the electrode produced in Example 34 on a nickel mesh electric power feeder. 22 is a schematic diagram of an electrode produced in Example 35. FIG. It is a schematic diagram of the structure used in order to install the electrode produced in Example 35 on a nickel mesh electric power feeder. FIG. 11 is a schematic diagram of an electrode produced in Example 36. It is a schematic diagram of the structure used in order to install the electrode produced in Example 36 on a nickel mesh electric power feeder.

  Hereinafter, an embodiment of the present invention (hereinafter also referred to as the present embodiment) will be described in detail with reference to the drawings as necessary. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the following contents. The accompanying drawings show an example of the embodiment, and the form is not construed as being limited thereto. The present invention can be implemented with appropriate modifications within the scope of the gist thereof. Note that the positional relationship such as up, down, left, and right in the drawing is based on the positional relationship shown in the drawing unless otherwise specified. The dimensions and ratios of the drawings are not limited to those shown in the drawings.

[Laminate]
The laminate of the present embodiment includes an electrode for electrolysis and a diaphragm or a power supply body in contact with the electrode for electrolysis, and a force per unit mass / unit area of the electrode for electrolysis applied to the diaphragm or the power supply body. Is less than 1.5 N / mg · cm ² . Since it is comprised in this way, the laminated body of this embodiment can improve the working efficiency at the time of the electrode update in an electrolytic cell, and also can express the outstanding electrolysis performance after the update.
That is, when the electrode is renewed by the laminate of the present embodiment, the electrode is renewed by a simple operation similar to the renewal of the diaphragm without a complicated work such as peeling off the existing electrode fixed to the electrolytic cell. Work efficiency is greatly improved.
Furthermore, according to the laminate of the present invention, the electrolytic performance can be maintained or improved when new. Therefore, an electrode fixed to a conventional new electrolytic cell and functioning as an anode and a cathode only needs to function as a power feeder, and the catalyst coating can be greatly reduced or eliminated.
The laminated body of the present embodiment can be stored and transported to a customer, for example, in a state (roll shape or the like) wound around a PVC pipe or the like, and handling becomes much easier.
In addition, as a power supply body in this embodiment, various base materials to be described later can be applied, such as a deteriorated electrode (that is, an existing electrode) or an electrode that is not coated with a catalyst.
Moreover, as long as the laminated body of this embodiment has an above-described structure, it may have a fixing part in part. That is, when the laminate of the present embodiment has a fixing portion, the portion not having the fixing is subjected to measurement, and the force per unit mass / unit area of the obtained electrode for electrolysis is 1.5 N. / Mg · cm ² is sufficient.

[Electrode for electrolysis]
The electrode for electrolysis of this embodiment has good handling properties, and has good adhesion to diaphragms such as ion exchange membranes and microporous membranes, power feeders (degraded electrodes and electrodes without catalyst coating), etc. from the viewpoint of having, such a force per unit mass and unit area is less than 1.5 N / mg · cm ^2, preferably not more than 1.2 N / mg · cm ^2, more preferably 1.20N / mg · cm ² or less. Still more preferably not more than 1.1N / mg · cm ^2, still more preferably not more than 1.10N / mg · cm ^2, even more preferably at 1.0N / mg · cm ² or less, even more preferably 1 0.000 N / mg · cm ² or less.
From the viewpoint of improving the electrolysis performance, preferably 0.005N / (mg · cm ²⁾ greater, more preferably 0.08N / (mg · cm ²⁾ or more, more preferably 0.1 N / mg · It is cm ² or more, more preferably 0.14 N / (mg · cm ² ) or more. From the viewpoint of easy handling at a large size (for example, size 1.5 m × 2.5 m), 0.2 N / (mg · cm ² ) or more is even more preferable.
The force can be set to the above range by appropriately adjusting, for example, the aperture ratio, electrode thickness, arithmetic average surface roughness, and the like, which will be described later. More specifically, for example, when the aperture ratio is increased, the force tends to decrease, and when the aperture ratio is decreased, the force tends to increase.
In addition, good handleability is obtained, and it has good adhesion with diaphragms such as ion exchange membranes and microporous membranes, deteriorated electrodes and power supply bodies that are not coated with a catalyst, and from the viewpoint of economy The mass per unit area is preferably 48 mg / cm ² or less, more preferably 30 mg / cm ² or less, and further preferably 20 mg / cm ² or less. In addition, it is preferably 15 mg / cm ² or less from a comprehensive viewpoint that combines economic efficiency. Although a lower limit is not specifically limited, For example, it is about 1 mg / cm < ² >.
The mass per unit area can be set to the above range by appropriately adjusting, for example, the porosity described later, the thickness of the electrode, and the like. More specifically, for example, with the same thickness, increasing the aperture ratio tends to decrease the mass per unit area, and decreasing the aperture ratio tends to increase the mass per unit area. is there.

Such force can be measured by the following method (i) or (ii), and details are as described in Examples. The force is a value obtained by the measurement of the method (i) (also referred to as “force (1)”) and a value obtained by the measurement of the method (ii) (also referred to as “force (2)”). May be the same or different from each other, but any value is less than 1.5 N / mg · cm ² .

[Method (i)]
Inorganic particles and a binder were applied to both surfaces of a nickel plate (thickness 1.2 mm, 200 mm square) obtained by blasting with alumina having a grain number 320 and a perfluorocarbon polymer film into which ion exchange groups were introduced. An ion exchange membrane (170 mm square, the details of the ion exchange membrane here are as described in the examples) and an electrode sample (130 mm square) are laminated in this order, and this laminate is made of pure water. After sufficient immersion, a sample for measurement is obtained by removing excess water adhering to the surface of the laminate. In addition, the arithmetic average surface roughness (Ra) of the nickel plate after blasting is 0.5 to 0.8 μm. The specific calculation method of arithmetic average surface roughness (Ra) is as described in the examples.
Under conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode sample in the measurement sample was raised at 10 mm / min in the vertical direction using a tensile / compression tester, Measure the load when rising 10 mm vertically. This measurement is performed 3 times and an average value is calculated.
The 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 electrode sample of the portion overlapping the ion exchange membrane, and the force per unit mass / unit area (1) (N / Mg · cm ² ).

The force (1) per unit mass / unit area obtained by the method (i) provides good handling properties, and includes membranes such as ion exchange membranes and microporous membranes, deteriorated electrodes and catalyst coatings. from the standpoint of having no power feeder and good adhesion, less than 1.5N / mg · cm ^2, preferably in 1.2N / mg · cm ² or less, more preferably 1.20N / mg · cm ² or less, more preferably 1.1 N / mg · cm ² or less, even more preferably 1.10 N / mg · cm ² or less, and even more preferably 1.0 N / mg · cm ² or less. More preferably 1.00 N / mg · cm ² or less. From the viewpoint of further improving electrolytic performance, preferably 0.005N / (mg · cm ²⁾ greater, more preferably 0.08N / (mg · cm ²⁾ or more, more preferably, 0. 1 N / (mg · cm ² ) or more, and more preferably 0.14 N / (mg from the viewpoint that handling at a large size (for example, size 1.5 m × 2.5 m) is facilitated. · Cm ² ), more preferably 0.2 N / (mg · cm ² ) or more.
When the electrode for electrolysis according to the present embodiment satisfies the force (1), for example, the electrode can be used integrally with a diaphragm such as an ion exchange membrane or a microporous membrane or a power feeding body (that is, as a laminate). When renewing, the work of replacing the cathode and the anode fixed to the electrolysis cell by a method such as welding becomes unnecessary, and the working efficiency is greatly improved. Moreover, by using the electrode for electrolysis of the present embodiment as a laminated body integrated with an ion exchange membrane, a microporous membrane, or a power feeding body, the electrolysis performance can be equal to or improved with the performance of a new article.
When shipping a new electrolysis cell, conventionally, the catalyst coating was applied to the electrode fixed to the electrolysis cell, but only by combining the electrode for electrolysis of this embodiment with the electrode not coated with the catalyst, Since it can be used as an electrode, it is possible to greatly reduce or eliminate the manufacturing process and the amount of catalyst for performing catalyst coating. The conventional electrode in which the catalyst coating is greatly reduced or zero can be electrically connected to the electrode for electrolysis of the present embodiment, and can function as a power feeder for flowing current.

[Method (ii)]
A nickel plate (thickness 1.2 mm, 200 mm square, nickel plate similar to the above method (i)) obtained by blasting with alumina of grain number 320 and an electrode sample (130 mm square) are laminated in this order. After sufficiently immersing this laminate in pure water, a sample for measurement is obtained by removing excess water adhering to the surface of the laminate. Under conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, only the electrode sample in the measurement sample was raised at 10 mm / min in the vertical direction using a tensile / compression tester, and the electrode sample was Measure the load when rising 10 mm vertically. This measurement is performed 3 times and an average value is calculated.
By dividing this average value by the area of the overlapping part of the electrode sample and the nickel plate and the mass of the electrode sample in the overlapping part of the nickel plate, the adhesive force per unit mass / unit area (2) (N / mg Calculate cm ² ).

The force (2) per unit mass / unit area obtained by the method (ii) provides good handling properties, and includes membranes such as ion exchange membranes and microporous membranes, deteriorated electrodes and catalyst coatings. from the standpoint of having no power feeder and good adhesion, less than 1.5N / mg · cm ^2, preferably in 1.2N / mg · cm ² or less, more preferably 1.20N / mg · cm ² or less, more preferably 1.1 N / mg · cm ² or less, even more preferably 1.10 N / mg · cm ² or less, and even more preferably 1.0 N / mg · cm ² or less. More preferably 1.00 N / mg · cm ² or less. From the viewpoint of improving the electrolysis performance, preferably 0.005N / (mg · cm ²⁾ greater, more preferably 0.08N / (mg · cm ²⁾ or more, more preferably, 0.1 N / (Mg · cm ² ) or more, more preferably still more preferably from the viewpoint that handling at a large size (for example, size 1.5 m × 2.5 m) is facilitated, still more preferably 0.14 N / (Mg · cm ² ) or more.
When the electrode for electrolysis of the present embodiment satisfies the force (2), for example, it can be stored in a state wound in a PVC pipe or the like (roll shape), transported to a customer, etc. Will be much easier. Further, by attaching the electrode for electrolysis of the present embodiment to a deteriorated existing electrode to form a laminate, the electrolysis performance can be equal to or improved with the performance of a new article.

  When the electrode for electrolysis of this embodiment is an electrode having a wide elastic deformation region, better handling is obtained, and a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode, and a power supply that is not coated with a catalyst. From the viewpoint of having better adhesion to the body and the like, the thickness of the electrode for electrolysis is preferably 315 μm or less, more preferably 220 μm or less, further preferably 170 μm or less, still more preferably 150 μm or less, and particularly preferably 145 μm or less, It is more preferably 140 μm or less, still more preferably 138 μm or less, and even more preferably 135 μm or less. If it is 135 micrometers or less, favorable handling property will be obtained. Further, from the same viewpoint as described above, it is preferably 130 μm or less, more preferably less than 130 μm, still more preferably 115 μm or less, and even more preferably 65 μm or less. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. In the present embodiment, “the elastic deformation region is wide” means that the electrode for electrolysis is wound into a wound body, and after the wound state is released, the warp derived from the winding is less likely to occur. . Moreover, the thickness of the electrode for electrolysis means the thickness which match | combined the electrode base material for electrolysis and the catalyst layer, when the below-mentioned catalyst layer is included.

  It is preferable that the electrode for electrolysis of this embodiment includes an electrode substrate for electrolysis and a catalyst layer. The thickness (gauge thickness) of the electrode substrate for electrolysis is not particularly limited, but good handling properties are obtained, and a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode (feeder) and a catalyst coating are applied. It has good adhesive strength with non-electrode (power supply body), can be suitably wound in a roll shape, can be folded well, and can be easily handled in large size (for example, size 1.5m x 2.5m) From the viewpoint of becoming, it is preferably 300 μm or less, more preferably 205 μm or less, still more preferably 155 μm or less, still more preferably 135 μm or less, still more preferably 125 μm or less, even more preferably 120 μm or less, and even more preferably 100 μm or less, From the viewpoint of handling properties and economy, 50 μm or less is even more preferable. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

In the present embodiment, a diaphragm and an electrode such as an ion exchange membrane or a microporous membrane, or a metal porous plate or a metal plate (that is, a power feeder) such as an existing electrode that has deteriorated or is not coated with a catalyst and an electrode for electrolysis. It is preferable that a liquid intervenes. As the liquid, any liquid that generates surface tension, such as water or an organic solvent, can be used. Since the force applied between the diaphragm and the electrode for electrolysis, or the metal porous plate or the metal plate and the electrode for electrolysis increases as the surface tension of the liquid increases, a liquid having a large surface tension is preferable. Examples of the liquid include the following (the numerical value in parentheses is the surface tension of the liquid at 20 ° C.).
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) water (72.76 mN) / M)
If the liquid has a large surface tension, the diaphragm and the electrode for electrolysis, or the metal porous plate or metal plate (feeder) and the electrode for electrolysis are integrated (a laminate), and the electrode can be easily renewed. The liquid between the diaphragm and the electrode for electrolysis, or the metal perforated plate or metal plate (feeder) and the electrode for electrolysis may be in such an amount that it sticks to each other due to surface tension, and as a result, the amount of liquid is small. Even if it is mixed with the electrolytic solution after being installed in the electrolytic cell, it does not affect the electrolysis itself.
From a practical viewpoint, it is preferable to use a liquid having a surface tension of 24 mN / m to 80 mN / m, such as ethanol, ethylene glycol, or water. In particular, water or an aqueous solution in which caustic soda, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate or the like is dissolved in water to make it alkaline is preferable. Moreover, surfactant can be included in these liquids, and surface tension can also be adjusted. By including the surfactant, the adhesiveness between the diaphragm and the electrode for electrolysis, or the metal porous plate or metal plate (feeder) and the electrode for electrolysis changes, and the handling property can be adjusted. There is no restriction | limiting in particular as surfactant, Both an ionic surfactant and a nonionic surfactant can be used.

The electrode for electrolysis of the present embodiment is not particularly limited, but good handling properties can be obtained, a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode (power supply body), and an electrode without a catalyst coating (power supply) The proportion measured by the following method (2) is preferably 90% or more, more preferably 92% or more, and a large size ( For example, it is more preferably 95% or more from the viewpoint of easy handling at a size of 1.5 m × 2.5 m). The upper limit is 100%.
[Method (2)]
An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on the curved surface of a polyethylene pipe (outer diameter 280 mm) so that the electrode sample in the laminate is on the outside. And the pipe is sufficiently immersed in pure water to remove excess water adhering to the surface of the laminate and the pipe, and after 1 minute, the portion where the ion exchange membrane (170 mm square) and the electrode sample are in close contact Measure the area percentage (%).

The electrode for electrolysis of the present embodiment is not particularly limited, but good handling properties can be obtained, a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode (power supply body), and an electrode without a catalyst coating (power supply) Body) and a good adhesive force, suitably wound in a roll shape, and from the viewpoint that it can be folded well, the ratio measured by the following method (3) is preferably 75% or more, It is more preferably 80% or more, and further preferably 90% or more from the viewpoint of easy handling in a large size (for example, size 1.5 m × 2.5 m). The upper limit is 100%.
[Method (3)]
An ion exchange membrane (170 mm square) and an electrode sample (130 mm square) are laminated in this order. Under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, the laminate is placed on the curved surface of a polyethylene pipe (outer diameter 145 mm) so that the electrode sample in the laminate is on the outside. And the pipe is sufficiently immersed in pure water to remove excess water adhering to the surface of the laminate and the pipe, and after 1 minute, the portion where the ion exchange membrane (170 mm square) and the electrode sample are in close contact Measure the area percentage (%).

The electrode for electrolysis of the present embodiment is not particularly limited, but good handling properties can be obtained, a diaphragm such as an ion exchange membrane or a microporous membrane, a deteriorated electrode (power supply body), and an electrode without a catalyst coating (power supply) From the viewpoint of preventing adhesion of gas generated during electrolysis with a good adhesion to the body, it is preferable to have a porous structure and a porosity or porosity of 5 to 90% or less. Is more preferably 10 to 80% or less, still more preferably 20 to 75%.
In addition, a hole area rate is the ratio of the hole part per unit volume. There are various calculation methods depending on whether the aperture is also considered to the submicron order or only the visible aperture is considered. In this embodiment, the volume V was calculated from the values of the gauge thickness, width, and length of the electrode, and the weight W was measured to calculate the aperture ratio A by the following formula.
A = (1− (W / (V × ρ)) × 100
ρ is the density (g / cm ³ ) of the electrode material. For example, in the case of nickel 8.908g / cm ^3, in the case of titanium which is 4.506g / cm ^3. For punching metal, the hole area ratio can be adjusted by changing the punched metal area per unit area. For expanded metal, SW (minor axis), LW (major axis), and changing the feed value. Changes the wire diameter and mesh number of metal fibers, changes the photoresist pattern used for electroforming, changes the metal fiber diameter and fiber density for non-woven fabrics, and forms voids for foam metal It adjusts suitably by the method of changing the casting_mold | template for making it.

In the electrode for electrolysis in the present embodiment, the value measured by the following method (A) is preferably 40 mm or less, more preferably 29 mm or less, and further preferably 10 mm or less from the viewpoint of handling properties. Still more preferably, it is 6.5 mm or less. The specific measurement method is as described in the examples.
[Method (A)]
A sample obtained by laminating an ion exchange membrane and the electrode for electrolysis under conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5% is wound around a curved surface of a vinyl chloride core material having an outer diameter of φ32 mm, and fixed. When the electrolysis electrode is separated and placed on a horizontal plate after standing for 6 hours, the vertical heights L ₁ and L ₂ at both ends of the electrolysis electrode are measured, and the average value thereof is measured. Is the measured value.

The electrode for electrolysis in this embodiment has a size of 50 mm × 50 mm, the temperature is 24 ° C., the relative humidity is 32%, the piston speed is 0.2 cm / s, and the air flow rate is 0.4 cc / cm ² / s. The airflow resistance (hereinafter also referred to as “airflow resistance 1”) in the case (hereinafter also referred to as “measurement condition 1”) is preferably 24 kPa · s / m or less. High ventilation resistance means that it is difficult for air to flow, and indicates a high density state. In this state, electrolysis products remain in the electrode and the reaction substrate is less likely to diffuse inside the electrode, so that the electrolysis performance (voltage, etc.) tends to deteriorate. In addition, the concentration on the film surface tends to increase. Specifically, the caustic concentration tends to increase on the cathode surface, and the supply of salt water tends to decrease on the anode surface. As a result, the product stays at a high concentration at the interface where the diaphragm and the electrode are in contact, which leads to damage to the diaphragm, and tends to lead to voltage increase on the cathode surface, film damage, and film damage on the anode surface. . In the present embodiment, in order to prevent these problems, the ventilation resistance is preferably 24 kPa · s / m or less. From the same viewpoint as described above, it is more preferably less than 0.19 kPa · s / m, further preferably 0.15 kPa · s / m or less, and further more preferably 0.07 kPa · s / m or less. preferable.
In this embodiment, if the airflow resistance is larger than a certain value, NaOH generated in the electrode tends to stay at the interface between the electrode and the diaphragm in the case of the cathode, and tends to become a high concentration. In order to prevent damage to the diaphragm, which may occur due to such retention, it may be less than 0.19 kPa · s / m. Preferably, it is 0.15 kPa · s / m or less, more preferably 0.07 kPa · s / m or less.
On the other hand, when the ventilation resistance is low, the area of the electrode is small, so that the electrolytic area is small and the electrolytic performance (voltage, etc.) tends to be poor. When the ventilation resistance is zero, since no electrode for electrolysis is installed, the power feeder functions as an electrode, and the electrolysis performance (voltage, etc.) tends to be remarkably deteriorated. From this point, a preferable lower limit value specified as the ventilation resistance 1 is not particularly limited, but is preferably more than 0 kPa · s / m, more preferably 0.0001 kPa · s / m or more, and still more preferably. 0.001 kPa · s / m or more.
In addition, if the ventilation resistance 1 is 0.07 kPa · s / m or less, sufficient measurement accuracy may not be obtained due to the measurement method. From such a viewpoint, for the electrode for electrolysis having a ventilation resistance 1 of 0.07 kPa · s / m or less, the ventilation resistance (hereinafter referred to as “ventilation resistance”) by the following measurement method (hereinafter also referred to as “measurement condition 2”). 2).) Is also possible. That is, the ventilation resistance 2 is the ventilation resistance when the electrode for electrolysis is 50 mm × 50 mm in size, the temperature is 24 ° C., the relative humidity is 32%, the piston speed is 2 cm / s, and the air flow rate is 4 cc / cm ² / s.
A specific method for measuring the ventilation resistances 1 and 2 is as described in the examples.
The ventilation resistances 1 and 2 can be set to the above range by appropriately adjusting, for example, the aperture ratio described later and the thickness of the electrode. More specifically, for example, if the aperture ratio is increased, the ventilation resistances 1 and 2 tend to decrease when the aperture ratio is increased, and the ventilation resistances 1 and 2 tend to increase when the aperture ratio is decreased. is there.

As described above, in the electrode for electrolysis of this embodiment, the force per unit mass / unit area of the electrode for electrolysis on the diaphragm or the power feeding body is less than 1.5 N / mg · cm ² . Thus, the electrode for electrolysis of this embodiment comprises a laminated body with a diaphragm or a power feeding body by contacting with a diaphragm or a power feeding body (for example, an existing anode or cathode in an electrolytic cell) with an appropriate adhesive force. can do. That is, it is not necessary to firmly bond the diaphragm or power supply body and the electrode for electrolysis by a complicated method such as thermocompression bonding. Since only a relatively weak force such as the above adheres to form a laminated body, the laminated body can be easily configured with any scale. Furthermore, since such a laminate exhibits excellent electrolytic performance, the laminate of the present embodiment is suitable for electrolysis applications, and is particularly preferably used for, for example, an electrolytic cell member or an application related to renewal of the member. be able to.

Hereinafter, one mode of the electrode for electrolysis of the present embodiment will be described.
The electrode for electrolysis according to the present embodiment preferably includes an electrode substrate for electrolysis and a catalyst layer. The catalyst layer may be composed of a plurality of layers as described below, or may have a single layer structure.
As shown in FIG. 1, the electrode for electrolysis 100 according to this embodiment includes an electrode substrate for electrolysis 10 and a pair of first layers 20 that cover both surfaces of the electrode substrate for electrolysis 10. The first layer 20 preferably covers the entire electrode substrate 10 for electrolysis. Thereby, the catalyst activity and durability of the electrode for electrolysis are easily improved. The first layer 20 may be laminated only on one surface of the electrode base material 10 for electrolysis.
Further, as shown in FIG. 1, the surface of the first layer 20 may be covered with a second layer 30. The second layer 30 preferably covers the entire first layer 20. Further, the second layer 30 may be laminated only on one surface of the first layer 20.

(Electrode base material for electrolysis)
Although it does not specifically limit as the electrode base material 10 for electrolysis, For example, the valve metal represented by nickel, nickel alloy, stainless steel, or titanium can be used, from nickel (Ni) and titanium (Ti). It is preferable to contain at least one element selected.
When stainless steel is used in a high-concentration alkaline aqueous solution, in consideration of elution of iron and chromium and that the electrical conductivity of stainless steel is about 1/10 that of nickel, A substrate containing nickel (Ni) is preferred.
Moreover, when the electrode base material 10 for electrolysis is used in the chlorine gas generation atmosphere in the high concentration salt solution near saturation, it is also preferable that a material is titanium with high corrosion resistance.
The shape of the electrode base material 10 for electrolysis is not particularly limited, and an appropriate shape can be selected depending on the purpose. As the shape, any of punching metal, non-woven fabric, foam metal, expanded metal, metal porous foil formed by electroforming, so-called woven mesh produced by knitting metal wire, and the like can be used. Among these, punching metal or expanded metal is preferable. Electroforming is a technique for manufacturing a metal thin film with a precise pattern by combining photoengraving and electroplating. In this method, a pattern is formed with a photoresist on a substrate, and electroplating is performed on a portion not protected by the resist to obtain a thin metal.
About the shape of the electrode base material for electrolysis, there exists a suitable specification with the distance of the anode and cathode in an electrolytic cell. Although it is not particularly limited, when the anode and the cathode have a finite distance, an expanded metal or punching metal shape can be used. For example, a woven mesh knitted with a thin line, a wire net, a foam metal, a metal nonwoven fabric, an expanded metal, a punching metal, and a metal porous foil can be used.
Examples of the electrode base material 10 for electrolysis include a metal porous foil, a wire mesh, a metal nonwoven fabric, a punching metal, an expanded metal, and a foam metal.
As a plate material before being processed into a punching metal or an expanded metal, a rolled plate material, an electrolytic foil, or the like is preferable. It is preferable that the electrolytic foil is further plated with the same element as the base material as a post-treatment to make unevenness on one side or both sides.
Further, as described above, the thickness of the electrode substrate 10 for electrolysis is preferably 300 μm or less, more preferably 205 μm or less, still more preferably 155 μm or less, and even more preferably 135 μm or less. Preferably, it is still more preferably 125 μm or less, still more preferably 120 μm or less, even more preferably 100 μm or less, and even more preferably 50 μm or less from the viewpoint of handling properties and economy. preferable. Although a lower limit is not specifically limited, For example, it is 1 micrometer, Preferably it is 5 micrometers, More preferably, it is 15 micrometers.

  In the electrode base material for electrolysis, it is preferable to relieve the residual stress during processing by annealing the electrode base material for electrolysis in an oxidizing atmosphere. In addition, in order to improve the adhesion with the catalyst layer coated on the surface of the electrode substrate for electrolysis, irregularities are formed using a steel grid, alumina powder, etc., and then the surface area is increased by acid treatment. It is preferable to increase. Alternatively, it is preferable to increase the surface area by plating with the same element as the base material.

  The electrolysis electrode substrate 10 is preferably subjected to a treatment for increasing the surface area in order to bring the first layer 20 and the surface of the electrolysis electrode substrate 10 into close contact with each other. Examples of the treatment for increasing the surface area include a blast treatment using a cut wire, a steel grid, an alumina grid, etc., an acid treatment using sulfuric acid or hydrochloric acid, and a plating treatment using the same element as the substrate. The arithmetic average 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, and still more preferably 0.1 to 8 μm.

Next, the case where the electrode for electrolysis of this embodiment is used as an anode for salt electrolysis will be described.
(First layer)
In FIG. 1, the first layer 20 that is a catalyst layer includes at least one oxide of ruthenium oxide, iridium oxide, and titanium oxide. Ruthenium oxide includes RuO _{2 and the} like. Examples of the iridium oxide include IrO ₂ . Examples of the titanium oxide include TiO ₂ . It is preferable that the first layer 20 includes two kinds of oxides of ruthenium oxide and titanium oxide, or contains three kinds of oxides of ruthenium oxide, iridium oxide, and titanium oxide. Thereby, the first layer 20 becomes a more stable layer, and the adhesion with the second layer 30 is further improved.

  When the first layer 20 contains two kinds of oxides of ruthenium oxide and titanium oxide, titanium oxide contained in the first layer 20 with respect to 1 mol of ruthenium oxide contained in the first layer 20. The product is preferably 1 to 9 mol, more preferably 1 to 4 mol. By setting the composition ratio of the two types of oxides within this range, the electrode for electrolysis 100 exhibits excellent durability.

  When the first layer 20 includes three kinds of oxides of ruthenium oxide, iridium oxide, and titanium oxide, it is included in the first layer 20 with respect to 1 mole of ruthenium oxide included in the first layer 20. The iridium oxide is preferably 0.2 to 3 mol, and more preferably 0.3 to 2.5 mol. Moreover, it is preferable that the titanium oxide contained in the 1st layer 20 is 0.3-8 mol with respect to 1 mol of ruthenium oxide contained in the 1st layer 20, and it is more preferable that it is 1-7 mol. preferable. By setting the composition ratio of the three kinds of oxides within this range, the electrode for electrolysis 100 exhibits excellent durability.

  When the first layer 20 includes at least two kinds of oxides selected from ruthenium oxide, iridium oxide, and titanium oxide, it is preferable that these oxides form a solid solution. By forming the oxide solid solution, the electrode for electrolysis 100 exhibits excellent durability.

  In addition to the above composition, various compositions can be used as long as they contain at least one oxide of ruthenium oxide, iridium oxide, and titanium oxide. For example, an oxide coating called ruthenium, iridium, tantalum, niobium, titanium, tin, cobalt, manganese, platinum, or the like, called DSA (registered trademark), can be used as the first layer 20.

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

(Second layer)
The second layer 30 preferably contains ruthenium and titanium. Thereby, the chlorine overvoltage immediately after electrolysis can be further reduced.

  The second layer 30 preferably contains palladium oxide, a solid solution of palladium oxide and platinum, or an alloy of palladium and platinum. Thereby, the chlorine overvoltage immediately after electrolysis can be further reduced.

  The thicker the second layer 30 is, the longer the period during which the electrolytic performance can be maintained, but it is preferable that the thickness is 0.05 to 3 μm from the viewpoint of economy.

Next, the case where the electrode for electrolysis of this embodiment is used as a cathode for salt electrolysis will be described.
(First layer)
The components of the first layer 20 as the catalyst layer include 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, Lu and the like, and oxides or hydroxides of the metal.
At least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and an alloy containing a platinum group metal may or may not be included.
Platinum group metal, platinum group metal oxide, platinum group metal hydroxide, platinum group metal oxide, platinum group metal hydroxide, platinum group metal hydroxide, platinum group The alloy containing a metal preferably contains at least one platinum group metal among platinum, palladium, rhodium, ruthenium, and iridium.
The platinum group metal preferably contains platinum.
The platinum group metal oxide preferably contains ruthenium oxide.
The platinum group metal hydroxide preferably contains ruthenium hydroxide.
The platinum group metal alloy preferably includes an alloy of platinum and nickel, iron, or cobalt.
Furthermore, it is preferable that an oxide or hydroxide of a lanthanoid element is included as the second component as necessary. Thereby, the electrode 100 for electrolysis shows the outstanding durability.
The oxide or hydroxide of the lanthanoid element preferably contains at least one selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, and dysprosium.
Furthermore, it is preferable to contain a transition metal oxide or hydroxide as the third component as required.
By adding the third component, the electrode for electrolysis 100 exhibits better durability, and the electrolysis voltage can be reduced.
Examples of preferred combinations are 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 + sulfur, ruthenium + Neodymium + lead, ruthenium + neodymium + nickel, ruthenium + neodymium + copper, ruthenium + samarium, ruthenium + samarium + manganese, ruthenium + summary Ru + 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, platinum and iron Alloys, etc.
When a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, or an alloy containing a platinum group metal is not included, the main component of the catalyst is preferably a nickel element.
It is preferable to include at least one of nickel metal, oxide, and hydroxide.
A transition metal may be added as the second component. The second component to be added preferably contains at least one element of titanium, tin, molybdenum, cobalt, manganese, iron, sulfur, zinc, copper, and carbon.
Preferred combinations include nickel + tin, nickel + titanium, nickel + molybdenum, nickel + cobalt and the like.
If necessary, an intermediate layer can be provided between the first layer 20 and the electrode base material 10 for electrolysis. By installing the intermediate layer, the durability of the electrode for electrolysis 100 can be improved.
As the intermediate layer, one having affinity for both the first layer 20 and the electrode substrate 10 for electrolysis is preferable. The intermediate layer is preferably nickel oxide, platinum group metal, platinum group metal oxide, or platinum group metal hydroxide. The intermediate layer can be formed by applying and baking a solution containing a component for forming the intermediate layer, or by subjecting the base material to heat treatment at a temperature of 300 to 600 ° C. in an air atmosphere, and surface oxidation. A physical layer can also be formed. In addition, it can be formed by a known method such as thermal spraying or ion plating.

(Second layer)
The components of the first layer 30 that is the catalyst layer include C, Si, P, S, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, and 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, Lu and the like, and oxides or hydroxides of the metal.
At least one of a platinum group metal, a platinum group metal oxide, a platinum group metal hydroxide, and an alloy containing a platinum group metal may or may not be included. Examples of preferable combinations of elements contained in the second layer include the combinations mentioned in the first layer. The combination of the first layer and the second layer may be the same composition and different composition ratios, or may be a combination of different compositions.

  As the thickness of the catalyst layer, the total thickness of the formed catalyst layer and intermediate layer is preferably 0.01 μm to 20 μm. If it is 0.01 micrometer or more, it can fully exhibit a function as a catalyst. If it is 20 μm or less, it is possible to form a strong catalyst layer with little falling off from the substrate. 0.05 μm to 15 μm is more preferable. More preferably, it is 0.1 μm to 10 μm. More preferably, it is 0.2 μm to 8 μm.

  The thickness of the electrode for the electrode, that is, 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, still more preferably 170 μm or less, from the viewpoint of the handleability of the electrode for electrolysis. 150 μm or less is even more preferred, 145 μm or less is particularly preferred, 140 μm or less is more preferred, 138 μm or less is even more preferred, and 135 μm or less is even more preferred. If it is 135 micrometers or less, favorable handling property will be obtained. Further, from the same viewpoint as described above, it is preferably 130 μm or less, more preferably less than 130 μm, still more preferably 115 μm or less, and still more preferably 65 μm or less. Although a lower limit is not specifically limited, 1 micrometer or more is preferable, 5 micrometers or more are more preferable practically, and it is more preferable that it is 20 micrometers or more. The thickness of the electrode can be determined by measuring with a Digimatic Sixness Gauge (Mitutoyo Corporation, minimum display 0.001 mm). The thickness of the electrode substrate for electrodes can be measured in the same manner as the thickness of the electrode for electrodes. 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 electrodes.

(Method for producing electrode for electrolysis)
Next, an embodiment of a method for manufacturing the electrode for electrolysis 100 will be described in detail.
In the present embodiment, the first layer 20, preferably the second layer, is formed on the electrode substrate for electrolysis by a method such as baking (thermal decomposition) of the coating film in an oxygen atmosphere or ion plating, plating, thermal spraying, or the like. By forming 30, the electrode for electrolysis 100 can be manufactured. In such a manufacturing method of this embodiment, high productivity of the electrode for electrolysis 100 can be realized. Specifically, the catalyst layer is formed on the electrode substrate for electrolysis by an application step of applying a coating solution containing a catalyst, a drying step of drying the coating solution, and a thermal decomposition step of performing thermal decomposition. Here, the thermal decomposition means heating the metal salt as a precursor to decompose into a metal or metal oxide and a gaseous substance. Although the decomposition products differ depending on the type of metal used, the type of salt, the atmosphere in which pyrolysis is performed, etc., many metals tend to form oxides in an oxidizing atmosphere. In the industrial manufacturing process of electrodes, pyrolysis is usually performed in air, and in many cases, metal oxides or metal hydroxides are formed.

(Formation of the first layer of the anode)
(Coating process)
The first layer 20 is formed by applying a solution in which at least one metal salt of ruthenium, iridium and titanium is dissolved (first coating solution) to the electrode substrate for electrolysis and then thermally decomposing (baking) in the presence of oxygen. Obtained. The contents of ruthenium, iridium and titanium in the first coating solution are substantially equal to those of the first layer 20.

  The metal salt may be chloride, nitrate, sulfate, metal alkoxide, or any other form. The solvent of the first coating solution can be selected according to the type of metal salt, but water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in consideration of the thickness of the coating film formed by one coating.

  As a method of applying the first coating solution onto the electrode substrate 10 for electrolysis, a dipping method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution, a method of applying the first coating solution with a brush, a first coating solution A roll method using a sponge-like roll impregnated with an electrode, an electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid are charged to opposite charges and sprayed are used. Among these, the roll method or the electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)
After apply | coating a 1st coating liquid to the electrode base material 100 for electrolysis, it dries at the temperature of 10-90 degreeC, and thermally decomposes with the baking furnace heated at 350-650 degreeC. You may implement temporary baking at 100-350 degreeC as needed between drying and thermal decomposition. The drying, calcination and thermal decomposition temperature can be appropriately selected depending on the composition of the first coating solution and the solvent type. Although it is preferable that the thermal decomposition time per one time is long, it is preferably 3 to 60 minutes and more preferably 5 to 20 minutes from the viewpoint of electrode productivity.

  The coating (first layer 20) is formed to a predetermined thickness by repeating the coating, drying, and thermal decomposition cycles described above. After the first layer 20 is formed, the stability of the first layer 20 can be further improved by performing post-heating after further baking as necessary.

(Formation of the second layer)
The second layer 30 is formed as necessary. For example, after applying a solution containing a palladium compound and a platinum compound or a solution containing a ruthenium compound and a titanium compound (second coating solution) on the first layer 20, Obtained by thermal decomposition in the presence of oxygen.

(Formation of the first layer of the cathode by pyrolysis)
(Coating process)
The first layer 20 is obtained by applying a solution (first coating solution) in which various combinations of metal salts are dissolved to the electrode substrate for electrolysis and then thermally decomposing (baking) in the presence of oxygen. The metal content in the first coating solution is substantially equal to that of the first layer 20.

  The metal salt may be chloride, nitrate, sulfate, metal alkoxide, or any other form. The solvent of the first coating solution can be selected according to the type of metal salt, but water and alcohols such as butanol can be used. As the solvent, water or a mixed solvent of water and alcohols is preferable. The total metal concentration in the first coating solution in which the metal salt is dissolved is not particularly limited, but is preferably in the range of 10 to 150 g / L in consideration of the thickness of the coating film formed by one coating.

  As a method of applying the first coating solution onto the electrode substrate 10 for electrolysis, a dipping method in which the electrode substrate 10 for electrolysis is immersed in the first coating solution, a method of applying the first coating solution with a brush, a first coating solution A roll method using a sponge-like roll impregnated with an electrode, an electrostatic coating method in which the electrode base material 10 for electrolysis and the first coating liquid are charged to opposite charges and sprayed are used. Among these, the roll method or the electrostatic coating method which is excellent in industrial productivity is preferable.

(Drying process, pyrolysis process)
After apply | coating a 1st coating liquid to the electrode base material 10 for electrolysis, it dries at the temperature of 10-90 degreeC, and thermally decomposes with the baking furnace heated at 350-650 degreeC. You may implement temporary baking at 100-350 degreeC as needed between drying and thermal decomposition. The drying, calcination and thermal decomposition temperature can be appropriately selected depending on the composition of the first coating solution and the solvent type. Although it is preferable that the thermal decomposition time per one time is long, it is preferably 3 to 60 minutes and more preferably 5 to 20 minutes from the viewpoint of electrode productivity.

  The coating (first layer 20) is formed to a predetermined thickness by repeating the coating, drying, and thermal decomposition cycles described above. After the first layer 20 is formed, the stability of the first layer 20 can be further improved by performing post-heating after further baking as necessary.

(Formation of intermediate layer)
An intermediate | middle layer is formed as needed, for example, after apply | coating the solution (2nd coating liquid) containing a palladium compound or a platinum compound on a base material, it obtains by thermally decomposing in presence of oxygen. Alternatively, the nickel oxide intermediate layer may be formed on the surface of the substrate simply by heating the substrate without applying the solution.

(Formation of first layer of cathode by ion plating)
The first layer 20 can also be formed by ion plating.
As an example, a method of fixing a substrate in a chamber and irradiating a metal ruthenium target with an electron beam can be mentioned. The evaporated metal ruthenium particles are positively charged in the plasma in the chamber and are deposited on the negatively charged substrate. The plasma atmosphere is argon and oxygen, and ruthenium is deposited on the substrate as ruthenium oxide.

(Formation of the first layer of the cathode by plating)
The first layer 20 can also be formed by a plating method.
As an example, when the substrate is used as a cathode and electrolytic plating is performed in an electrolytic solution containing nickel and tin, an alloy plating of nickel and tin can be formed.

(Formation of the first layer of the cathode by thermal spraying)
The first layer 20 can also be formed by a thermal spraying method.
As an example, a catalyst layer in which metallic nickel and nickel oxide are mixed can be formed by plasma spraying nickel oxide particles on a substrate.

The electrode for electrolysis of the present embodiment can be used integrally with a diaphragm such as an ion exchange membrane or a microporous membrane. Therefore, it can be used as a membrane-integrated electrode, and the work of replacing the cathode and anode when renewing the electrode is not required, and the working efficiency is greatly improved.
In addition, according to the integral electrode with a diaphragm such as an ion exchange membrane or a microporous membrane, the electrolysis performance can be equal to or improved with the performance when new.

Hereinafter, the ion exchange membrane will be described in detail.
[Ion exchange membrane]
The ion exchange membrane has a membrane body containing a hydrocarbon polymer or a fluorine-containing polymer having an ion exchange group, and a coating layer provided on at least one surface of the membrane body. The coating layer includes inorganic particles and a binder, and the specific surface area of the coating layer is 0.1 to 10 m ² / g. The ion exchange membrane having such a structure has little influence on the electrolysis performance by the gas generated during electrolysis, and can exhibit stable electrolysis performance.
The above-mentioned membrane of perfluorocarbon polymer into which an ion exchange group is introduced is a sulfonic acid having an ion exchange group derived from a sulfo group (a group represented by —SO ₃ —, hereinafter also referred to as “sulfonic acid group”). And a carboxylic acid layer having an ion exchange group derived from a carboxyl group (a group represented by —CO ₂ —, hereinafter also referred to as “carboxylic acid group”). From the viewpoint of strength and dimensional stability, it is preferable to further have a reinforcing core material.
The inorganic particles and the binder will be described in detail below in the description of the coating layer.

  FIG. 2 is a schematic cross-sectional view showing an embodiment of an ion exchange membrane. The ion exchange membrane 1 has a membrane body 10 containing a hydrocarbon polymer or a fluorine-containing polymer having an ion exchange group, and coating layers 11 a and 11 b formed on both surfaces of the membrane body 10.

In the ion exchange membrane 1, the membrane body 10 includes a sulfonic acid layer 3 having an ion exchange group derived from a sulfo group (a group represented by —SO ₃ ^— , hereinafter also referred to as “sulfonic acid group”), and a carboxyl group-derived. And a carboxylic acid layer 2 having an ion exchange group (a group represented by —CO ₂ ^— , hereinafter also referred to as “carboxylic acid group”), and the strength and dimensional stability are enhanced by the reinforcing core material 4. . Since the ion exchange membrane 1 includes the sulfonic acid layer 3 and the carboxylic acid layer 2, it is suitably used as a cation exchange membrane.

  The ion exchange membrane may have only one of a sulfonic acid layer and a carboxylic acid layer. Further, the ion exchange membrane does not necessarily need to be reinforced by the reinforcing core material, and the arrangement state of the reinforcing core material is not limited to the example of FIG.

(Membrane body)
First, the membrane body 10 constituting the ion exchange membrane 1 will be described.
The membrane body 10 may have any function as long as it has a function of selectively permeating cations and includes a hydrocarbon polymer or a fluorine-containing polymer having an ion exchange group, and its configuration and material are not particularly limited. However, a suitable one can be selected as appropriate.

  The hydrocarbon polymer or fluorine-containing polymer having an ion exchange group in the membrane body 10 is, for example, a hydrocarbon polymer or fluorine-containing polymer having an ion exchange group precursor that can become an ion exchange group by hydrolysis or the like. Can be obtained from coalescence. Specifically, for example, the main chain is made of a fluorinated hydrocarbon, has a group (ion exchange group precursor) that can be converted into an ion exchange group by hydrolysis or the like as a pendant side chain, and can be melt processed. After preparing the precursor of the membrane body 10 using a polymer (hereinafter sometimes referred to as “fluorinated polymer (a)”), the membrane is obtained by converting the ion exchange group precursor into an ion exchange group. The main body 10 can be obtained.

  The fluorine-containing polymer (a) includes, for example, 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: It can be produced by copolymerization. Moreover, it can also manufacture by the homopolymerization of the monomer of 1 type chosen from either the following 1st group, the following 2nd group, and the following 3rd group.

  Examples of the first group of monomers include vinyl fluoride compounds. Examples of the vinyl fluoride compound include vinyl fluoride, tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and the like. In particular, when the ion exchange membrane is used as a membrane for alkaline electrolysis, the vinyl fluoride compound is preferably a perfluoro monomer, and is selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. A fluoromonomer is preferred.

Examples of the second group of monomers include vinyl compounds having a functional group that can be converted into a carboxylic acid type ion exchange group (carboxylic acid group). Examples of the vinyl compound having a functional group that can be converted into a carboxylic acid group include monomers represented by CF ₂ ═CF (OCF ₂ CYF) _s —O (CZF) _t —COOR (here, , S represents an integer of 0 to 2, t represents an integer of 1 to 12, Y and Z each independently represent F or CF ₃ , and R represents a lower alkyl group. , For example, an alkyl group having 1 to 3 carbon atoms.).

Among _{them, CF 2 = CF (OCF 2} CYF) n -O (CF 2) a compound represented by _m -COOR are preferred. Here, n represents an integer of 0 to 2, m represents an integer of 1 to 4, Y represents F or CF ₃ , and R represents CH ₃ , C ₂ H ₅ , or C ₃ H ₇ .

  When the ion exchange membrane is used as a cation exchange membrane for alkaline electrolysis, it is preferable to use at least a perfluoro compound as a monomer. However, the alkyl group of the ester group (see R above) is heavy when it is hydrolyzed. Since the alkyl group (R) is lost from the coalescence, the alkyl group (R) may not be a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

As the second group of monomers, monomers shown below are more preferable among the above.
_{CF 2 = CFOCF 2 -CF (CF} 3) OCF 2 COOCH 3,
CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₂ COOCH ₃ ,
_{CF 2 = CF [OCF 2 -CF} (CF 3)] 2 O (CF 2) 2 COOCH 3,
CF ₂ = CFOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ COOCH ₃ ,
CF ₂ = CFO (CF ₂ ) ₂ COOCH ₃ ,
_{CF 2 = CFO (CF 2)} 3 COOCH 3.

Examples of the third group of monomers include vinyl compounds having a functional group that can be converted into a sulfone-type ion exchange group (sulfonic acid group). The vinyl compound having a functional group that can be converted to sulfonic acid groups, e.g., CF ₂ = monomer represented by _{CFO-X-CF 2 -SO 2} F are preferred (wherein, X is perfluoroalkylene group Represents.) Specific examples thereof include the monomers shown below.
CF ₂ = CFOCF ₂ CF ₂ SO ₂ F,
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F,
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₂ SO ₂ F,
CF ₂ = CF (CF ₂ ) ₂ SO ₂ F,
CF ₂ = CFO [CF ₂ CF (CF ₃ ) O] ₂ CF ₂ CF ₂ SO ₂ F,
_{CF 2 = CFOCF 2 CF (CF} 2 OCF 3) OCF 2 CF 2 SO 2 F.

Among _{them, CF 2 = CFOCF 2 CF (} CF 3) OCF 2 CF 2 CF 2 SO 2 F, and _{CF 2 = CFOCF 2 CF (CF} 3) OCF 2 CF 2 SO 2 F is more preferred.

  Copolymers obtained from these monomers can be produced by polymerization methods developed for homopolymerization and copolymerization of fluorinated ethylene, in particular, general polymerization methods used for tetrafluoroethylene. . For example, in the non-aqueous method, an inert solvent such as perfluorohydrocarbon or chlorofluorocarbon is used, and in the presence of a radical polymerization initiator such as perfluorocarbon peroxide or azo compound, the temperature is 0 to 200 ° C., the pressure is 0. The polymerization reaction can be performed under conditions of 1 to 20 MPa.

  In the copolymerization, the type of monomer combination and the ratio thereof are not particularly limited, and are selected and determined depending on the type and amount of functional groups to be imparted to the resulting fluorinated polymer. For example, when a fluorine-containing polymer containing only a carboxylic acid group is used, at least one monomer may be selected from the first group and the second group and copolymerized. Further, when a fluorine-containing polymer containing only a sulfonic acid group is used, at least one monomer may be selected from each of the first group and third group monomers and copolymerized. Further, when a fluorine-containing polymer having a carboxylic acid group and a sulfonic acid group is used, at least one monomer is selected from the monomers of the first group, the second group, and the third group, respectively. What is necessary is just to superpose | polymerize. In this case, the desired fluorine-containing system can also be obtained by separately polymerizing the copolymer consisting of the first group and the second group and the copolymer consisting of the first group and the third group and mixing them later. A polymer can be obtained. Further, the mixing ratio of each monomer is not particularly limited, but when increasing the amount of the functional group per unit polymer, if the ratio of the monomer selected from the second group and the third group is increased. Good.

  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, and more preferably 0.6 to 1.5 mg equivalent / g. Here, the total ion exchange capacity refers to the equivalent of exchange groups per unit weight of the dry resin, and can be measured by neutralization titration or the like.

  In the membrane body 10 of the ion exchange membrane 1, a sulfonic acid layer 3 containing a fluorinated polymer having a sulfonic acid group and a carboxylic acid layer 2 containing a fluorinated polymer having a carboxylic acid group are laminated. Yes. By setting it as the film | membrane main body 10 of such a layer structure, the selective permeability of cations, such as a sodium ion, can be improved further.

  When the ion exchange membrane 1 is arranged in the electrolytic cell, it is usually arranged so that the sulfonic acid layer 3 is located on the anode side of the electrolytic cell and the carboxylic acid layer 2 is located on the cathode side of the electrolytic cell.

  The sulfonic acid layer 3 is preferably made of a material having low electric resistance, and the film thickness is preferably thicker than that of the carboxylic acid layer 2 from the viewpoint of film strength. The film thickness of the sulfonic acid layer 3 is preferably 2 to 25 times that of the carboxylic acid layer 2, and more preferably 3 to 15 times.

  It is preferable that the carboxylic acid layer 2 has a high anion exclusion property even if the film thickness is thin. The term “anion-exclusion” as used herein refers to a property that tends to prevent the penetration and permeation of anions into the ion exchange membrane 1. In order to increase the anion exclusion property, it is effective to arrange a carboxylic acid layer having a small ion exchange capacity with respect to the sulfonic acid layer.

Examples of the fluorine-containing polymer used for the sulfonic acid layer 3 include polymers obtained using CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F as the third group of monomers. Is preferred.

As the fluorine-containing polymer used for the carboxylic acid layer 2, for example, a polymer obtained using CF ₂ = CFOCF ₂ CF (CF ₂ ) O (CF ₂ ) ₂ COOCH ₃ as the second group of monomers Is preferred.

(Coating layer)
The ion exchange membrane has a coating layer on at least one surface of the membrane body. Further, as shown in FIG. 2, in the ion exchange membrane 1, coating layers 11 a and 11 b are formed on both surfaces of the membrane body 10, respectively.
The coating layer includes inorganic particles and a binder.

  The average particle size of the inorganic particles is more preferably 0.90 μm or more. When the average particle size of the inorganic particles is 0.90 μm or more, not only gas adhesion but also durability against impurities is greatly improved. That is, a particularly remarkable effect can be obtained by increasing the average particle diameter of the inorganic particles and satisfying the above-mentioned value of the specific surface area. In order to satisfy such an average particle size and specific surface area, irregular inorganic particles are preferable. Inorganic particles obtained by melting and inorganic particles obtained by crushing raw stones can be used. Preferably, inorganic particles obtained by pulverizing raw stones can be suitably used.

  The average particle size of the inorganic particles can be 2 μm or less. If the average particle size of the inorganic particles is 2 μm or less, the membrane can be prevented from being damaged by the inorganic particles. The average particle diameter of the inorganic particles is more preferably 0.90 to 1.2 μm.

  Here, the average particle diameter can be measured by a particle size distribution meter (“SALD2200”, Shimadzu Corporation).

  The shape of the inorganic particles is preferably an irregular shape. Improves resistance to impurities. The particle size distribution of the inorganic particles is preferably broad.

  The inorganic particles may include at least one inorganic material selected from the group consisting of oxides of Group IV elements of the periodic table, nitrides of Group IV elements of the periodic table, and carbides of Group IV elements of the periodic table. preferable. More preferred are zirconium oxide particles from the viewpoint of durability.

  The inorganic particles are inorganic particles produced by pulverizing the raw particles of the inorganic particles, or the spherical particles having the same particle diameter are obtained by melting and purifying the raw particles of the inorganic particles. Particles are preferred.

  The raw stone crushing method is not particularly limited, and examples thereof include a ball mill, a bead mill, a colloid mill, a conical mill, a disk mill, an edge mill, a milling mill, a hammer mill, a pellet mill, a VSI mill, a wheelie mill, a roller mill, and a jet mill. Moreover, it is preferable to wash | clean after grinding | pulverization, and it is preferable as an washing | cleaning method at that time to carry out an acid treatment. Thereby, impurities such as iron adhering to the surface of the inorganic particles can be reduced.

  The coating layer preferably contains a binder. The binder is a component that forms a coating layer by holding inorganic particles on the surface of the ion exchange membrane. The binder preferably contains a fluorine-containing polymer from the viewpoint of resistance to an electrolytic solution or a product by electrolysis.

  The binder is more preferably a fluorine-containing polymer having a carboxylic acid group or a sulfonic acid group from the viewpoint of resistance to an electrolytic solution or a product by electrolysis and adhesion to the surface of an ion exchange membrane. preferable. When a coating layer is provided on a layer containing a fluorinated polymer having a sulfonic acid group (sulfonic acid layer), it is more preferable to use a fluorinated polymer having a sulfonic acid group as a binder for the coating layer. . Moreover, when providing a coating layer on the layer (carboxylic acid layer) containing the fluorine-containing polymer which has a carboxylic acid group, it is using the fluorine-containing polymer which has a carboxylic acid group as a binder of the said coating layer. Further preferred.

  In the coating layer, the content of inorganic particles is preferably 40 to 90% by mass, and more preferably 50 to 90% by mass. Moreover, it is preferable that it is 10-60 mass%, and, as for content of a binder, it is more preferable that it is 10-50 mass%.

The distribution density of the coating layer in the ion exchange membrane is preferably 0.05 to ² mg per 1 cm ² . Moreover, when the ion exchange membrane has an uneven shape on the surface, the distribution density of the coating layer is preferably 0.5 to ² mg per 1 cm ² .

  It does not specifically limit as a method of forming a coating layer, A well-known method can be used. For example, the method of apply | coating the coating liquid which disperse | distributed the inorganic substance particle | grains in the solution containing binder by spray etc. is mentioned.

(Reinforced core material)
The ion exchange membrane preferably has a reinforcing core disposed inside the membrane body.

  The reinforcing core material is a member that reinforces the strength and dimensional stability of the ion exchange membrane. By arranging the reinforcing core material inside the membrane body, in particular, the expansion and contraction of the ion exchange membrane can be controlled within a desired range. Such an ion exchange membrane does not expand and contract more than necessary during electrolysis and can maintain excellent dimensional stability over a long period of time.

  The configuration of the reinforcing core material is not particularly limited. For example, the reinforcing core material may be formed by spinning a yarn called a reinforcing yarn. The reinforcing yarn here is a member constituting a reinforcing core material, which can impart desired dimensional stability and mechanical strength to the ion exchange membrane, and can exist stably in the ion exchange membrane. It means a thread. By using a reinforcing core material obtained by spinning such reinforcing yarns, it is possible to impart more excellent dimensional stability and mechanical strength to the ion exchange membrane.

  The material of the reinforcing core material and the reinforcing yarn used therefor is not particularly limited, but is preferably a material resistant to acids, alkalis, etc., and needs long-term heat resistance and chemical resistance. A fiber made of a polymer is preferred.

  Examples of the fluorine-containing polymer used for the reinforcing core material include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-ethylene copolymer (ETFE). , Tetrafluoroethylene-hexafluoropropylene copolymer, trifluorochloroethylene-ethylene copolymer, and vinylidene fluoride polymer (PVDF). Among these, it is preferable to use a fiber made of polytetrafluoroethylene particularly from the viewpoint of heat resistance and chemical resistance.

  The yarn diameter of the reinforcing yarn used for the reinforcing core material is not particularly limited, but is preferably 20 to 300 denier, more preferably 50 to 250 denier. The weaving density (the number of driving per unit length) is preferably 5 to 50 / inch. The form of the reinforcing core material is not particularly limited, and for example, a woven cloth, a non-woven cloth, a knitted cloth or the like is used, but a woven cloth is preferable. The thickness of the woven fabric is preferably 30 to 250 μm, more preferably 30 to 150 μm.

  As the woven fabric or knitted fabric, monofilaments, multifilaments or yarns thereof, slit yarns, or the like can be used.

  The weaving method and arrangement of the reinforcing core material in the membrane body are not particularly limited, and can be suitably arranged in consideration of the size and shape of the ion exchange membrane, the physical properties desired for the ion exchange membrane, the usage environment, and the like. .

  For example, the reinforcing core material may be disposed along a predetermined direction of the membrane body, but from the viewpoint of dimensional stability, the reinforcing core material is disposed along a predetermined first direction, and the first It is preferable to arrange another reinforcing core material along a second direction that is substantially perpendicular to the direction. By disposing a plurality of reinforcing cores so as to be substantially perpendicular to the inside of the membrane body in the longitudinal direction, more excellent dimensional stability and mechanical strength can be imparted in multiple directions. For example, an arrangement in which a reinforcing core material (warp yarn) arranged along the longitudinal direction and a reinforcing core material (weft yarn) arranged along the transverse direction is woven on the surface of the membrane body is preferable. A plain weave woven by weaving up and down alternately with warp and weft, or a twine weaving with weft while twisting two warps, or weaving the same number of wefts into two or several warps It is more preferable to use a diagonal weave from the viewpoint of dimensional stability, mechanical strength and manufacturability.

  In particular, it is preferable that the reinforcing core material is disposed along both the MD direction (Machine Direction direction) and the TD direction (Transverse Direction direction) of the ion exchange membrane. That is, it is preferable that plain weaving is performed in the MD direction and the TD direction. Here, the MD direction refers to the direction (flow direction) in which the membrane body and various core materials (for example, reinforcing core material, reinforcing yarn, sacrificial yarn described later, etc.) are transported in the ion exchange membrane manufacturing process described later. The TD direction is a direction substantially perpendicular to the MD direction. And the yarn woven along the MD direction is called MD yarn, and the yarn woven along the TD direction is called TD yarn. Usually, an ion exchange membrane used for electrolysis has a rectangular shape, and the longitudinal direction is often the MD direction and the width direction is often the TD direction. By weaving the reinforcing core material that is MD yarn and the reinforcing core material that is TD yarn, it is possible to impart more excellent dimensional stability and mechanical strength in multiple directions.

  The arrangement interval of the reinforcing core material is not particularly limited, and may be suitably arranged in consideration of the physical properties desired for the ion exchange membrane and the use environment.

  The aperture ratio of the reinforcing core material is not particularly limited, and is preferably 30% or more, more preferably 50% or more and 90% or less. The aperture ratio is preferably 30% or more from the viewpoint of the electrochemical properties of the ion exchange membrane, and preferably 90% or less from the viewpoint of the mechanical strength of the ion exchange membrane.

  The aperture ratio of the reinforcing core is the total surface through which substances such as ions (electrolyte and cations (for example, sodium ions)) such as ions in the area (A) of either surface of the membrane body can pass. The ratio (B / A) of area (B). The total surface area (B) through which substances such as ions can pass is the total area of the ion exchange membrane where cations, electrolytes, etc. are not blocked by the reinforcing core material contained in the ion exchange membrane. it can.

  FIG. 3 is a schematic view for explaining the aperture ratio of the reinforcing core material constituting the ion exchange membrane. FIG. 3 is an enlarged view of a part of the ion exchange membrane, and only the arrangement of the reinforcing cores 21 and 22 in the region is illustrated, and illustration of other members is omitted.

From the area (A) of the region including the area of the reinforcing core material, which is surrounded by the reinforcing core material 21 arranged along the vertical direction and the reinforcing core material 22 arranged in the horizontal direction, the reinforcing core material By subtracting the total area (C), the total area (B) of the region through which substances such as ions in the area (A) of the region described above can pass can be obtained. That is, the aperture ratio can be obtained by the following formula (I).
Opening ratio = (B) / (A) = ((A) − (C)) / (A) (I)

  Among the reinforcing core materials, a particularly preferable form is a tape yarn containing PTFE or a highly oriented monofilament from the viewpoint of chemical resistance and heat resistance. Specifically, a tape yarn obtained by slitting a high-strength porous sheet made of PTFE into a tape shape, or a highly oriented monofilament made of PTFE of 50 to 300 denier, and a weave density of 10 to 50 / More preferably, the reinforcing core material is a plain weave that is inches, and has a thickness in the range of 50 to 100 μm. The aperture ratio of the ion exchange membrane containing such a reinforcing core is more preferably 60% or more.

  Examples of the shape of the reinforcing yarn include round yarn and tape-like yarn.

(Communication hole)
The ion exchange membrane preferably has a communication hole inside the membrane body.

  The communication hole refers to a hole that can serve as a flow path for ions generated during electrolysis or an electrolytic solution. The communication hole is a tubular hole formed inside the membrane body, and is formed by elution of a sacrificial core material (or sacrificial yarn) described later. The shape and diameter of the communication hole can be controlled by selecting the shape and diameter of the sacrificial core material (sacrificial yarn).

  By forming the communication hole in the ion exchange membrane, the mobility of the electrolytic solution can be ensured during electrolysis. The shape of the communication hole is not particularly limited, but according to the manufacturing method described later, the shape of the sacrificial core material used for forming the communication hole can be obtained.

  The communication hole is preferably formed so as to alternately pass through the anode side (sulfonic acid layer side) and the cathode side (carboxylic acid layer side) of the reinforcing core material. By adopting such a structure, in the portion where the communication hole is formed on the cathode side of the reinforcing core material, ions (for example, sodium ions) transported through the electrolyte filled in the communication hole are transferred to the reinforcing core material. It can also flow to the cathode side. As a result, since the cation flow is not shielded, the electric resistance of the ion exchange membrane can be further reduced.

  The communication hole may be formed along only one predetermined direction of the membrane body constituting the ion exchange membrane, but from the viewpoint of exhibiting more stable electrolysis performance, the longitudinal direction and the lateral direction of the membrane body It is preferable that it is formed in both directions.

〔Production method〕
As a suitable manufacturing method of an ion exchange membrane, the method which has the following (1) process-(6) processes is mentioned.
(1) Process: The process of manufacturing the fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.
(2) Step: If necessary, by interweaving at least a plurality of reinforcing core materials and a sacrificial yarn having a property of dissolving in acid or alkali and forming a communicating hole, between adjacent reinforcing core materials A step of obtaining a reinforcing material having a sacrificial yarn disposed therebetween.
(3) Process: The process of film-forming the said fluorine-containing polymer which has an ion exchange group or the ion exchange group precursor which can become an ion exchange group by hydrolysis.
(4) Step: A step of embedding the reinforcing material in the film as necessary to obtain a membrane body in which the reinforcing material is disposed.
(5) Step: A step of hydrolyzing the membrane body obtained in the step (4) (hydrolysis step).
(6) Step: A step of providing a coating layer on the film body obtained in the step (5) (coating step).

  Hereinafter, each process is explained in full detail.

(1) Step: Step of producing a fluorine-containing polymer In the step (1), a fluorine-containing polymer is produced using the raw material monomers described in the first group to the third group. In order to control the ion exchange capacity of the fluorine-containing polymer, the mixing ratio of raw material monomers may be adjusted in the production of the fluorine-containing polymer forming each layer.

(2) Process: Manufacturing process of a reinforcing material A reinforcing material is a woven fabric or the like woven with reinforcing yarn. The reinforcing core material is formed by embedding the reinforcing material in the film. When an ion exchange membrane having communication holes is used, the sacrificial yarn is also woven into the reinforcing material. In this case, the blended amount of the sacrificial yarn is preferably 10 to 80% by mass, more preferably 30 to 70% by mass, based on the entire reinforcing material. By weaving the sacrificial yarn, misalignment of the reinforcing core material can be prevented.

  The sacrificial yarn has solubility in the film production process or in an electrolytic environment, and rayon, polyethylene terephthalate (PET), cellulose, polyamide, or the like is used. Polyvinyl alcohol having a thickness of 20 to 50 denier and made of monofilament or multifilament is also preferable.

  In the step (2), by adjusting the arrangement of the reinforcing core material and the sacrificial yarn, the aperture ratio, the arrangement of the communication holes, and the like can be controlled.

(3) Step: Filming step In the (3) step, the fluorine-containing polymer obtained in the step (1) is formed into a film using an extruder. The film may have a single layer structure, as described above, may have a two-layer structure of a sulfonic acid layer and a carboxylic acid layer, or may have a multilayer structure of three or more layers.

Examples of the method for forming a film include the following.
A method in which a fluorine-containing polymer having a carboxylic acid group and a fluorine-containing polymer having a sulfonic acid group are separately formed into films.
A method of forming a composite film by coextrusion of a fluorinated polymer having a carboxylic acid group and a fluorinated polymer having a sulfonic acid group.

  A plurality of films may be used. Also, co-extrusion of different types of films is preferable because it contributes to increasing the adhesive strength at the interface.

(4) Step: Step of obtaining the membrane body In the step (4), in the step (2), the reinforcing material obtained in the step (2) is embedded in the film obtained in the step (3), so that the membrane body in which the reinforcing material is present is obtained. obtain.

  As a preferable method for forming the film body, (i) a fluorine-containing polymer having a carboxylic acid group precursor (for example, a carboxylic acid ester functional group) located on the cathode side (hereinafter, a layer formed thereof is referred to as a first layer). And a fluorine-containing polymer having a sulfonic acid group precursor (for example, a sulfonyl fluoride functional group) (hereinafter, a layer composed of the fluorine-containing polymer is referred to as a second layer) by coextrusion, and a heating source and Using a vacuum source, a reinforcing material and a second layer / first layer composite film are laminated in this order on a flat plate or drum having a large number of pores on the surface through a heat-resistant release paper having air permeability. And (ii) including a sulfonic acid group precursor separately from the second layer / first layer composite film, while removing the air between the layers by reducing the pressure at a temperature at which each polymer melts. Fluorine polymerization (Third layer) is made into a single film in advance, using a heat source and a vacuum source, if necessary, through a flat plate having a large number of pores on the surface or a heat-resistant release paper having air permeability on the drum. Then, the third layer film, the reinforcing core material, and the composite film composed of the second layer / first layer are laminated in this order, and are integrated while removing air between the layers by reducing the pressure at a temperature at which each polymer melts. A method is mentioned.

  Here, co-extrusion of the first layer and the second layer contributes to increasing the adhesive strength at the interface.

  Moreover, the method of integrating under reduced pressure has the characteristic that the thickness of the 3rd layer on a reinforcing material becomes large compared with the press-pressing method. Furthermore, since the reinforcing material is fixed to the inner surface of the membrane main body, it has a performance that can sufficiently maintain the mechanical strength of the ion exchange membrane.

  In addition, the variation of the lamination | stacking demonstrated here is an example, it considers the layer structure of a desired film | membrane main body, a physical property, etc., and after selecting a suitable lamination pattern (for example, combination of each layer etc.), it is a coextrusion. can do.

  For the purpose of further improving the electrical performance of the ion exchange membrane, a second polymer comprising a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor between the first layer and the second layer. It is also possible to further interpose four layers, or to use a fourth layer made of a fluorine-containing polymer having both a carboxylic acid group precursor and a sulfonic acid group precursor instead of the second layer.

  The method for forming the fourth layer may be a method in which a fluorine-containing polymer having a carboxylic acid group precursor and a fluorine-containing polymer having a sulfonic acid group precursor are separately produced and then mixed. A method using a copolymer of a monomer having a group precursor and a monomer having a sulfonic acid group precursor may also be used.

  When the fourth layer is configured as an ion exchange membrane, a coextruded film of the first layer and the fourth layer is formed, and the third layer and the second layer are separately formed into a film, It may be laminated by a method, or three layers of the first layer / fourth layer / second layer may be coextruded at a time to form a film.

  In this case, the direction in which the extruded film flows is the MD direction. In this way, a membrane body containing a fluorine-containing polymer having an ion exchange group can be formed on the reinforcing material.

  Moreover, it is preferable that an ion exchange membrane has the protrusion part which consists of the fluoropolymer which has a sulfonic acid group, ie, a convex part, on the surface side which consists of a sulfonic acid layer. The method for forming such a convex portion is not particularly limited, and a known method for forming the convex portion on the resin surface can be employed. Specifically, for example, a method of embossing the surface of the film main body can be mentioned. For example, when the composite film and the reinforcing material are integrated with each other, the above-described convex portions can be formed by using a release paper that has been embossed in advance. When forming a convex part by embossing, control of the height and arrangement density of a convex part can be performed by controlling the emboss shape (shape of release paper) to transfer.

(5) Hydrolysis step In the step (5), the membrane body obtained in the step (4) is hydrolyzed to convert the ion exchange group precursor into an ion exchange group (hydrolysis step).

  In the step (5), elution holes can be formed in the membrane body by dissolving and removing the sacrificial yarn contained in the membrane body with acid or alkali. The sacrificial yarn may be left in the communication hole without being completely dissolved and removed. Further, the sacrificial yarn remaining in the communication hole may be dissolved and removed by the electrolytic solution when the ion exchange membrane is subjected to electrolysis.

  The sacrificial yarn is soluble in acid or alkali in the ion exchange membrane manufacturing process or in an electrolytic environment, and the sacrificial yarn is eluted to form a communication hole at the site.

  The step (5) can be performed by immersing the membrane body obtained in the step (4) in a hydrolysis solution containing an acid or an alkali. As the hydrolysis solution, for example, a mixed solution containing KOH and DMSO (dimethylsulfoxide) can be used.

  The mixed solution preferably contains 2.5 to 4.0 N of KOH and 25 to 35% by mass of DMSO.

  The hydrolysis temperature is preferably 70 to 100 ° C. The higher the temperature, the greater the apparent thickness. More preferably, it is 75-100 degreeC.

  The hydrolysis time is preferably 10 to 120 minutes. The longer the time, the thicker the apparent thickness. More preferably, it is 20 to 120 minutes.

  Here, the step of forming the communication hole by eluting the sacrificial yarn will be described in more detail. FIGS. 4A and 4B are schematic views for explaining a method of forming the communication hole of the ion exchange membrane.

  4 (a) and 4 (b), only the communication hole 504 formed by the reinforcing yarn 52, the sacrificial yarn 504a, and the sacrificial yarn 504a is illustrated, and other members such as the membrane body are not illustrated. ing.

  First, the reinforcing yarn 52 that forms the reinforcing core material in the ion exchange membrane and the sacrificial yarn 504a for forming the communication hole 504 in the ion exchange membrane are used as a braided reinforcing material. Then, the communication hole 504 is formed by the elution of the sacrificial yarn 504a in the step (5).

  According to the above method, the method of weaving the reinforcing yarn 52 and the sacrificial yarn 504a may be adjusted according to the arrangement of the reinforcing core material and the communication hole in the membrane body of the ion exchange membrane.

  FIG. 4A illustrates a plain weave reinforcing material in which reinforcing yarns 52 and sacrificial yarns 504a are woven in both the vertical and horizontal directions on the paper surface. However, the reinforcing yarns 52 in the reinforcing material are used as necessary. And the arrangement of the sacrificial yarn 504a can be changed.

(6) Coating step In the step (6), a coating liquid containing inorganic particles obtained by crushing or melting a raw stone and a binder is prepared, and the coating liquid is prepared from the ion exchange membrane obtained in the step (5). A coating layer can be formed by applying and drying on the surface.

As a binder, a fluorine-containing polymer having an ion exchange group precursor is hydrolyzed with an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH), and then immersed in hydrochloric acid to form a pair of ion exchange groups. A binder in which ions are substituted with H ⁺ (for example, a fluorine-containing polymer having a carboxyl group or a sulfo group) is preferable. This is preferable because it is easy to dissolve in water or ethanol described later.

  This binder is dissolved in a mixed solution of water and ethanol. In addition, the preferable volume ratio of water and ethanol is 10: 1 to 1:10, more preferably 5: 1 to 1: 5, and still more preferably 2: 1 to 1: 2. The inorganic particles are dispersed by a ball mill in the solution thus obtained to obtain a coating solution. At this time, the average particle diameter and the like of the particles can be adjusted by adjusting the time and the rotational speed at the time of dispersion. In addition, the preferable compounding quantity of an inorganic particle and a binder is as above-mentioned.

  The concentration of the inorganic particles and the binder in the coating solution is not particularly limited, but a thin coating solution is preferable. As a result, it is possible to uniformly coat the surface of the ion exchange membrane.

  Further, when dispersing the inorganic particles, a surfactant may be added to the dispersion. As the surfactant, a nonionic surfactant surfactant is preferable, and examples thereof include NOF Corporation HS-210, NS-210, P-210, E-212, and the like.

  An ion exchange membrane is obtained by apply | coating the obtained coating liquid on the surface of an ion exchange membrane by spray application or roll coating.

[Microporous membrane]
As described above, the microporous membrane of the present embodiment is not particularly limited as long as it can be an electrode for electrolysis and a laminate, and various microporous membranes can be applied.
Although the porosity of the microporous film of this embodiment is not specifically limited, For example, it can be set to 20-90, Preferably it is 30-85. The porosity can be calculated by the following formula, for example.
Porosity = (1− (weight of membrane in dry state) / (weight calculated from volume and thickness of membrane material calculated from thickness, width and length of membrane)) × 100
The average pore diameter of the microporous membrane of the present embodiment is not particularly limited, but may be, for example, 0.01 μm to 10 μm, and preferably 0.05 μm to 5 μm. For example, the average pore diameter is obtained by cutting the membrane perpendicular to the thickness direction and observing the cut surface with FE-SEM. It can be obtained by measuring about 100 diameters of the observed holes and averaging them.
Although the thickness of the microporous film of this embodiment is not specifically limited, For example, it can be set as 10 micrometers-1000 micrometers, Preferably it is 50 micrometers-600 micrometers. The thickness can be measured using, for example, a micrometer (manufactured by Mitutoyo Corporation).
Specific examples of the microporous film as described above include Zirfon Perl UTP 500 (also referred to as Zirfon film in this embodiment) manufactured by Agfa, International Publication No. 2013-183854, International Publication No. 2006-203701. And the like.

  The reason why the laminate with the diaphragm of the present embodiment exhibits excellent electrolytic performance is estimated as follows. When the diaphragm and the electrode, which are conventional techniques, are firmly bonded by a method such as thermocompression bonding, the electrode is physically bonded in a state of being embedded in the diaphragm. This adhesion portion hinders the movement of sodium ions in the film, and the voltage increases greatly. On the other hand, when the electrode for electrolysis is in contact with the diaphragm or the power feeder with an appropriate adhesive force as in this embodiment, the movement of sodium ions in the membrane, which is a problem in the prior art, is not hindered. Thereby, when the diaphragm or power supply body and the electrode for electrolysis are in contact with each other with an appropriate adhesive force, excellent electrolysis performance can be expressed even though the diaphragm or power supply body and the electrode for electrolysis are integrated.

[Turn-up body]
The wound body of the present embodiment includes the stacked body of the present embodiment. That is, the wound body of the present embodiment is formed by winding the laminated body of the present embodiment. Like the wound body of this embodiment, handling property can be improved more by winding the laminated body of this embodiment and reducing the size.

[Electrolysis tank]
The electrolytic cell of this embodiment includes the laminate of this embodiment. Hereinafter, an embodiment of an electrolytic cell will be described in detail by taking as an example the case of performing salt electrolysis using an ion exchange membrane as a diaphragm.

[Electrolysis cell]
FIG. 5 is a cross-sectional view of the electrolysis cell 1.
The electrolysis cell 1 was installed in the anode chamber 10, the cathode chamber 20, the partition wall 30 installed between the anode chamber 10 and the cathode chamber 20, the anode 11 installed in the anode chamber 10, and the cathode chamber 20. A cathode 21. If necessary, the substrate 18a and the reverse current absorption layer 18b formed on the substrate 18a may be provided, and the reverse current absorber 18 installed in the cathode chamber may be provided. The anode 11 and the cathode 21 belonging to one electrolytic cell 1 are electrically connected to each other. In other words, the electrolytic cell 1 includes the following cathode structure. The cathode structure 40 includes a cathode chamber 20, a cathode 21 installed in the cathode chamber 20, and a reverse current absorber 18 installed in the cathode chamber 20, and the reverse current absorber 18 is shown in FIG. As shown, it has a base material 18a and a reverse current absorption layer 18b formed on the base material 18a, and the cathode 21 and the reverse current absorption layer 18b are electrically connected. The cathode chamber 20 further includes a current collector 23, a support 24 that supports the current collector, and a metal elastic body 22. The metal elastic body 22 is installed between the current collector 23 and the cathode 21. The support 24 is installed between the current collector 23 and the partition wall 30. The current collector 23 is electrically connected to the cathode 21 via the metal elastic body 22. The partition wall 30 is electrically connected to the current collector 23 via the support 24. Therefore, the partition wall 30, the support 24, the current collector 23, the metal elastic body 22, and the cathode 21 are electrically connected. The cathode 21 and the reverse current absorption layer 18b are electrically connected. The cathode 21 and the reverse current absorption layer may be directly connected, or may be indirectly connected via a current collector, a support, a metal elastic body, a partition wall, or the like. The entire surface of the cathode 21 is preferably covered with a catalyst layer for the reduction reaction. In addition, the form of electrical connection is that the partition wall 30 and the support 24, the support 24 and the current collector 23, the current collector 23 and the metal elastic body 22 are directly attached, and the cathode 21 is laminated on the metal elastic body 22. It may be a form. As a method for directly attaching these constituent members to each other, welding or the like can be mentioned. Further, the reverse current absorber 18, the cathode 21, and the current collector 23 may be collectively referred to as a cathode structure 40.

  FIG. 6 is a cross-sectional view of two electrolytic cells 1 adjacent in the electrolytic cell 4. FIG. 7 shows the electrolytic cell 4. FIG. 8 shows a process of assembling the electrolytic cell 4. As shown in FIG. 6, the electrolytic cell 1, the cation exchange membrane 2, and the electrolytic cell 1 are arranged in series in this order. An ion exchange membrane 2 is disposed between the anode chamber of one electrolytic cell 1 and the cathode chamber of the other electrolytic cell 1 of two adjacent electrolytic cells in the electrolytic cell. That is, the anode chamber 10 of the electrolysis cell 1 and the cathode chamber 20 of the electrolysis cell 1 adjacent thereto are separated by the cation exchange membrane 2. As shown in FIG. 7, the electrolytic cell 4 is composed of a plurality of electrolytic cells 1 connected in series via an ion exchange membrane 2. That is, the electrolytic cell 4 is a bipolar electrolytic cell including a plurality of electrolytic cells 1 arranged in series and an ion exchange membrane 2 arranged between adjacent electrolytic cells 1. As shown in FIG. 8, the electrolytic cell 4 is assembled by arranging a plurality of electrolytic cells 1 in series via an ion exchange membrane 2 and connecting them by a press 5.

  The electrolytic cell 4 has an anode terminal 7 and a cathode terminal 6 connected to a power source. The anode 11 of the electrolytic cell 1 located at the end of the plurality of electrolytic cells 1 connected in series in the electrolytic cell 4 is electrically connected to the anode terminal 7. Among the plurality of electrolytic cells 2 connected in series in the electrolytic cell 4, the cathode 21 of the electrolytic cell located at the end opposite to the anode terminal 7 is electrically connected to the cathode terminal 6. The current during electrolysis flows from the anode terminal 7 side toward the cathode terminal 6 via the anode and cathode of each electrolysis cell 1. In addition, you may arrange | position the electrolysis cell (anode terminal cell) which has only an anode chamber, and the electrolysis cell (cathode terminal cell) which has only a cathode chamber in the both ends of the connected electrolysis cell 1. FIG. In this case, the anode terminal 7 is connected to the anode terminal cell arranged at one end, and the cathode terminal 6 is connected to the cathode terminal cell arranged at the other end.

  When performing electrolysis of salt water, salt water is supplied to each anode chamber 10, and pure water or a low-concentration sodium hydroxide aqueous solution is supplied to the cathode chamber 20. Each liquid is supplied to each electrolytic cell 1 from an electrolytic solution supply pipe (not shown) via an electrolytic solution supply hose (not shown). Moreover, the electrolytic solution and the product by electrolysis are collected from an electrolytic solution collection pipe (not shown in the drawing). In electrolysis, sodium ions in brine move from the anode chamber 10 of one electrolytic cell 1 through the ion exchange membrane 2 to the cathode chamber 20 of the adjacent electrolytic cell 1. Therefore, the current during electrolysis flows along the direction in which the electrolysis cells 1 are connected in series. That is, current flows from the anode chamber 10 toward the cathode chamber 20 through the cation exchange membrane 2. Accompanying the electrolysis of salt water, chlorine gas is generated on the anode 11 side, and sodium hydroxide (solute) and hydrogen gas are generated on the cathode 21 side.

(Anode chamber)
The anode chamber 10 has an anode 11 or an anode feeder 11. When the electrode for electrolysis according to the present embodiment is inserted on the anode side, 11 functions as an anode feeder. When the electrode for electrolysis of this embodiment is not inserted into the anode side, 11 functions as an anode. Further, the anode chamber 10 is disposed above the anode-side electrolyte supply unit that supplies the electrolyte to the anode chamber 10 and the anode-side electrolyte supply unit, and is disposed so as to be substantially parallel or oblique to the partition wall 30. It is preferable to have a baffle plate and an anode-side gas-liquid separator that is disposed above the baffle plate and separates the gas from the electrolyte mixed with the gas.

(anode)
When the electrode for electrolysis of this embodiment is not inserted on the anode side, an anode 11 is provided in the frame of the anode chamber 10. As the anode 11, a metal electrode such as so-called DSA (registered trademark) can be used. DSA is a titanium-based electrode whose surface is coated with an oxide containing ruthenium, iridium and titanium.
As the shape, any of punching metal, non-woven fabric, foam metal, expanded metal, metal porous foil formed by electroforming, so-called woven mesh produced by knitting metal wire, and the like can be used.

(Anode feeder)
When the electrode for electrolysis of the present embodiment is inserted on the anode side, an anode power supply 11 is provided in the frame of the anode chamber 10. As the anode power supply 11, a metal electrode such as a so-called DSA (registered trademark) can be used, or titanium without a catalyst coating can be used. Also, DSA with a thin catalyst coating thickness can be used. Furthermore, a used anode can also be used.
As the shape, any of punching metal, non-woven fabric, foam metal, expanded metal, metal porous foil formed by electroforming, so-called woven mesh produced by knitting metal wire, and the like can be used.

(Anode-side electrolyte supply unit)
The anode side electrolyte solution supply unit supplies the electrolyte solution to the anode chamber 10 and is connected to the electrolyte solution supply pipe. The anode-side electrolyte supply unit is preferably arranged below the anode chamber 10. As the anode-side electrolyte supply part, for example, a pipe (dispersion pipe) having an opening formed on the surface can be used. More preferably, such a pipe is arranged along the surface of the anode 11 in parallel with the bottom 19 of the electrolysis cell. This pipe is connected to an electrolytic solution supply pipe (liquid supply nozzle) that supplies the electrolytic solution into the electrolytic cell 1. The electrolytic solution supplied from the liquid supply nozzle is conveyed into the electrolytic cell 1 by a pipe, and is supplied into the anode chamber 10 through an opening provided on the surface of the pipe. It is preferable to arrange the pipe along the surface of the anode 11 in parallel with the bottom portion 19 of the electrolytic cell, because the electrolyte can be uniformly supplied into the anode chamber 10.

(Anode-side gas-liquid separator)
It is preferable that the anode side gas-liquid separator is disposed above the baffle plate. During electrolysis, the anode-side gas-liquid separator has a function of separating the generated gas such as chlorine gas and the electrolytic solution. Unless otherwise specified, the upper direction means the upward direction in the electrolysis cell 1 in FIG. 5, and the lower direction means the downward direction in the electrolysis cell 1 in FIG. 5.

  During electrolysis, when the product gas and electrolyte generated in the electrolytic cell 1 become a mixed phase (gas-liquid mixed phase) and are discharged out of the system, vibration is generated due to pressure fluctuations inside the electrolytic cell 1, and the physical properties of the ion exchange membrane are generated. May cause damage. In order to suppress this, it is preferable that the electrolytic cell 1 of the present embodiment is provided with an anode-side gas-liquid separation unit for separating gas and liquid. It is preferable that a defoaming plate for eliminating bubbles is installed in the anode side gas-liquid separation unit. When the gas-liquid mixed phase flow passes through the defoaming plate, the bubbles are repelled, so that the electrolyte and gas can be separated. As a result, vibration during electrolysis can be prevented.

(Baffle plate)
It is preferable that the baffle plate is disposed above the anode side electrolyte supply unit and is disposed substantially parallel or oblique to the partition wall 30. The baffle plate is a partition plate that controls the flow of the electrolytic solution in the anode chamber 10. By providing the baffle plate, an electrolytic solution (salt water or the like) can be circulated in the anode chamber 10 to make the concentration uniform. In order to cause internal circulation, the baffle plate is preferably disposed so as to separate the space near the anode 11 and the space near the partition wall 30. From this point of view, the baffle plate is preferably provided so as to face each surface of the anode 11 and the partition wall 30. In the space in the vicinity of the anode partitioned by the baffle plate, the electrolytic solution concentration (salt water concentration) decreases due to the progress of electrolysis, and product gas such as chlorine gas is generated. Thereby, the specific gravity difference of a gas-liquid arises in the space near the anode 11 partitioned by the baffle plate and the space near the partition 30. By utilizing this, the internal circulation of the electrolytic solution in the anode chamber 10 can be promoted, and the concentration distribution of the electrolytic solution in the anode chamber 10 can be made more uniform.

  Although not shown in FIG. 5, a current collector may be separately provided inside the anode chamber 10. Such a current collector may have the same material and configuration as the current collector of the cathode chamber described later. In the anode chamber 10, the anode 11 itself can also function as a current collector.

(Partition wall)
The partition wall 30 is disposed between the anode chamber 10 and the cathode chamber 20. The partition wall 30 is sometimes called a separator, and partitions the anode chamber 10 and the cathode chamber 20. As the partition walls 30, known separators for electrolysis can be used, and examples include partition walls in which a plate made of nickel on the cathode side and titanium on the anode side is welded.

(Cathode room)
The cathode chamber 20 functions as a cathode power supply when the electrode for electrolysis of the present embodiment is inserted to the cathode side, and 21 when the electrode for electrolysis of the present embodiment is not inserted to the cathode side. Functions as a cathode. In the case of having a reverse current absorber, the cathode or the cathode power supply 21 and the reverse current absorber are electrically connected. Similarly to the anode chamber 10, the cathode chamber 20 preferably includes a cathode side electrolyte supply unit and a cathode side gas-liquid separation unit. Note that the description of the same parts as those constituting the anode chamber 10 among the parts constituting the cathode chamber 20 is omitted.

(cathode)
When the electrode for electrolysis of this embodiment is not inserted on the cathode side, a cathode 21 is provided in the frame of the cathode chamber 20. The cathode 21 preferably has a nickel base and a catalyst layer covering the nickel base. The components of the catalyst layer on the nickel substrate include 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, Examples thereof include metals such as Dy, Ho, Er, Tm, Yb, and Lu, and oxides or hydroxides of the metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and thermal spraying. These methods may be combined. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Moreover, you may perform a reduction process to the cathode 21 as needed. In addition, as the base material of the cathode 21, nickel, nickel alloy, iron or stainless steel plated with nickel may be used.
As the shape, any of punching metal, non-woven fabric, foam metal, expanded metal, metal porous foil formed by electroforming, so-called woven mesh produced by knitting metal wire, and the like can be used.

(Cathode feeder)
When the electrode for electrolysis of this embodiment is inserted on the cathode side, a cathode power supply 21 is provided in the frame of the cathode chamber 20. The cathode power supply 21 may be coated with a catalyst component. The catalyst component may originally be used as a cathode and remain. Components of the catalyst layer include 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, Lu, and the like, and oxides or hydroxides of the metals. Examples of the method for forming the catalyst layer include plating, alloy plating, dispersion / composite plating, CVD, PVD, thermal decomposition, and thermal spraying. These methods may be combined. The catalyst layer may have a plurality of layers and a plurality of elements as necessary. Further, nickel, nickel alloy, iron, or stainless steel that is not coated with a catalyst may be plated with nickel. In addition, as a base material of the cathode power supply body 21, nickel, nickel alloy, iron or stainless steel plated with nickel may be used.
As the shape, any of punching metal, non-woven fabric, foam metal, expanded metal, metal porous foil formed by electroforming, so-called woven mesh produced by knitting metal wire, and the like can be used.

(Reverse current absorption layer)
A material having a redox potential lower than that of the element for the cathode catalyst layer described above can be selected as the material for the reverse current absorption layer. For example, nickel, iron, etc. are mentioned.

(Current collector)
The cathode chamber 20 preferably includes a current collector 23. Thereby, the current collection effect increases. In the present embodiment, the current collector 23 is a perforated plate, and is preferably disposed substantially parallel to the surface of the cathode 21.

  The current collector 23 is preferably made of an electrically conductive metal such as nickel, iron, copper, silver, or titanium. The current collector 23 may be a mixture, alloy or composite oxide of these metals. The shape of the current collector 23 may be any shape as long as it functions as a current collector, and may be a plate shape or a net shape.

(Metal elastic body)
By installing the metal elastic body 22 between the current collector 23 and the cathode 21, each cathode 21 of the plurality of electrolysis cells 1 connected in series is pressed against the ion exchange membrane 2, and each anode 11 and each cathode The distance to the cathode 21 is shortened, and the voltage applied to the entire plurality of electrolysis cells 1 connected in series can be reduced. By reducing the voltage, the power consumption can be reduced. Moreover, when the laminated body including the electrode for electrolysis according to the present embodiment is installed in an electrolysis cell by the metal elastic body 22 being installed, the electrode for electrolysis is stabilized by the pressing pressure of the metal elastic body 22. Can be kept in place.

  As the metal elastic body 22, a spiral member, a spring member such as a coil, a cushioning mat, or the like can be used. As the metal elastic body 22, a suitable material can be adopted as appropriate in consideration of stress that presses the ion exchange membrane. The metal elastic body 22 may be provided on the surface of the current collector 23 on the cathode chamber 20 side, or may be provided on the surface of the partition wall on the anode chamber 10 side. Normally, both chambers are partitioned so that the cathode chamber 20 is smaller than the anode chamber 10, so that the metal elastic body 22 is placed between the current collector 23 and the cathode 21 in the cathode chamber 20 from the viewpoint of the strength of the frame. It is preferable to provide in. Moreover, it is preferable that the metal elastic body 23 consists of metals which have electrical conductivity, such as nickel, iron, copper, silver, and titanium.

(Support)
The cathode chamber 20 preferably includes a support 24 that electrically connects the current collector 23 and the partition wall 30. Thereby, an electric current can be sent efficiently.

  The support 24 is preferably made of a metal having electrical conductivity such as nickel, iron, copper, silver, or titanium. Further, the shape of the support 24 may be any shape as long as it can support the current collector 23, and may be a rod shape, a plate shape, or a net shape. The support 24 is, for example, a plate shape. The plurality of supports 24 are disposed between the partition wall 30 and the current collector 23. The plurality of supports 24 are arranged so that their surfaces are parallel to each other. The support 24 is disposed substantially perpendicular to the partition wall 30 and the current collector 23.

(Anode side gasket, cathode side gasket)
The anode side gasket is preferably disposed on the surface of the frame constituting the anode chamber 10. The cathode side gasket is preferably arranged on the surface of the frame constituting the cathode chamber 20. The electrolytic cells are connected to each other so that the anode side gasket provided in one electrolytic cell and the cathode side gasket of the electrolytic cell adjacent thereto sandwich the ion exchange membrane 2 (see FIGS. 5 and 6). With these gaskets, when a plurality of electrolytic cells 1 are connected in series via the ion exchange membrane 2, airtightness can be imparted to the connection location.

  A gasket seals between an ion exchange membrane and an electrolysis cell. Specific examples of the gasket include a frame-shaped rubber sheet having an opening formed in the center. Gaskets are required to be resistant to corrosive electrolytes and generated gases and to be usable for a long period of time. Therefore, from the viewpoint of chemical resistance and hardness, vulcanized products of ethylene / propylene / diene rubber (EPDM rubber), ethylene / propylene rubber (EPM rubber), peroxide crosslinked products, and the like are usually used as gaskets. If necessary, use a gasket in which the area in contact with the liquid (liquid contact portion) is covered with a fluororesin such as polytetrafluoroethylene (PTFE) or tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA). You can also. These gaskets only have to have openings so as not to hinder the flow of the electrolyte solution, and the shape thereof is not particularly limited. For example, a frame-shaped gasket is attached with an adhesive or the like along the peripheral edge of each opening of the anode chamber frame constituting the anode chamber 10 or the cathode chamber frame constituting the cathode chamber 20. For example, when two electrolytic cells 1 are connected via the ion exchange membrane 2 (see FIG. 6), each electrolytic cell 1 to which a gasket is attached via the ion exchange membrane 2 may be tightened. Thereby, it can suppress that the electrolyte solution, the alkali metal hydroxide produced | generated by electrolysis, chlorine gas, hydrogen gas, etc. leak to the exterior of the electrolytic cell 1. FIG.

(Ion exchange membrane)
The ion exchange membrane 2 is as described above in the section of the ion exchange membrane.

(Water electrolysis)
The electrolytic cell according to the present embodiment, in the case of performing water electrolysis, has a configuration in which the ion exchange membrane in the electrolytic cell in the case of performing salt electrolysis is changed to a microporous membrane. Moreover, it differs from the electrolytic cell in the case of performing the salt electrolysis mentioned above in that the raw material to be supplied is water. About another structure, the structure similar to the electrolytic cell in the case of performing salt electrolysis can also be employ | adopted for the electrolytic cell in the case of performing water electrolysis. In the case of salt electrolysis, since chlorine gas is generated in the anode chamber, titanium is used as the material of the anode chamber. However, in the case of water electrolysis, only oxygen gas is generated in the anode chamber. The same material as can be used. For example, nickel etc. are mentioned. Moreover, the anode coating is suitably a catalyst coating for generating oxygen. Examples of catalyst coatings include platinum group metals and transition metal metals, oxides, hydroxides, and the like. For example, elements such as platinum, iridium, palladium, ruthenium, nickel, cobalt, and iron can be used.

(Use of laminates)
As described above, the laminate of the present embodiment can improve the working efficiency at the time of electrode renewal in the electrolytic cell, and can also exhibit excellent electrolytic performance after renewal. In other words, the laminated body of this embodiment can be used suitably as a laminated body for member replacement of an electrolytic cell. In addition, the laminated body at the time of applying to such a use is especially called a “membrane electrode assembly”.

(Packaging body)
It is preferable that the laminated body of this embodiment performs conveyance etc. in the state enclosed with the packaging material. That is, the package of this embodiment includes the laminate of this embodiment and a packaging material for packaging the laminate. Since the package of the present embodiment is configured as described above, it is possible to prevent adhesion and damage of dirt that may occur when the laminate of the present embodiment is transported. When it is intended for replacement of an electrolytic cell member, it is particularly preferable to carry it as the package of the present embodiment. The packaging material in the present embodiment is not particularly limited, and various known packaging materials can be applied. Moreover, the packaging body of this embodiment is not limited to the following, For example, it can manufacture by the method of packaging the laminated body of this embodiment with the packaging material of a clean state, and encapsulating then.

  The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples.

〔Evaluation method〕
(1) Opening ratio The electrode was cut into a size of 130 mm × 100 mm. Using a Digimatic Sixness Gauge (manufactured by Mitutoyo Corporation, minimum display 0.001 mm), an average value obtained by uniformly measuring 10 points within the surface was calculated. Using this as the electrode thickness (gauge thickness), the volume was calculated. Thereafter, the mass was measured with an electronic balance, and the porosity or porosity was calculated from the specific gravity of the metal (specific gravity of nickel = 8.908 g / cm ³ , specific gravity of titanium = 4.506 g / cm ³ ).

  Opening ratio (porosity) (%) = (1− (electrode mass) / (electrode volume × metal specific gravity)) × 100

(2) Mass per unit area (mg / cm ² )
The electrode was cut into a size of 130 mm × 100 mm, and the mass was measured with an electronic balance. The value was divided by the area (130 mm × 100 mm) to calculate the mass per unit area.

(3) Force applied per unit mass / unit area (1) (Adhesive strength) (N / mg · cm ² ))
[Method (i)]
A tensile / compression tester was used for the measurement (Imata Manufacturing Co., Ltd., tester body: SDT-52NA type tensile / compression tester, weight meter: SL-6001 type load meter).

  A nickel plate having a thickness of 1.2 mm and a 200 mm square was blasted with alumina having a grain number of 320. The arithmetic average surface roughness (Ra) of the nickel plate after blasting was 0.7 μm. Here, a stylus type surface roughness measuring machine SJ-310 (Mitutoyo Corporation) was used for the surface roughness measurement. A measurement sample was placed on a surface plate parallel to the ground, and the arithmetic average roughness Ra was measured under the following measurement conditions. The average value was described when the measurement was performed 6 times.

<Shape shape> Conical taper angle = 60 °, tip radius = 2 μm, static measuring force = 0.75 mN
<Roughness standard> JIS2001
<Evaluation curve> R
<Filter> GAUSS
<Cutoff value λc> 0.8mm
<Cutoff value λs> 2.5μm
<Number of sections> 5
<Pre-run, Post-run> Existence This nickel plate was fixed to the lower chuck of the tensile and compression tester so as to be vertical.

The following ion exchange membrane A was used as the diaphragm.
As the reinforcing core material, a 90 denier monofilament made of polytetrafluoroethylene (PTFE) was used (hereinafter referred to as PTFE yarn). As the sacrificial yarn, a yarn in which a twist of 35 deniers and 6 filaments of polyethylene terephthalate (PET) was applied 200 times / m was used (hereinafter referred to as PET yarn). First, in each of the TD and MD directions, a plain woven fabric was obtained by plain weaving so that 24 PTFE yarns / inch and two sacrificial yarns were arranged between adjacent PTFE yarns. The obtained woven fabric was pressure-bonded with a roll to obtain a woven fabric having a thickness of 70 μm.
Next, a resin A and CF of a dry resin, which is a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ and has an ion exchange capacity of 0.85 mg equivalent / g A resin B of a dry resin having an ion exchange capacity of 1.03 mg equivalent / g, which is a copolymer of ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F, was prepared.
Using these resins A and B, a two-layer film X having a resin A layer thickness of 15 μm and a resin B layer thickness of 104 μm was obtained by coextrusion T-die method.
Subsequently, on the hot plate having a heating source and a vacuum source inside and having fine holes on the surface, release paper (conical embossing with a height of 50 μm), a reinforcing material and a film X are laminated in this order. After heating and depressurizing for 2 minutes under conditions of a hot plate surface temperature of 223 ° C. and a degree of vacuum of 0.067 MPa, a release film was removed to obtain a composite film.
The obtained composite membrane was saponified by immersing it in an 80 ° C. aqueous solution containing 30% by mass of dimethyl sulfoxide (DMSO) and 15% by mass of potassium hydroxide (KOH) for 20 minutes. Then, it was immersed in an aqueous solution containing sodium hydroxide (NaOH) 0.5N at 50 ° C. for 1 hour to replace the counter ion of the ion exchange group with Na, followed by washing with water. Furthermore, it dried at 60 degreeC.
Furthermore, 20% by mass of zirconium oxide having a primary particle diameter of 1 μm was added to a 5% by mass ethanol solution of an acid type resin of resin B, and a dispersed suspension was prepared. Spraying was performed on both sides of the membrane to form a coating of zirconium oxide on the surface of the composite membrane, whereby an ion exchange membrane A was obtained. When the coating density of zirconium oxide was measured by fluorescent X-ray measurement, it was 0.5 mg / cm ² . The average particle size was measured by a particle size distribution meter (“SALD (registered trademark) 2200” manufactured by Shimadzu Corporation).
The ion exchange membrane (diaphragm) obtained above was immersed in pure water for 12 hours or more and then used for the test. It was brought into contact with the nickel plate sufficiently wetted with pure water and adhered with water tension. At this time, it installed so that the position of the upper end of a nickel plate and an ion exchange membrane might match.

Electrolytic electrode samples (electrodes) used for measurement were cut into 130 mm squares. The ion exchange membrane A was cut into 170 mm square. Two sides of the electrode were sandwiched between two stainless plates (thickness 1 mm, length 9 mm, width 170 mm), aligned so that the centers of the stainless plate and the electrodes were aligned, and then fixed equally with four clips. The center of the stainless steel plate was sandwiched between the upper chuck of the tensile and compression tester, and the electrode was suspended. At this time, the load applied to the testing machine was set to 0N. Once the stainless steel plate, electrode, and clip were removed from the tensile / compression tester, the electrode was immersed in a bat containing pure water to fully wet the electrode with pure water. Thereafter, the center of the stainless steel plate was sandwiched between the upper chuck of the tensile and compression tester and the electrode was suspended.
The upper chuck of the tensile and compression tester was lowered, and the electrode sample for electrolysis was adhered to the surface of the ion exchange membrane with the surface tension of pure water. The adhesive surface at this time was 130 mm wide and 110 mm long. Pure water placed in a washing bottle was sprayed on the entire electrode and ion exchange membrane, so that the membrane and the electrode were sufficiently wetted again. Then, while pressing a roller in which an independent foam type EPDM sponge rubber having a thickness of 5 mm was wound around a polyvinyl chloride tube (outer diameter: 38 mm) lightly from above the electrode, it was rolled from the top to the bottom to remove excess pure water. The roller was applied only once.

The weight measurement was started by raising the electrode at a speed of 10 mm / min, and the weight when the overlapping portion of the electrode and the diaphragm was 130 mm wide and 100 mm long was recorded. This measurement was performed 3 times and the average value was calculated.
The average value was divided by the area of the overlapping portion of the electrode and the ion exchange membrane and the electrode mass of the portion overlapping the ion exchange membrane to calculate the force (1) per unit mass / unit area. The electrode mass of the portion overlapping the ion exchange membrane was determined by proportional calculation from the value obtained in the mass per unit area (mg / cm ² ) in (2) above.
The environment of the measurement chamber was a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%.
The electrodes used in Examples and Comparative Examples were able to adhere independently without slipping down or peeling off when adhered to an ion exchange membrane adhered to a vertically fixed nickel plate with surface tension.
In addition, the schematic diagram of the evaluation method of this force (1) was shown in FIG.
In addition, the measurement lower limit of the tensile tester was 0.01 (N).

(4) Force applied per unit mass / unit area (2) (Adhesive strength) (N / mg · cm ² ))
[Method (ii)]
A tensile / compression tester was used for the measurement (Imata Manufacturing Co., Ltd., tester body: SDT-52NA type tensile / compression tester, weight meter: SL-6001 type load meter).
The same nickel plate as in method (i) was fixed to the lower chuck of the tensile and compression tester so as to be vertical.
Electrolytic electrode samples (electrodes) used for measurement were cut into 130 mm squares. The ion exchange membrane A was cut into 170 mm square. Two sides of the electrode were sandwiched between two stainless plates (thickness 1 mm, length 9 mm, width 170 mm), aligned so that the centers of the stainless plate and the electrodes were aligned, and then fixed equally with four clips. The center of the stainless steel plate was sandwiched between the upper chuck of the tensile and compression tester, and the electrode was suspended. At this time, the load applied to the testing machine was set to 0N. Once the stainless steel plate, electrode, and clip were removed from the tensile / compression tester, the electrode was immersed in a bat containing pure water to fully wet the electrode with pure water. Thereafter, the center of the stainless steel plate was sandwiched between the upper chuck of the tensile and compression tester and the electrode was suspended.

The upper chuck of the tensile and compression tester was lowered, and the electrode sample for electrolysis was adhered to the surface of the nickel plate with the surface tension of the solution. The adhesive surface at this time was 130 mm wide and 110 mm long. Pure water placed in the washing bottle was sprayed on the entire electrode and nickel plate, so that the nickel plate and the electrode were sufficiently wetted again. Thereafter, while rolling a roller in which an independent foaming type EPDM sponge rubber having a thickness of 5 mm was wound around a polyvinyl chloride tube (outer diameter: 38 mm) from the top of the electrode, it was rolled from the top to the bottom to remove the excess solution. The roller was applied only once.
The weight measurement was started by raising the electrode at a speed of 10 mm / min, and the weight when the overlapping portion of the electrode and the nickel plate in the vertical direction reached 100 mm was recorded. This measurement was performed 3 times and the average value was calculated.
The average value was divided by the area of the overlapping portion of the electrode and the nickel plate and the electrode mass of the portion overlapping the nickel plate to calculate the force (2) per unit mass / unit area. The electrode mass of the portion overlapping with the diaphragm was obtained by proportional calculation from the value obtained in the mass per unit area (mg / cm ² ) in (2) above.
The environment of the measurement chamber was a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%.
The electrodes used in Examples and Comparative Examples were able to adhere independently without slipping down or peeling off when adhered to a vertically fixed nickel plate with surface tension.
In addition, the measurement lower limit of the tensile tester was 0.01 (N).

(5) 280 mm diameter cylindrical winding evaluation method (1) (%)
(Membrane and cylinder)
Evaluation method (1) was carried out by the following procedure.
The ion exchange membrane A (diaphragm) prepared by [Method (i)] was cut into a 170 mm square size. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. In Comparative Examples 1 and 2, since the electrode was integrated with the ion exchange membrane by hot pressing, an integrated body of the ion exchange membrane and the electrode was prepared (the electrode was 130 mm square). The ion exchange membrane was sufficiently immersed in pure water and then placed on the curved surface of a plastic (polyethylene) pipe having an outer diameter of 280 mm. Thereafter, excess solution was removed with a roller in which an independent foam type EPDM sponge rubber having a thickness of 5 mm was wound around a polyvinyl chloride tube (outer diameter: 38 mm). The roller rolled on the ion exchange membrane from left to right in the schematic diagram shown in FIG. The roller was applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane and the plastic pipe electrode having an outer diameter of 280 mm were in close contact with each other was measured.

(6) 280 mm diameter cylindrical winding evaluation method (2) (%)
(Membrane and electrode)
Evaluation method (2) was carried out by the following procedure.
The ion exchange membrane A (diaphragm) prepared by [Method (i)] was cut to a size of 170 mm square and the electrode was cut to 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) pipe having an outer diameter of 280 mm so that the electrodes were on the outside. Then, while gently pressing a roller wrapped with an independent foaming type EPDM sponge rubber having a thickness of 5 mm around a PVC pipe (outer diameter: 38 mm) from the top of the electrode, it is rolled from the left to the right in the schematic diagram shown in FIG. Excess solution was removed. The roller was applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane and the electrode were in close contact was measured.

(7) 145 mm diameter cylindrical winding evaluation method (3) (%)
(Membrane and electrode)
Evaluation method (3) was performed in the following procedure.
The ion exchange membrane A (diaphragm) prepared by [Method (i)] was cut to a size of 170 mm square and the electrode was cut to 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) pipe having an outer diameter of 145 mm so that the electrodes were on the outside. Then, while gently pressing a roller wrapped with an independent foaming type EPDM sponge rubber having a thickness of 5 mm around a PVC pipe (outer diameter: 38 mm) from the top of the electrode, it was rolled from the left to the right in the schematic diagram shown in FIG. Excess solution was removed. The roller was applied only once. After 1 minute, the ratio of the portion where the ion exchange membrane and the electrode were in close contact was measured.

(8) Handling (sensitivity evaluation)
(A) The ion exchange membrane A (diaphragm) prepared by [Method (i)] was cut to a size of 170 mm square, and the electrode was cut to 95 × 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 a sodium bicarbonate aqueous solution, a 0.1N NaOH aqueous solution, and pure water, and then laminated and placed on a Teflon (registered trademark) plate. The interval between the anode cell and the cathode cell used in the electrolysis evaluation was set to about 3 cm, and the laminated body which was statically ground was lifted, and inserted and sandwiched between them. When performing this operation, it was confirmed while operating whether the electrodes were not displaced or not dropped.

(B) The ion exchange membrane A (diaphragm) prepared by [Method (i)] was cut to a 170 mm square size and the electrode was cut to 95 × 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 a sodium bicarbonate aqueous solution, a 0.1N NaOH aqueous solution, and pure water, and then laminated and placed on a Teflon (registered trademark) plate. The two adjacent corners of the film portion of the laminate were held by hand and lifted so that the laminate was vertical. From this state, the two corners held by the hand were moved closer so that the film became convex and concave. This was repeated once more to confirm the followability of the electrode to the film. The result was evaluated in four stages of 1-4 based on the following indices.
1: Good handling 2: Handling is possible 3: Handling is difficult 4: Handling is almost impossible Here, in the sample of Comparative Example 5, the electrode is 1.3 m × 2.5 m, and the ion exchange membrane is 1.5 m × 2.8 m. The handling was carried out with the same size as the large electrolysis cell of size. The evaluation result of Comparative Example 5 (“3” as described later) was used as an index for evaluating the difference between the evaluations (A) and (B) and the large size. That is, when the results of evaluating a small laminate were “1” and “2”, it was evaluated that there was no problem in handling even when the large size was used.

(9) Electrolytic evaluation (voltage (V), current efficiency (%), sodium chloride concentration in sodium hydroxide (ppm, converted to 50%))
The electrolytic performance was evaluated by the following electrolysis experiment.
A titanium anode cell (anode terminal cell) having an anode chamber in which an anode was installed faced a cathode cell having a nickel cathode chamber (cathode terminal cell) in which a cathode was installed. A pair of gaskets was disposed between the cells, and a laminate (a laminate of the ion exchange membrane A and the electrode for electrolysis) was sandwiched between the pair of gaskets. And an anode cell, a gasket, a laminated body, a gasket, and a cathode were stuck, an electrolysis cell was obtained, and an electrolyzer containing this was prepared.

  The anode was prepared by applying, drying, and firing a mixed solution of ruthenium chloride, iridium chloride, and titanium tetrachloride on a titanium base that had been subjected to blasting and acid etching treatment as a pretreatment. The anode was fixed to the anode chamber by welding. As the cathode, those described in the examples and comparative examples were used. As the current collector for the cathode chamber, nickel expanded metal was used. The size of the current collector was 95 mm long × 110 mm wide. As the metal elastic body, a mattress knitted with a nickel fine wire was used. A mattress, which is a metal elastic body, was placed on the current collector. A nickel mesh in which a nickel wire having a diameter of 150 μm was plain woven with a mesh opening of 40 mesh was covered thereon, and the four corners of the Ni mesh were fixed to the current collector with a string made of Teflon (registered trademark). This Ni mesh was used as a power feeder. This electrolysis cell has a zero gap structure utilizing the repulsive force of the mattress which is a metal elastic body. As the gasket, a rubber gasket made of EPDM (ethylene propylene diene) was used. As the diaphragm, the ion exchange membrane A (160 mm square) prepared by [Method (i)] was used.

Sodium chloride was electrolyzed using the electrolytic cell. The salt water concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The sodium hydroxide concentration in the cathode chamber was adjusted to 32% by mass. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolysis cell was 90 ° C. Sodium chloride electrolysis was performed at a current density of 6 kA / m ² , and voltage, current efficiency, and sodium chloride concentration in caustic soda were measured. Here, the current efficiency is the ratio of the amount of generated caustic soda to the flowed current. Efficiency is reduced. The current efficiency was determined by dividing the number of moles of caustic soda produced in a certain time by the number of moles of electrons of the current flowing during that time. The number of moles of caustic soda was determined by collecting caustic soda generated by electrolysis in a plastic tank and measuring its mass. The salt concentration in caustic soda showed a value obtained by converting the caustic soda concentration to 50%.
In addition, in Table 1, the specification of the electrode and electric power feeding body which were used by the Example and the comparative example was shown.

(11) Measurement of catalyst layer thickness, electrode base material for electrolysis, electrode thickness measurement The thickness of the electrode base material for electrolysis is in-plane using a digimatic sixness gauge (manufactured by Mitutoyo Corporation, minimum display 0.001 mm). An average value obtained by uniformly measuring 10 points was calculated. This was made into the thickness (gauge thickness) of the electrode base material for electrolysis. The thickness of the electrode was calculated as an average value obtained by uniformly measuring 10 points within the surface with a digimatic sixness gauge in the same manner as the electrode substrate. This was defined as the electrode thickness (gauge thickness). The thickness of the catalyst layer was determined by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.

(12) Elastic deformation test of electrode The ion exchange membrane A (diaphragm) and electrode prepared by [Method (i)] were cut into a 110 mm square size. The ion exchange membrane was immersed in pure water for 12 hours or more and then used for the test. After producing a laminate by stacking the ion exchange membrane and the electrode under the conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 30 ± 5%, as shown in FIG. It was wrapped so that there was no gap. The wound laminate was fixed using a polyethylene binding band so that the wound laminate was not peeled off or loosened from the PVC pipe. This state was maintained for 6 hours. Thereafter, the binding band was removed, and the laminate was rewound from the PVC pipe. Only the electrode was placed on the surface plate, and the heights L ₁ and L ₂ of the part that floated from the surface plate were measured, and the average value was obtained. This value was used as an index of electrode deformation. That is, a smaller value means that deformation is less likely.
In addition, when using expanded metal, there are two types of SW direction and LW direction when winding. In this test, it was wound in the SW direction.
Further, the softness after plastic deformation was evaluated by the method shown in FIG. 15 for the deformed electrode (the electrode that did not return to the original flat state). That is, the deformed electrode is placed on a diaphragm sufficiently immersed in pure water, one end is fixed, the opposite opposite end is pressed against the diaphragm, the force is released, and the deformed electrode Evaluated whether or not to follow the diaphragm.

(13) Membrane damage evaluation The following ion exchange membrane B was used as the diaphragm.
As the reinforcing core material, polytetrafluoroethylene (PTFE), which was formed into a yarn shape by applying a twist of 900 times / m to a 100-denier tape yarn (hereinafter referred to as PTFE yarn) was used. As sacrificial yarn for warp, a yarn obtained by twisting 200 deniers / polyethylene terephthalate (PET) of 35 denier and 8 filaments (hereinafter referred to as PET yarn) was used. As a weft sacrificial yarn, a yarn of 35 denier, 8-filament polyethylene terephthalate (PET) twisted 200 times / m was used. First, plain weaving was performed so that 24 PTFE yarns / inch and two sacrificial yarns were arranged between adjacent PTFE yarns to obtain a woven fabric having a thickness of 100 μm.
Next, a polymer (A1) of a dry resin which is a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ and has an ion exchange capacity of 0.92 mg equivalent / g A polymer (B1) of a dry resin, which is a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and has an ion exchange capacity of 1.10 mg equivalent / g Got ready. Using these polymers (A1) and (B1), a co-extrusion T die method is used to obtain a two-layer film X having a polymer (A1) layer thickness of 25 μm and a polymer (B1) layer thickness of 89 μm. It was. In addition, the ion exchange capacity of each polymer showed the ion exchange capacity at the time of hydrolyzing the ion exchange group precursor of each polymer, and converting into the ion exchange group.
Separately, a polymer (B2) of a dry resin having an ion exchange capacity of 1.10 mg equivalent / g, which is a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F. ) Was prepared. This polymer was monolayer extruded to obtain a film Y of 20 μm.
Subsequently, a release paper, a film Y, a reinforcing material and a film X are laminated in this order on a hot plate having a heating source and a vacuum source inside and having fine holes on the surface, and the hot plate temperature is 225 ° C. and the degree of pressure reduction. After heating and depressurizing for 2 minutes under the condition of 0.022 MPa, the release paper was removed to obtain a composite film. The obtained composite membrane was saponified by immersing it in an aqueous solution containing dimethyl sulfoxide (DMSO) and potassium hydroxide (KOH) for 1 hour, and then immersed in 0.5N NaOH for 1 hour to attach ion exchange groups. The ions were replaced with Na, followed by washing with water. Furthermore, it dried at 60 degreeC.
Further, a polymer (B3) of a dry resin having an ion exchange capacity of 1.05 mg equivalent / g, which is a copolymer of CF ₂ = CF ₂ and CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F Was hydrolyzed and acidified with hydrochloric acid. This acid type polymer (B3 ′) was dissolved in a 50/50 (mass ratio) mixture of water and ethanol at a ratio of 5% by mass with an oxidation of an average primary particle size of 0.02 μm. Zirconium particles were added so that the mass ratio of the polymer (B3 ′) to the zirconium oxide particles was 20/80. Then, it was dispersed in a suspension of zirconium oxide particles with a ball mill to obtain a suspension.
This suspension was applied to both surfaces of the ion exchange membrane by a spray method and dried to obtain an ion exchange membrane B having a coating layer containing a polymer (B3 ′) and zirconium oxide particles. When the application density of zirconium oxide was measured by fluorescent X-ray measurement, it was 0.35 mg / cm ² .

The anode used was the same as in (9) Electrolytic evaluation.
The cathode described in each example and comparative example was used. The current collector, mattress, and power feeder in the cathode chamber were the same as those in (9) Electrolytic evaluation. That is, a zero-gap structure has been obtained by using the repulsive force of a mattress, which is a metal elastic body, using Ni mesh as a power feeder. The same gasket as in (9) Electrolytic evaluation was used. As the diaphragm, the ion exchange membrane B prepared by the above method was used. That is, an electrolytic cell similar to (9) was prepared except that the laminate of the ion exchange membrane B and the electrode for electrolysis was sandwiched between a pair of gaskets.

Sodium chloride was electrolyzed using the electrolytic cell. The salt water concentration (sodium chloride concentration) in the anode chamber was adjusted to 205 g / L. The sodium hydroxide concentration in the cathode chamber was adjusted to 32% by mass. Each temperature of the anode chamber and the cathode chamber was adjusted so that the temperature in each electrolytic cell was 70 ° C. Salt electrolysis was performed at a current density of 8 kA / m ² . After 12 hours from the start of electrolysis, the electrolysis was stopped, the ion exchange membrane B was taken out, and the damaged state was observed.
“0” means that there was no damage. “1 to 3” means that there is damage. The larger the number, the greater the degree of damage.

(14) Ventilation Resistance of Electrode The ventilation resistance of the electrode was measured using an air permeability tester KES-F8 (trade name, Kato Tech Co., Ltd.). The unit of the ventilation resistance value is kPa · s / m. The measurement was performed 5 times, and the average value is shown in Table 2. The measurement was performed under the following two conditions. The temperature in the measurement chamber was 24 ° C. and the relative humidity was 32%.
・ Measurement condition 1 (Ventilation resistance 1)
Piston speed: 0.2 cm / s
Aeration rate: 0.4 cc / cm ² / s
Measurement range: SENSE L (low)
Sample size: 50mm x 50mm
・ Measurement condition 2 (Ventilation resistance 2)
Piston speed: 2 cm / s
Ventilation rate: 4cc / cm ² / s
Measurement range: SENSE M (medium) or H (high)
Sample size: 50mm x 50mm

[Example 1]
As an electrode substrate for cathode electrolysis, an electrolytic nickel foil having a gauge thickness of 16 μm was prepared. One surface of the nickel foil was roughened by electrolytic nickel plating. The arithmetic average roughness Ra of the roughened surface was 0.71 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted.
This nickel foil was punched into a circular hole to form a porous foil. The open area ratio was 49%.

A coating solution for forming an electrode catalyst was prepared by the following procedure. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) having a ruthenium concentration of 100 g / L and cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of ruthenium element to cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode coating solution.
A bat containing the coating solution was placed at the bottom of the roll coating apparatus. A coating roll in which a closed-cell type foamed EPDM (ethylene propylene diene rubber) rubber (INOAC Corporation, E-4088, thickness 10 mm) is wound around a PVC (polyvinyl chloride) tube always comes in contact with the coating liquid. Installed. A coating roll around which the same EPDM was wound was installed on the top, and a roller made of PVC was further installed thereon. The coating liquid was applied through the electrode substrate between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying at 50 ° C. for 10 minutes, preliminary firing at 150 ° C. for 3 minutes, and firing at 350 ° C. for 10 minutes were performed. A series of operations of coating, drying, pre-baking, and baking was repeated until a predetermined coating amount was reached. The thickness of the electrode produced in Example 1 was 24 μm. The thickness of the catalyst layer was 8 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode. A coating was also formed on the non-roughened surface. The total thickness of ruthenium oxide and cerium oxide.
Table 2 shows the measurement results of the adhesive strength of the electrodes produced by the above method. Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0028 (kPa · s / m).

The electrode produced by the above method was cut into a size of 95 mm length and 110 mm width for electrolytic evaluation. The roughened surface of the electrode is made to face the center position on the carboxylic acid layer side of the ion exchange membrane A (size: 160 mm × 160 mm) prepared in [Method (i)] equilibrated with 0.1N NaOH aqueous solution. The solution was brought into close contact with the surface tension of the aqueous solution.
Even if you hang the membrane integrated electrode so that it is parallel to the ground with the four corners of the membrane part of the membrane integrated electrode where the membrane and electrode are integrated, I never did. Further, even when the both ends of one side were pinched and the membrane-integrated electrode was suspended so as to be perpendicular to the ground, the electrode was not peeled off or shifted.
The membrane integrated electrode was sandwiched between the anode cell and the cathode cell so that the surface on which the electrode was attached was on the cathode chamber side. The cross-sectional structure forms a zero gap structure in the order of the current collector, mattress, nickel mesh power feeder, electrode, film, and anode from the cathode chamber side.
Electrolysis evaluation was performed about the obtained electrode. The results are shown in Table 2.
It showed low voltage, high current efficiency and low caustic concentration. The handling property was also “1”. The film damage evaluation was also “0”.
Further, when the coating amount after electrolysis was measured by XRF (fluorescence X-ray analysis), almost 100% of the coating remained on the roughened surface, and the coating on the non-roughened surface decreased. This indicates that the surface facing the membrane (roughened surface) contributes to electrolysis, and the opposite surface not facing the membrane can exhibit good electrolytic performance even if there is little or no coating. ing.

[Example 2]
In Example 2, an electrolytic nickel foil having a gauge thickness of 22 μm was used as an electrode substrate for cathodic electrolysis. One surface of the nickel foil was roughened by electrolytic nickel plating. The arithmetic average roughness Ra of the roughened surface was 0.96 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. The open area ratio was 44%. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 29 μm. The thickness of the catalyst layer was 7 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode. A coating was also formed on the non-roughened surface.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0033 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.
Further, when the coating amount after electrolysis was measured by XRF, almost 100% of the coating remained on the roughened surface, and the coating on the non-roughened surface decreased. This indicates that the surface facing the membrane (roughened surface) contributes to electrolysis, and the opposite surface not facing the membrane can exhibit good electrolytic performance even if there is little or no coating. ing.

[Example 3]
In Example 3, an electrolytic nickel foil having a gauge thickness of 30 μm was used as an electrode substrate for cathodic electrolysis. One surface of the nickel foil was roughened by electrolytic nickel plating. The arithmetic average roughness Ra of the roughened surface was 1.38 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. The open area ratio was 44%. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 38 μm. The thickness of the catalyst layer was 8 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode. A coating was also formed on the non-roughened surface.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0027 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.
Further, when the coating amount after electrolysis was measured by XRF, almost 100% of the coating remained on the roughened surface, and the coating on the non-roughened surface decreased. This indicates that the surface facing the membrane (roughened surface) contributes to electrolysis, and the opposite surface not facing the membrane can exhibit good electrolytic performance even if there is little or no coating. ing.

[Example 4]
In Example 4, an electrolytic nickel foil having a gauge thickness of 16 μm was used as an electrode substrate for cathodic electrolysis. One side of this nickel foil was subjected to a roughening treatment by electrolytic nickel plating. The arithmetic average roughness Ra of the roughened surface was 0.71 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. The open area ratio was 75%. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 24 μm. The thickness of the catalyst layer was 8 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0023 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.
Further, when the coating amount after electrolysis was measured by XRF, almost 100% of the coating remained on the roughened surface, and the coating on the non-roughened surface decreased. This indicates that the surface facing the membrane (roughened surface) contributes to electrolysis, and the opposite surface not facing the membrane can exhibit good electrolytic performance even if there is little or no coating. ing.

[Example 5]
In Example 5, an electrolytic nickel foil having a gauge thickness of 20 μm was prepared as an electrode substrate for cathodic electrolysis. Both surfaces of this nickel foil were roughened by electrolytic nickel plating. The arithmetic average roughness Ra of the roughened surface was 0.96 μm. Both sides had the same roughness. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. The open area ratio was 49%. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 30 μm. The thickness of the catalyst layer was 10 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode. A coating was also formed on the non-roughened surface.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0023 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.
Further, when the coating amount after electrolysis was measured by XRF, almost 100% coating remained on both sides. When considered in comparison with Examples 1 to 4, the opposite surface not facing the membrane indicates that it can exhibit good electrolysis performance even when there is little or no coating.

[Example 6]
In Example 6, the evaluation was performed in the same manner as in Example 1 except that the coating to the electrode substrate for cathodic electrolysis was performed by ion plating, and the results are shown in Table 2. The ion plating was performed using a Ru metal target at a heating temperature of 200 ° C. and an argon / oxygen atmosphere at a film forming pressure of 7 × 10 ⁻² Pa. The coating formed was ruthenium oxide.
The electrode thickness was 26 μm. The thickness of the catalyst layer was 10 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0028 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 7]
In Example 7, an electrode base material for cathode electrolysis was prepared by an electroforming method. The shape of the photomask was a shape in which squares of 0.485 mm × 0.485 mm were arranged vertically and horizontally at intervals of 0.15 mm. By performing exposure, development, and electroplating in order, a nickel porous foil having a gauge thickness of 20 μm and a porosity of 56% was obtained. The arithmetic average roughness Ra of the surface was 0.71 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 37 μm. The thickness of the catalyst layer was 17 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0032 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 8]
Example 8 was prepared by an electroforming method as an electrode substrate for cathodic electrolysis, and had a gauge thickness of 50 μm and an aperture ratio of 56%. The arithmetic average roughness Ra of the surface was 0.73 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 60 μm. The thickness of the catalyst layer was 10 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0032 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 9]
In Example 9, a nickel nonwoven fabric (manufactured by Nikko Techno Co., Ltd.) having a gauge thickness of 150 μm and a porosity of 76% was used as an electrode substrate for cathodic electrolysis. The nonwoven fabric had a nickel fiber diameter of about 40 μm and a basis weight of 300 g / m ² . Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 165 μm. The thickness of the catalyst layer was 15 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 29 mm, and it did not return to the original flat state. Then, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastically deformed, it was possible to contact the diaphragm with a small force, and it was confirmed that this electrode has good handling properties.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0612 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handleability was “2”, and it could be judged that handling as a large laminate was possible. The film damage evaluation was “0” and good.

[Example 10]
In Example 10, a nickel nonwoven fabric (manufactured by Nikko Techno Co., Ltd.) having a gauge thickness of 200 μm and a porosity of 72% was used as an electrode substrate for cathodic electrolysis. The nonwoven fabric had a nickel fiber diameter of about 40 μm and a basis weight of 500 g / m ² . Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 215 μm. The thickness of the catalyst layer was 15 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 40 mm, and it did not return to the original flat state. Then, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastically deformed, it was possible to contact the diaphragm with a small force, and it was confirmed that this electrode has good handling properties.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0164 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handleability is “2”, and it can be determined that the large laminate can be handled. The film damage evaluation was “0” and good.

[Example 11]
In Example 11, nickel foam (manufactured by Mitsubishi Materials Corporation) having a gauge thickness of 200 μm and a porosity of 72% was used as an electrode substrate for cathodic electrolysis. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 210 μm. The thickness of the catalyst layer was 10 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When the deformation test of the electrode was performed, the average value of L ₁ and L ₂ was 17 mm, and it did not return to the original flat state. Then, when the softness after plastic deformation was evaluated, the electrode followed the diaphragm by surface tension. From this, even if plastically deformed, it was possible to contact the diaphragm with a small force, and it was confirmed that this electrode has good handling properties.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0402 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handleability is “2”, and it can be determined that the large laminate can be handled. The film damage evaluation was “0” and good.

[Example 12]
In Example 12, a nickel mesh having a wire diameter of 50 μm, 200 mesh, a gauge thickness of 100 μm, and a porosity of 37% was used as the electrode base material for cathodic electrolysis. Blasting was performed with alumina with grain number 320. Even when the blast treatment was performed, the hole area ratio did not change. Since it is difficult to measure the surface roughness of the wire mesh, in Example 12, a nickel plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The arithmetic average roughness Ra of one wire mesh was 0.64 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 110 μm. The thickness of the catalyst layer was 10 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0.5 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0154 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 13]
In Example 13, a nickel mesh having a wire diameter of 65 μm, 150 mesh, a gauge thickness of 130 μm, and a porosity of 38% was used as an electrode substrate for cathodic electrolysis. Blasting was performed with alumina with grain number 320. Even when the blast treatment was performed, the hole area ratio did not change. Since it is difficult to measure the surface roughness of the wire mesh, in Example 13, a nickel plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The arithmetic average roughness Ra was 0.66 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Otherwise, the same evaluation as in Example 1 was performed, and the results are shown in Table 2.
The electrode thickness was 133 μm. The thickness of the catalyst layer was 3 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 6.5 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0124 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handleability is “2”, and it can be determined that the large laminate can be handled. The film damage evaluation was also “0”.

[Example 14]
In Example 14, the same substrate as that of Example 3 (gauge thickness: 30 μm, porosity: 44%) was used as the electrode substrate for cathodic electrolysis. Electrolytic evaluation was performed with the same configuration as Example 1 except that no nickel mesh power feeder was installed. That is, the cross-sectional structure of the cell forms a zero gap structure in the order of the current collector, mattress, membrane integrated electrode, and anode from the cathode chamber side, and the mattress functions as a power feeder. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0027 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 15]
In Example 15, the same base material as that of Example 3 (gauge thickness: 30 μm, porosity: 44%) was used as the electrode base material for cathodic electrolysis. Instead of the nickel mesh power supply, the cathode used in Reference Example 1 with deteriorated and increased electrolytic voltage was installed. Otherwise, the electrolytic evaluation was performed in the same configuration as in Example 1. That is, the cross-sectional structure of the cell is from the cathode chamber side in the order of current collector, mattress, degraded cathode (which functions as a power feeder), electrode for electrolysis (cathode), diaphragm, and anode. A zero gap structure is formed side by side, and a cathode that has deteriorated and has an increased electrolysis voltage functions as a power feeder. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0027 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 16]
A titanium foil having a gauge thickness of 20 μm was prepared as an electrode substrate for anodic electrolysis. A roughening treatment was performed on both sides of the titanium foil. This titanium foil was punched to make a circular hole to obtain a porous foil. The hole diameter was 1 mm and the hole area ratio was 14%. The arithmetic average roughness Ra of the surface was 0.37 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted.
A coating solution for forming an electrode catalyst was prepared by the following procedure. Ruthenium chloride solution (Tanaka Kikinzoku Kogyo Co., Ltd.) with a ruthenium concentration of 100 g / L, iridium chloride (Tanaka Kikinzoku Kogyo Co., Ltd.), titanium tetrachloride (Wako Pure Chemical Industries, Ltd.) with an iridium concentration of 100 g / L, ruthenium element The iridium element and the titanium element were mixed at a molar ratio of 0.25: 0.25: 0.5. This mixed solution was sufficiently stirred and used as an anode coating solution.

A bat containing the coating solution was placed at the bottom of the roll coating apparatus. A coating roll in which a closed-cell type foamed EPDM (ethylene propylene diene rubber) rubber (INOAC Corporation, E-4088, thickness 10 mm) is wound around a PVC (polyvinyl chloride) tube always comes in contact with the coating liquid. Installed. A coating roll around which the same EPDM was wound was installed on the top, and a roller made of PVC was further installed thereon. The coating liquid was applied through the electrode substrate between the second coating roll and the uppermost PVC roller (roll coating method). After the coating liquid was applied to the titanium porous foil, drying at 60 ° C. for 10 minutes and baking at 475 ° C. for 10 minutes were performed. After repeating the series of operations of coating, drying, pre-baking, and baking, baking was performed at 520 ° C. for 1 hour.
The electrode produced by the above method was cut into a size of 95 mm length and 110 mm width for electrolytic evaluation. The ion exchange membrane A (size: 160 mm × 160 mm) prepared in [Method (i)] equilibrated with a 0.1N NaOH aqueous solution was brought into close contact with the substantially central position on the sulfonic acid layer side by the surface tension of the aqueous solution.

The cathode was prepared by the following procedure. First, a nickel wire mesh having a wire diameter of 150 μm and 40 mesh was prepared as a base material. Blasting with alumina was carried out as a pretreatment, followed by immersion in 6N hydrochloric acid for 5 minutes, sufficient washing with pure water, and drying.
Next, a ruthenium chloride solution with a ruthenium concentration of 100 g / L (Tanaka Kikinzoku Kogyo Co., Ltd.) and cerium chloride (Kishida Chemical Co., Ltd.) are mixed so that the molar ratio of ruthenium element to cerium element is 1: 0.25. did. This mixed solution was sufficiently stirred and used as a cathode coating solution.
A bat containing the coating solution was placed at the bottom of the roll coating apparatus. A coating roll in which a closed-cell type foamed EPDM (ethylene propylene diene rubber) rubber (INOAC Corporation, E-4088, thickness 10 mm) is wound around a PVC (polyvinyl chloride) tube always comes in contact with the coating liquid. Installed. A coating roll around which the same EPDM was wound was installed on the top, and a roller made of PVC was further installed thereon. The coating liquid was applied through the electrode substrate between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying at 50 ° C. for 10 minutes, preliminary firing at 300 ° C. for 3 minutes, and firing at 550 ° C. for 10 minutes were performed. Thereafter, baking was performed at 550 ° C. for 1 hour. A series of operations of coating, drying, pre-baking, and baking was repeated.

As the current collector for the cathode chamber, nickel expanded metal was used. The size of the current collector was 95 mm long × 110 mm wide. As the metal elastic body, a mattress knitted with a nickel fine wire was used. A mattress, which is a metal elastic body, was placed on the current collector. The cathode prepared by the above method was placed thereon, and the four corners of the mesh were fixed to the current collector with strings made of Teflon (registered trademark).
Even if you hang the membrane integrated electrode parallel to the ground with the four corners of the membrane part of the membrane integrated electrode where the membrane and anode are integrated and the electrode is on the ground side, the electrode will be peeled off or displaced I never did. Further, even when the both ends of one side were pinched and the membrane-integrated electrode was suspended so as to be perpendicular to the ground, the electrode was not peeled off or shifted.

  In the anode cell, the anode used in Reference Example 3 whose electrolytic voltage was deteriorated and was increased was fixed by welding, and the above-mentioned membrane-integrated electrode was attached to the anode chamber so that the surface on which the electrode was adhered was on the anode chamber side. And the cathode cell. That is, the cross-sectional structure of the cell is arranged in the order from the cathode chamber side to the current collector, mattress, cathode, diaphragm, electrode for electrolysis (titanium porous foil anode), and anode having deteriorated electrolysis voltage and zero gap A structure was formed. The anode whose electrolytic voltage became high due to deterioration functioned as a power feeder. It should be noted that the titanium porous foil anode and the anode whose electrolytic voltage was increased due to deterioration were only in physical contact and were not fixed by welding.

With this configuration, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2.
The electrode thickness was 26 μm. The thickness of the catalyst layer was 6 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 4 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0060 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 17]
In Example 17, a titanium foil having a gauge thickness of 20 μm and a porosity of 30% was used as an electrode substrate for anodic electrolysis. The arithmetic average roughness Ra of the surface was 0.37 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that, evaluation was implemented similarly to Example 16, and the result was shown in Table 2.
The electrode thickness was 30 μm. The thickness of the catalyst layer was 10 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 5 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0030 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 18]
In Example 18, a titanium foil having a gauge thickness of 20 μm and a porosity of 42% was used as an electrode substrate for anodic electrolysis. The arithmetic average roughness Ra of the surface was 0.38 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that, evaluation was implemented similarly to Example 16, and the result was shown in Table 2.
The electrode thickness was 32 μm. The thickness of the catalyst layer was 12 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 2.5 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0022 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 19]
In Example 19, a titanium foil having a gauge thickness of 50 μm and a porosity of 47% was used as an electrode substrate for anodic electrolysis. The arithmetic average roughness Ra of the surface was 0.40 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that, evaluation was implemented similarly to Example 16, and the result was shown in Table 2.
The electrode thickness was 69 μm. The thickness of the catalyst layer was 19 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 8 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0024 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 20]
In Example 20, a titanium nonwoven fabric having a gauge thickness of 100 μm, a titanium fiber diameter of about 20 μm, a basis weight of 100 g / m ² , and a porosity of 78% was used as an electrode substrate for anodic electrolysis. Other than that, evaluation was implemented similarly to Example 16, and the result was shown in Table 2.
The electrode thickness was 114 μm. The thickness of the catalyst layer was 14 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 2 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0228 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

[Example 21]
In Example 21, a titanium wire net having a gauge thickness of 120 μm, a titanium fiber diameter of about 60 μm, and 150 mesh was used as an electrode substrate for anodic electrolysis. The open area ratio was 42%. Blasting was performed with alumina with grain number 320. Since it is difficult to measure the roughness of the wire mesh surface, in Example 21, a titanium plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the titanium plate was made the surface roughness of the wire mesh. The arithmetic average roughness Ra was 0.60 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that, evaluation was implemented similarly to Example 16, and the result was shown in Table 2.
The electrode thickness was 140 μm. The thickness of the catalyst layer was 20 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
Adequate adhesion was observed.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 10 mm. It was found that the electrode has a wide elastic deformation region.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0132 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation was also “0”.

  [Example 22]

In Example 22, as in the case of Example 16, the anode having deteriorated and the electrolytic voltage was increased was used as the anode power supply, and the same titanium non-woven fabric as in Example 20 was used as the anode. In the same manner as in Example 15, a cathode whose electrolytic voltage was increased due to deterioration was used as the cathode power supply, and the same nickel foil electrode as in Example 3 was used as the cathode. The cross-sectional structure of the cell is as follows: from the cathode chamber side, current collector, mattress, cathode with deteriorated voltage, nickel porous foil cathode, diaphragm, titanium non-woven anode, anode with deteriorated electrolysis voltage A zero gap structure is formed side by side, and a cathode and an anode whose electrolytic voltage is increased due to deterioration function as a power feeder. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The thickness of the electrode (anode) was 114 μm, and the thickness of the catalyst layer was 14 μm by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode (anode). The thickness of the electrode (cathode) was 38 μm, and the thickness of the catalyst layer was 8 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode (cathode).
Adequate adhesion was observed for both the anode and cathode.
When the deformation test of the electrode (anode) was carried out, the average value of L ₁ and L ₂ was 2 mm. When the deformation test of the electrode (cathode) was performed, the average value of L ₁ and L ₂ was 0 mm.
When the ventilation resistance of the electrode (anode) was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0228 (kPa · s / m). When the ventilation resistance of the electrode (cathode) was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0027 (kPa · s / m).
Moreover, low voltage, high current efficiency, and low sodium hydroxide concentration were shown. The handling property was also “1”. The film damage evaluation for both the anode and the cathode was also “0”. In Example 22, the membrane damage was evaluated by combining a cathode on one side of the diaphragm and an anode on the opposite side, and combining the cathode and anode.

[Example 23]
In Example 23, a microporous membrane “Zirfon Perl UTP 500” manufactured by Agfa was used.
The Zirfon membrane was immersed in pure water for 12 hours or more and then used for the test. Otherwise, the above evaluation was performed in the same manner as in Example 3, and the results are shown in Table 2.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm. It was found that the electrode has a wide elastic deformation region.
As in the case of using the ion exchange membrane as a diaphragm, a sufficient adhesive force was observed, the microporous membrane and the electrode were brought into close contact with each other by the surface tension, and the handling property was “1”.

[Example 24]
As an electrode base material for cathode electrolysis, a carbon cloth woven with carbon fibers having a gauge thickness of 566 μm was prepared. A coating solution for forming an electrode catalyst on the carbon cloth was prepared by the following procedure. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) having a ruthenium concentration of 100 g / L and cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of ruthenium element to cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode coating solution.
A bat containing the coating solution was placed at the bottom of the roll coating apparatus. A coating roll in which a closed cell type foamed EPDM (ethylene propylene diene rubber) rubber (INOAC Corporation, E-4088 (trade name), thickness 10 mm) is wound around a PVC (polyvinyl chloride) tube, It was installed so that the coating solution was always in contact. A coating roll around which the same EPDM was wound was placed on the top, and a PVC roller was placed thereon. The coating liquid was applied through the electrode substrate between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying at 50 ° C. for 10 minutes, preliminary firing at 150 ° C. for 3 minutes, and firing at 350 ° C. for 10 minutes were performed. A series of operations of coating, drying, pre-baking, and baking was repeated until a predetermined coating amount was reached. The thickness of the produced electrode was 570 μm. The thickness of the catalyst layer was 4 μm by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode. The thickness of the catalyst layer was the total thickness of ruthenium oxide and cerium oxide.

Electrolysis evaluation was performed about the obtained electrode. The results are shown in Table 2.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 0 mm.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.19 (kPa · s / m), and the measurement condition 2 was 0.176 (kPa · s / m).
Moreover, handling property was "2" and it was judged that it could be handled as a large laminate.
The voltage was high, the film damage evaluation was “1”, and film damage was confirmed. This was considered to be because NaOH generated in the electrode stayed at the interface between the electrode and the diaphragm due to the high ventilation resistance of the electrode of Example 24, resulting in a high concentration.

[Reference Example 1]
In Reference Example 1, a cathode that was used in a large electrolytic cell for 8 years as a cathode and deteriorated to increase the electrolysis voltage was used. The cathode was placed in place of the nickel mesh feeder on the mattress in the cathode chamber, and electrolytic evaluation was carried out with the ion exchange membrane A prepared by [Method (i)] interposed therebetween. In Reference Example 1, no membrane-integrated electrode is used, and the cross-sectional structure of the cell is from the cathode chamber side to the current collector, the mattress, the cathode whose ionization voltage has been increased due to deterioration, the ion exchange membrane A, and the anode. A zero gap structure was formed.
As a result of conducting electrolytic evaluation with this configuration, the voltage was 3.04 V, the current efficiency was 97.0%, and the sodium chloride concentration (50% equivalent value) in caustic soda was 20 ppm. High voltage due to cathode deterioration

[Reference Example 2]
In Reference Example 2, a nickel mesh power feeder was used as the cathode. That is, electrolysis was performed with a nickel mesh that was not coated with a catalyst.
A nickel mesh cathode was placed on the mattress in the cathode chamber, and electrolytic evaluation was performed with the ion exchange membrane A prepared by [Method (i)] interposed therebetween. The cross-sectional structure of the electric cell of Reference Example 2 was arranged in the order of current collector, mattress, nickel mesh, ion exchange membrane A, and anode from the cathode chamber side to form a zero gap structure.
As a result of conducting the electrolytic evaluation with this configuration, the voltage was 3.38 V, the current efficiency was 97.7%, and the sodium chloride concentration in sodium hydroxide (converted to 50%) was 24 ppm. The voltage was high because the cathode catalyst was not coated.

[Reference Example 3]
In Reference Example 3, an anode that was used in a large electrolytic cell for about 8 years as an anode and deteriorated to increase the electrolysis voltage was used.
The cross-sectional structure of the electrolytic cell of Reference Example 3 is as follows: from the cathode chamber side, current collector, mattress, cathode, ion exchange membrane A prepared by [Method (i)], and anode having deteriorated and increased electrolysis voltage A zero gap structure was formed.
As a result of conducting electrolytic evaluation with this configuration, the voltage was 3.18 V, the current efficiency was 97.0%, and the sodium chloride concentration (50% equivalent value) in caustic soda was 22 ppm. Since the anode was deteriorated, the voltage was high.

[Example 25]
In Example 25, nickel expanded metal having a gauge thickness of 100 μm after full roll processing and an open area ratio of 33% was used as the electrode base material for cathode electrolysis. Blasting was performed with alumina with grain number 320. Even after the blast treatment, the hole area ratio did not change. Since it is difficult to measure the surface roughness of the expanded metal, in Example 25, a nickel plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the nickel plate was made the surface roughness of the wire mesh. The arithmetic average roughness Ra was 0.68 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 114 μm. The thickness of the catalyst layer was 14 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
The mass per unit area was 67.5 (mg / cm ² ). The force per unit mass / unit area (1) was as small as 0.05 (N / mg · cm ² ). For this reason, the result of the 280 mm diameter cylindrical winding evaluation (2) was 64% and the result of the 145 mm diameter cylindrical winding evaluation (3) was 22%, and there were many portions where the electrode and the diaphragm were peeled off. This has the problem that when the membrane-integrated electrode is handled, the electrode is easily peeled off, and the electrode is peeled off from the membrane during handling. There was also a problem with handling performance of “4”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 13 mm.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0168 (kPa · s / m).

[Example 26]
In Example 26, a nickel expanded metal having a gauge thickness of 100 μm and a porosity of 16% after full roll processing was used as an electrode substrate for cathodic electrolysis. Blasting was performed with alumina with grain number 320. Even after the blast treatment, the hole area ratio did not change. Since it is difficult to measure the surface roughness of the expanded metal, in Example 26, a nickel plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the nickel plate was set to the surface roughness of the wire mesh. The arithmetic average roughness Ra was 0.64 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 107 μm. The thickness of the catalyst layer was 7 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
The mass per unit area was 78.1 (mg / cm ² ). The force (1) applied per unit mass / unit area was as small as 0.04 (N / mg · cm ² ). For this reason, the result of the 280 mm diameter cylindrical winding evaluation (2) was 37%, and the result of the 145 mm diameter cylindrical winding evaluation (3) was 25%, and there were many portions where the electrode and the diaphragm were peeled off. This has the problem that when the membrane-integrated electrode is handled, the electrode is easily peeled off, and the electrode is peeled off from the membrane during handling. There was also a problem with handling performance of “4”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 18.5 mm. When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0176 (kPa · s / m).

[Example 27]
In Example 27, a nickel expanded metal having a gauge thickness after full roll processing of 100 μm and an open area ratio of 40% was used as an electrode substrate for cathodic electrolysis. Blasting was performed with alumina with grain number 320. Even after the blast treatment, the hole area ratio did not change. Since it is difficult to measure the surface roughness of the expanded metal, in Example 27, a nickel plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The arithmetic average roughness Ra was 0.70 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. The electrode substrate for electrolysis was coated by the same ion plating as in Example 6. Other than that was evaluated similarly to Example 1, and the result was shown in Table 2.
The electrode thickness was 110 μm. The thickness of the catalyst layer was 10 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
The force (1) applied per unit mass / unit area was as small as 0.07 (N / mg · cm ² ). For this reason, the result of the 280 mm diameter cylindrical winding evaluation (2) was 80%, and the result of the 145 mm diameter cylindrical winding evaluation (3) was 32%, and the portion where the electrode and the diaphragm were peeled off increased. This has the problem that when the membrane-integrated electrode is handled, the electrode is easily peeled off, and the electrode is peeled off from the membrane during handling. There was also a problem with handling performance of “3”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 11 mm.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0030 (kPa · s / m).

[Example 28]
In Example 28, a nickel expanded metal having a gauge thickness after full roll processing of 100 μm and an open area ratio of 58% was used as an electrode substrate for cathodic electrolysis. Blasting was performed with alumina with grain number 320. Even after the blast treatment, the hole area ratio did not change. Since it is difficult to measure the surface roughness of the expanded metal, in Example 28, a nickel plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. The arithmetic average roughness Ra was 0.64 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that, evaluation was performed similarly to Example 1, and the results are shown in Table 2.
The electrode thickness was 109 μm. The thickness of the catalyst layer was 9 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
The force (1) applied per unit mass / unit area was as small as 0.06 (N / mg · cm ² ). For this reason, the result of the 280 mm diameter cylindrical winding evaluation (2) was 69%, and the result of the 145 mm diameter cylindrical winding evaluation (3) was 39%, and there were many portions where the electrode and the diaphragm were peeled off. This has the problem that when the membrane-integrated electrode is handled, the electrode is easily peeled off, and the electrode is peeled off from the membrane during handling. There was also a problem with handling performance of “3”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 11.5 mm.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0028 (kPa · s / m).

[Example 29]
In Example 29, a nickel wire mesh having a gauge thickness of 300 μm and a hole area ratio of 56% was used as an electrode substrate for cathodic electrolysis. Since it is difficult to measure the surface roughness of the wire mesh, in Example 29, a nickel plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the nickel plate was taken as the surface roughness of the wire mesh. Blasting was performed with alumina with grain number 320. Even after the blast treatment, the hole area ratio did not change. The arithmetic average roughness Ra was 0.64 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that, evaluation was performed similarly to Example 1, and the results are shown in Table 2.
The electrode thickness was 308 μm. The thickness of the catalyst layer was 8 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
The mass per unit area was 49.2 (mg / cm ² ). For this reason, the result of the 280 mm diameter cylindrical winding evaluation (2) was 88%, and the result of the 145 mm diameter cylindrical winding evaluation (3) was 42%, and the portions where the electrode and the diaphragm were peeled off increased. This is because when the membrane integrated electrode is handled, the electrode is likely to be peeled off, and the electrode is peeled off from the membrane during handling, and the handling property has a problem of “3”. Actually operating with a large size, it was possible to evaluate as “3”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 23 mm.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0034 (kPa · s / m).

[Example 30]
In Example 30, a nickel wire mesh having a gauge thickness of 200 μm and a porosity of 37% was used as the electrode base material for cathode electrolysis. Blasting was performed with alumina with grain number 320. Even after the blast treatment, the hole area ratio did not change. Since it is difficult to measure the surface roughness of the metal mesh, in Example 30, a nickel plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the nickel plate was taken as the surface roughness of the metal mesh. The arithmetic average roughness Ra was 0.65 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that carried out similarly to Example 1, electrode electrolysis evaluation, the measurement result of adhesive force, and adhesiveness were implemented. The results are shown in Table 2.
The electrode thickness was 210 μm. The thickness of the catalyst layer was 10 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
The mass per unit area was 56.4 mg / cm ² . For this reason, the result of the 145 mm diameter cylindrical winding evaluation method (3) was 63%, indicating that the adhesion between the electrode and the diaphragm was poor. This is because when the membrane integrated electrode is handled, the electrode is likely to be peeled off, and the electrode is peeled off from the membrane during handling, and the handling property has a problem of “3”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 19 mm.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0096 (kPa · s / m).

[Example 31]
In Example 31, a titanium expanded metal having a gauge thickness of 500 μm after full roll processing and a porosity of 17% was used as the electrode substrate for anodic electrolysis. Blasting was performed with alumina with grain number 320. Even after the blast treatment, the hole area ratio did not change. Since it is difficult to measure the surface roughness of the expanded metal, in Example 31, a titanium plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the titanium plate was set to the surface roughness of the wire mesh. The arithmetic average roughness Ra was 0.60 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that, evaluation was implemented similarly to Example 16, and the result was shown in Table 2.
The electrode thickness was 508 μm. The thickness of the catalyst layer was 8 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
The mass per unit area was 152.5 (mg / cm ² ). The force (1) applied per unit mass / unit area was as small as 0.01 (N / mg · cm ² ). For this reason, the result of the 280 mm diameter cylindrical winding evaluation (2) was less than 5%, and the result of the 145 mm diameter cylindrical winding evaluation (3) was less than 5%, and there were many portions where the electrode and the diaphragm were peeled off. This is because when the membrane integrated electrode is handled, the electrode is easily peeled off, and the electrode is peeled off from the membrane during handling. There was also a problem with handling performance of “4”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the electrode did not return to the shape of the PVC pipe, and the values of L ₁ and L ₂ could not be measured.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0072 (kPa · s / m).

[Example 32]
In Example 32, a titanium expanded metal having a gauge thickness of 800 μm after full roll processing and an open area ratio of 8% was used as the electrode substrate for anodic electrolysis. Blasting was performed with alumina with grain number 320. Even after the blast treatment, the hole area ratio did not change. Since it is difficult to measure the surface roughness of the expanded metal, in Example 32, a titanium plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the titanium plate was set to the surface roughness of the wire mesh. The arithmetic average roughness Ra was 0.61 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that was carried out similarly to Example 16, and the result was shown in Table 2.
The electrode thickness was 808 μm. The thickness of the catalyst layer was 8 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
The mass per unit area was 251.3 (mg / cm ² ). The force (1) applied per unit mass / unit area was as small as 0.01 (N / mg · cm ² ). For this reason, the result of the 280 mm diameter cylindrical winding evaluation (2) was less than 5%, and the result of the 145 mm diameter cylindrical winding evaluation (3) was less than 5%, and there were many portions where the electrode and the diaphragm were peeled off. This is because when the membrane integrated electrode is handled, the electrode is easily peeled off, and the electrode is peeled off from the membrane during handling. There was also a problem with handling performance of “4”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the electrode did not return to the shape of the PVC pipe, and the values of L ₁ and L ₂ could not be measured.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0172 (kPa · s / m).

[Example 33]
In Example 33, a titanium expanded metal having a gauge thickness of 1000 μm after full roll processing and an open area ratio of 46% was used as the electrode substrate for anodic electrolysis. Blasting was performed with alumina with grain number 320. Even after the blast treatment, the hole area ratio did not change. Since it is difficult to measure the surface roughness of the expanded metal, in Example 33, a titanium plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the titanium plate was set to the surface roughness of the wire mesh. The arithmetic average roughness Ra was 0.59 μm. The surface roughness was measured under the same conditions as the surface roughness measurement of the nickel plate that had been blasted. Other than that was carried out similarly to Example 16, and the result was shown in Table 2.
The electrode thickness was 1011 μm. The thickness of the catalyst layer was 11 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
The mass per unit area was 245.5 (mg / cm ² ). The force (1) applied per unit mass / unit area was as small as 0.01 (N / mg · cm ² ). For this reason, the result of the 280 mm diameter cylindrical winding evaluation (2) was less than 5%, and the result of the 145 mm diameter cylindrical winding evaluation (3) was less than 5%, and there were many portions where the electrode and the diaphragm were peeled off. This is because when the membrane integrated electrode is handled, the electrode is easily peeled off, and the electrode is peeled off from the membrane during handling. There was also a problem with handling performance of “4”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the electrode did not return to the shape of the PVC pipe, and the values of L ₁ and L ₂ could not be measured.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0027 (kPa · s / m).

[Example 34]
A nickel wire having a gauge thickness of 150 μm was prepared as an electrode substrate for cathode electrolysis. A surface roughening treatment was performed using the nickel wire. Since it is difficult to measure the surface roughness of the nickel wire, in Example 34, a nickel plate having a thickness of 1 mm was simultaneously blasted during blasting, and the surface roughness of the nickel plate was made the surface roughness of the nickel wire. Blasting was performed with alumina with grain number 320. The arithmetic average roughness Ra was 0.64 μm.
A coating solution for forming an electrode catalyst was prepared by the following procedure. A ruthenium nitrate solution (Furuya Metal Co., Ltd.) having a ruthenium concentration of 100 g / L and cerium nitrate (Kishida Chemical Co., Ltd.) were mixed so that the molar ratio of ruthenium element to cerium element was 1: 0.25. This mixed solution was sufficiently stirred and used as a cathode coating solution.
A bat containing the coating solution was placed at the bottom of the roll coating apparatus. A coating roll in which a closed cell type foamed EPDM (ethylene propylene diene rubber) rubber (INOAC Corporation, E-4088 (trade name), thickness 10 mm) is wound around a PVC (polyvinyl chloride) tube, It was installed so that the coating solution was always in contact. A coating roll around which the same EPDM was wound was placed on the top, and a PVC roller was placed thereon. The coating liquid was applied through the electrode substrate between the second coating roll and the uppermost PVC roller (roll coating method). Thereafter, drying at 50 ° C. for 10 minutes, preliminary firing at 150 ° C. for 3 minutes, and firing at 350 ° C. for 10 minutes were performed. A series of operations of coating, drying, pre-baking, and baking was repeated until a predetermined coating amount was reached. The thickness of one nickel wire produced in Example 34 was 158 μm.

The nickel wire produced by the above method was cut into lengths of 110 mm and 95 mm. As shown in FIG. 16, a 110 mm nickel wire and a 95 mm nickel wire are placed so as to vertically overlap each other at the center of each nickel wire, and the intersection portion is instant adhesive (Aron Alpha (registered trademark), Toa Gosei Co., Ltd.) The electrode was produced by bonding with The electrode was evaluated and the results are shown in Table 2.
The electrode was thickest at the portion where the nickel wires overlapped, and the electrode thickness was 306 μm. The thickness of the catalyst layer was 6 μm. The open area ratio was 99.7%.

The mass per unit area of the electrode was 0.5 (mg / cm ² ). The forces (1) and (2) applied per unit mass / unit area were both below the measurement lower limit of the tensile tester. For this reason, the result of 280 mm diameter cylindrical winding evaluation (1) was less than 5%, and there were many portions where the electrode and the diaphragm were peeled off. There was also a problem with handling performance of “4”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 15 mm.
When the ventilation resistance of the electrode was measured, the measurement condition 2 was 0.001 (kPa · s / m) or less. Under measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring device was set to H (high), the ventilation resistance value was 0.0002 (kPa · s / m).
Moreover, the electrode (cathode) was installed on the Ni mesh power feeder using the structure shown in FIG. 17, and the electrolytic evaluation was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.16V.

[Example 35]
In Example 35, using the electrode produced in Example 34, as shown in FIG. 18, a 110 mm nickel wire and a 95 mm nickel wire are placed so as to overlap vertically at the center of each nickel wire, and the intersection portion Were bonded with a momentary adhesive (Aron Alpha (registered trademark), Toa Gosei Co., Ltd.) to produce an electrode. The electrode was evaluated and the results are shown in Table 2.
The electrode was thickest at the portion where the nickel wires overlapped, and the electrode thickness was 306 μm. The thickness of the catalyst layer was 6 μm. The open area ratio was 99.4%.
The mass per unit area of the electrode was 0.9 (mg / cm ² ). The forces (1) and (2) applied per unit mass / unit area were both below the measurement lower limit of the tensile tester. For this reason, the result of 280 mm diameter cylindrical winding evaluation (1) was less than 5%, and there were many portions where the electrode and the diaphragm were peeled off. There was also a problem with handling performance of “4”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 16 mm.
When the ventilation resistance of the electrode was measured, the measurement condition 2 was 0.001 (kPa · s / m) or less. Under measurement conditions 2, when the SENSE (measurement range) of the ventilation resistance measuring device was set to H (high), the ventilation resistance was 0.0004 (kPa · s / m).
Moreover, the electrode (cathode) was installed on the Ni mesh power feeding body using the structure shown in FIG. 19, and the electrolytic evaluation was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18V.

[Example 36]
In Example 36, using the electrodes produced in Example 34, as shown in FIG. 20, a 110 mm nickel wire and a 95 mm nickel wire are placed so as to overlap vertically at the center of each nickel wire, and the intersection portion Were bonded with a momentary adhesive (Aron Alpha (registered trademark), Toa Gosei Co., Ltd.) to produce an electrode. The electrode was evaluated and the results are shown in Table 2.
The electrode was thickest at the portion where the nickel wires overlapped, and the electrode thickness was 306 μm. The thickness of the catalyst layer was 6 μm. The open area ratio was 98.8%.
The mass per unit area of the electrode was 1.9 (mg / cm ² ). The forces (1) and (2) applied per unit mass / unit area were both below the measurement lower limit of the tensile tester. For this reason, the result of 280 mm diameter cylindrical winding evaluation (1) was less than 5%, and there were many portions where the electrode and the diaphragm were peeled off. There was also a problem with handling performance of “4”. The film damage evaluation was “0”.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 14 mm.
Moreover, when the ventilation resistance of the electrode was measured, the measurement condition 2 was 0.001 (kPa · s / m) or less. Under the measurement condition 2, when the SENSE (measurement range) of the ventilation resistance measuring device was set to H (high), the ventilation resistance was 0.0005 (kPa · s / m).
Moreover, the electrode (cathode) was installed on the Ni mesh power feeding body using the structure shown in FIG. 21, and electrolytic evaluation was performed by the method described in (9) Electrolytic evaluation. As a result, the voltage was as high as 3.18V.

[Comparative Example 1]
In Comparative Example 1, a thermocompression bonded assembly was produced in which an electrode was thermocompression bonded to a diaphragm with reference to a prior document (Example of JP-A-58-48686).
Nickel expanded metal having a gauge thickness of 100 μm and a porosity of 33% was used as the electrode base material for cathode electrolysis, and electrode coating was performed in the same manner as in Example 1. Then, the inactivation process was implemented in the following procedure on the single side | surface of the electrode. A polyimide adhesive tape (Chuko Kasei Co., Ltd.) is applied to one side of the electrode, and PTFE dispersion (Mitsui DuPont Fluorochemical Co., Ltd., 31-JR (trade name)) is applied to the opposite side, and the muffle furnace at 120 ° C. for 10 minutes. Dried. The polyimide tape was peeled off and the sintering treatment was carried out for 10 minutes in a muffle furnace set at 380 ° C. This operation was repeated twice to inactivate one side of the electrode.

A film formed of two layers of a perfluorocarbon polymer (C polymer) having a terminal functional group of “—COOCH ₃ ” and a perfluorocarbon polymer (S polymer) having a terminal group of “—SO ₂ F” was manufactured. The thickness of the C polymer layer was 3 mil (mil), and the thickness of the S polymer layer was 4 mil (mil). This two-layer film was subjected to saponification treatment, and ion exchange groups were introduced by hydrolysis of the ends of the polymer. The C polymer end was hydrolyzed to a carboxylic acid group, and the S polymer end was hydrolyzed to a sulfo group. The ion exchange capacity as a sulfonic acid group was 1.0 meq / g, and the ion exchange capacity as a carboxylic acid group was 0.9 meq / g.
The surface having a carboxylic acid group as an ion exchange group was opposed to the deactivated electrode surface, and hot pressing was performed to integrate the ion exchange membrane and the electrode. Even after thermocompression bonding, one surface of the electrode was exposed, and there was no portion where the electrode penetrated the film.
Thereafter, a perfluorocarbon polymer mixture into which zirconium oxide and a sulfo group were introduced was applied on both surfaces in order to suppress the adhesion of bubbles generated during electrolysis to the film. In this way, the thermocompression bonding assembly of Comparative Example 1 was manufactured.

When the force (1) applied per unit mass and unit area was measured using this thermocompression bonded body, the electrode did not move upward because the electrode and the membrane were strongly bonded by thermocompression bonding. Therefore, when the ion exchange membrane and the nickel plate were fixed so as not to move and the electrode was pulled upward with a stronger force, when a force of 1.50 (N / mg · cm ² ) was applied, part of the membrane Was torn. The force (1) per unit mass / unit area of the thermocompression bonded body of Comparative Example 1 was at least 1.50 (N / mg · cm ² ), and was strongly bonded.

When the 280 mm diameter cylindrical winding evaluation (1) was performed, the contact area with the plastic pipe was less than 5%. On the other hand, when 280 mm diameter cylindrical winding evaluation (2) was performed, the electrode and the membrane were 100% bonded, but the diaphragm was wound around the column in the first place. The result of the 145 mm diameter cylindrical winding evaluation (3) was the same. This result meant that the handling of the film was impaired by the integrated electrode, making it difficult to wind or fold the film. There was a problem with the handling property of “3”. The film damage evaluation was “0”. Moreover, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the sodium chloride concentration (50% equivalent value) in caustic soda was high, and the electrolytic performance was deteriorated.
The electrode thickness was 114 μm. The thickness of the catalyst layer was 14 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 13 mm.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0168 (kPa · s / m).

[Comparative Example 2]
In Comparative Example 2, a nickel mesh having a wire diameter of 150 μm, 40 mesh, a gauge thickness of 300 μm, and an aperture ratio of 58% was used as an electrode substrate for cathodic electrolysis. Otherwise, a thermocompression bonded assembly was produced in the same manner as in Comparative Example 1.
When the force (1) applied per unit mass and unit area was measured using this thermocompression bonded body, the electrode did not move upward because the electrode and the membrane were strongly bonded by thermocompression bonding. Therefore, when the ion exchange membrane and the nickel plate were fixed so as not to move and the electrode was pulled upward with a stronger force, when a force of 1.60 (N / mg · cm ² ) was applied, a part of the membrane was Torn. The force (1) per unit mass / unit area of the thermocompression bonding assembly of Comparative Example 2 was at least 1.60 (N / mg · cm ² ) and was strongly bonded.

Using this thermocompression bonded body, a 280 mm diameter cylindrical winding evaluation (1) was performed, and the contact area with the plastic pipe was less than 5%. On the other hand, when 280 mm diameter cylindrical winding evaluation (2) was performed, the electrode and the membrane were 100% bonded, but the diaphragm was wound around the column in the first place. The result of the 145 mm diameter cylindrical winding evaluation (3) was the same. This result meant that the handling of the film was impaired by the integrated electrode, making it difficult to wind or fold the film. There was a problem with the handling property of “3”. Moreover, when the electrolytic evaluation was carried out, the voltage was high, the current efficiency was low, the salt concentration in the caustic soda was high, and the electrolysis performance deteriorated.
The electrode thickness was 308 μm. The thickness of the catalyst layer was 8 μm obtained by subtracting the thickness of the electrode substrate for electrolysis from the thickness of the electrode.
When an electrode deformation test was performed, the average value of L ₁ and L ₂ was 23 mm.
When the ventilation resistance of the electrode was measured, the measurement condition 1 was 0.07 (kPa · s / m) or less, and the measurement condition 2 was 0.0034 (kPa · s / m).

  In Table 2, in all the samples, before the measurement of “force per unit mass / unit area (1)” and “force per unit mass / unit area (2)”, it was able to stand on its own by surface tension ( That is, it did not slip down).

DESCRIPTION OF SYMBOLS FOR FIG. 1 10 ... Electrode electrode substrate, 20 ... First layer, 30 ... Second layer, 100 ... Electrode for electrolysis.

Explanation of reference numerals for FIGS. 2 to 4 1 ... ion exchange membrane, 2 ... carboxylic acid layer, 3 ... sulfonic acid layer, 4 ... reinforced core material, 10 ... membrane body, 11a, 11b ... coating layer, 21, 22 ... reinforced core 100, electrolytic cell, 200, anode, 300, cathode, 52, reinforcing yarn, 504a, sacrificial yarn, 504, communication hole 504.

DESCRIPTION OF SYMBOLS FOR FIGS. 5-9 1 ... Electrolytic cell, 2 ... Ion exchange membrane, 4 ... Electrolytic cell, 5 ... Press, 6 ... Cathode terminal, 7 ... Anode terminal DESCRIPTION OF SYMBOLS 10 ... Anode chamber, 11 ... Anode, 12 ... Anode gasket, 13 ... Cathode gasket, 18 ... Reverse current absorber, 18a ... Base material, 18b ... Reverse current Absorbing layer, 19 ... bottom of anode chamber, 20 ... cathode chamber, 21 ... cathode, 22 ... metal elastic body, 23 ... current collector, 24 ... support, 30. ..Barriers, 40 ... cathode structure for electrolysis

DESCRIPTION OF SYMBOLS FOR FIG. 10 1 ... Scissors jig (SUS), 2 ... Electrode, 3 ... Separator, 4 ... Nickel plate (grain number 320 alumina blasted), 100 ... Front 200 ... side.

Description of reference numerals for FIGS. 11 to 13: 1 ... diaphragm, 2a ... polyethylene pipe with outer diameter of 280 mm, 2b ... polyethylene pipe with outer diameter of 145 mm, 3 ... peeling part, 4 ... contact Part, 5 ... electrode.

Description of symbols for FIG. 14 1 ... PVC (polyvinyl chloride) pipe, 2 ... ion exchange membrane, 3 ... electrode, 4 ... surface plate

Explanation of reference numerals to FIG. 15 1... Surface plate 2... Deformed electrode 10... Jig for fixing the electrode 20.

DESCRIPTION OF SYMBOLS FOR FIGS. 16-21 1 ... 110 mm nickel wire, 2 ... 950 mm nickel wire, 3 ... frame

Claims (5)

An electrode for electrolysis;
A diaphragm or a power feeder in contact with the electrode for electrolysis;
With
The laminated body whose force per unit mass and unit area of the electrode for electrolysis with respect to the diaphragm or the power feeding body is less than 1.5 N / mg · cm ² . The laminate according to claim 1, wherein a force per unit mass / unit area of the electrode for electrolysis with respect to the diaphragm or the power feeding body is more than 0.005 N / mg · cm ² .   The laminated body according to claim 1 or 2, wherein the power feeder is a metal mesh, a metal nonwoven fabric, a punching metal, an expanded metal, or a foam metal.   The laminate according to any one of claims 1 to 3, which has a layer containing a mixture of hydrophilic oxide particles and a polymer into which an ion exchange group is introduced as at least one surface layer of the diaphragm.   The laminate according to any one of claims 1 to 4, wherein a liquid is interposed between the electrode for electrolysis and the diaphragm or the power feeding body.