WO2017158654A1 - Electrode unit manufacturing method, and electrolyzed water generating device manufacturing method - Google Patents

Abstract

This method, for manufacturing an electrode unit which is provided with an electrode and a porous membrane and which is used in an electrolyzed water generating device for generating electrolyzed water by electrolysis of an electrolytic solution, involves a step in which the porous membrane is immersed in a liquid having the property of being miscible with water and having a surface tension lower than that of water. This method of manufacturing an electrolyzed water generating device involves a step for manufacturing an electrode unit by means of the aforementioned electrode unit manufacturing method, and a step for installing the electrode unit in an electrolytic cell.

Description

Electrode unit manufacturing method and electrolyzed water generating device manufacturing method

The present invention relates to an electrode unit manufacturing method and an electrolyzed water generating device manufacturing method.

In recent years, an apparatus for generating electrolyzed water having various functions, such as alkaline ionized water, ozone water, or hypochlorous acid water, hydrogen, etc., by electrolyzing water has been proposed.

For example, when electricity is supplied to water to which an electrolyte such as sodium chloride is added, acidic water is generated on the anode side and alkaline water is generated on the cathode side. The acidic water produced on the anode side contains hypochlorous acid and has a bactericidal action. For this reason, hypochlorous acid water is used for disinfection and sterilization. Hypochlorous acid water is safe for the human body and approved as a food additive.

As an electrolyzed water generating device for generating hypochlorous acid water, various types of devices have been proposed. Among them, a two-chamber or three-chamber electrolyzed water generating device is provided between a pair of electrodes. A partition is provided. The partition wall is composed of, for example, an ion exchange membrane or a porous membrane having a property of selectively passing chloride ions, sodium ions, and the like.

JP 2006-322053 A

Since a porous membrane used as a partition wall has low affinity with water, it takes a certain amount of time to adjust to water or salt water. For this reason, in the electrolyzed water generating apparatus, a certain amount of time is required until the electrolysis is stably performed after the apparatus is started.

The present invention has been made under the above circumstances, and an object thereof is to shorten the rise time of the apparatus.

In order to solve the above problems, an electrode unit manufacturing method according to the present embodiment is used in an electrolyzed water generating device that generates electrolyzed water by electrolyzing an electrolytic solution, and includes an electrode and a porous film. A method for producing a unit, comprising the step of immersing the porous membrane in a liquid having a property of being mixed with water and having a surface tension lower than that of water.

It is a figure which shows schematic structure of the electrolyzed water generating apparatus which concerns on this embodiment. It is a figure which shows a porous membrane and an electrode typically. It is a perspective view of an electrode unit. It is an expansion perspective view of an electrode unit. It is a figure which expands and shows a porous membrane partially. It is a perspective view of an electrode. It is a perspective view of an electrode. It is sectional drawing of an electrode. It is sectional drawing of an electrode. It is a flowchart which shows the manufacturing method of an electrolyzed water generating apparatus. It is a figure for demonstrating the manufacturing method of an electrolyzed water generating apparatus. It is a figure for demonstrating the manufacturing method of an electrolyzed water generating apparatus. It is a perspective view of an electrolytic cell. It is a figure for demonstrating the manufacturing method of an electrolyzed water generating apparatus. It is a figure for demonstrating the manufacturing method of an electrolyzed water generating apparatus. It is a figure which shows the electrolytic cell which concerns on an Example. It is a table | surface for demonstrating the result of an Example and the result of a comparative example.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the description of the embodiment, an orthogonal coordinate system including an X axis, a Y axis, and a Z axis that are orthogonal to each other is used as appropriate.

"Device configuration"
FIG. 1 is a diagram illustrating a schematic configuration of an electrolyzed water generating apparatus 10 according to the present embodiment. The electrolyzed water generating apparatus 10 is an apparatus that generates acidic water containing acidic hypochlorous acid and alkaline water containing alkaline sodium hydroxide by electrolyzing salt water.

As shown in FIG. 1, the electrolyzed water generator 10 includes an electrolyzer 11, a salt water tank 12, a circulation pump 31, a pressure adjustment valve 32, and a DC power source 33.

The electrolytic cell 11 is a container made of, for example, resin or stainless steel. The inside of the electrolytic cell 11 is divided into an intermediate chamber S1, an anode chamber S2, and a cathode chamber S3 by a set of porous films 21 and 22. The porous membrane 21 is, for example chloride ion Cl ^- is a porous membrane having a property of passing anions such. The porous film 22 is a porous film having a property of passing cations such as sodium ion Na ⁺ , for example.

The intermediate chamber S1 is a space sandwiched between two porous films 21 and 22. The intermediate chamber S1 is filled with water containing sodium chloride (NaCl) as an electrolyte. The intermediate chamber S <b> 1 communicates with the outside through a water supply port 111 and a drain port 112 provided in the electrolytic cell 11.

The anode chamber S2 is a space adjacent to the intermediate chamber S1 through the porous membrane 21. An electrode 23 for generating acidic water is disposed in the anode chamber S2. The anode chamber S <b> 2 communicates with the outside through a water supply port 113 and a drain port 114 provided in the electrolytic cell 11.

The cathode chamber S3 is a space adjacent to the intermediate chamber S1 through the porous film 22. In the cathode chamber S3, an electrode 24 for generating alkaline water is disposed. The cathode chamber S3 communicates with the outside through a water supply port 115 and a water discharge port 116 provided in the electrolytic cell 11.

The electrode 23 serving as an anode is made of, for example, titanium (Ti), stainless steel (SUS), chromium (Cr), nickel (Ni), aluminum (Al), or an alloy thereof. The electrode 23 is shaped into a rectangular plate shape and has a plurality of openings.

From the viewpoint of efficiently promoting the electric field reaction, for example, a noble metal catalyst such as platinum (Pt) or an oxide catalyst such as iridium oxide is attached to the surface of the electrode 23.

The electrode 24 serving as a cathode is configured in the same manner as the electrode 23. In the electrode 24 serving as a cathode, a metal having corrosion resistance such as titanium or stainless steel can be used as it is without attaching a catalyst.

Raw water is supplied from the water supply ports 113 and 115 to the anode chamber S2 and the cathode chamber S3. As raw water, tap water, well water, etc. can be used, for example. The raw water supplied to the anode chamber S2 and the cathode chamber S3 is preferably soft water with reduced alkali components from the viewpoint of preventing the deposition of scales mainly composed of calcium carbonate. This type of soft water can be generated, for example, by using a water softener using an ion exchange resin.

The salt water tank 12 is a tank that stores salt water. The salt water tank 12 is provided with an outlet 121 and an inlet 122 for circulating salt water between the electrolytic tank 11.

As salt water, for example, salt water generated by adding sodium chloride (NaCl) as an electrolyte to water (H ₂ O), or by adding salt such as potassium chloride (KCl) containing chlorine to water. The resulting brine is used. The concentration of the salt water is not particularly limited, but considering the stability during electrolysis, it is preferable that the concentration is somewhat high. By using saturated sodium chloride as the salt water, it becomes easy to maintain a constant salt water concentration.

The pressure adjustment valve 32 is provided in a pipe line laid across the drain port 112 of the intermediate chamber S1 and the inlet 122 of the salt water tank 12.

The circulation pump 31 is provided in a pipe line laid across the outlet 121 of the salt water tank 12 and the water supply port 111 of the intermediate chamber S1. The circulation pump 31 supplies the salt water from the salt water tank 12 to the intermediate chamber S 1 of the electrolytic cell 11. Thereby, salt water circulates between the intermediate chamber S1 of the electrolytic cell 11 and the salt water tank 12. The flow rate of the salt water circulating between the intermediate chamber S1 and the salt water tank 12 is adjusted by the pressure adjusting valve 32.

DC power supply 33 applies voltage to electrode 23 and electrode 24. In the electrolyzed water generating apparatus 10, a voltage is applied to the electrodes 23 and 24 so that the electrode 23 is an anode and the electrode 24 is a cathode.

<Device operation>
Next, operation | movement of the electrolyzed water generating apparatus 10 comprised as mentioned above is demonstrated. In the electrolyzed water generating apparatus 10, when the circulation pump 31 is operated, the salt water in the salt water tank 12 is supplied to the intermediate chamber S 1 of the electrolyzer 11. When a certain amount of salt water is stored in the intermediate chamber S 1, the salt water from the intermediate chamber S 1 returns to the salt water tank 12 via the pressure adjustment valve 32. Thereby, salt water circulates between intermediate room S1 and salt water tank 12, and intermediate room S1 will be in the state where salt water of fixed concentration is stored.

Raw water is supplied to the anode chamber S2 and the cathode chamber S3 at a predetermined flow rate. When raw water is supplied to the anode chamber S2 and the cathode chamber S3, a voltage is applied to the electrodes 23 and 24 by the DC power source 33. Thereby, in the anode chamber S2, reactions represented by the following formulas (1), (2), and (3) occur. In the formula, M represents a catalyst.

From the equations (1) to (3), the reaction in the whole anode chamber S2 is represented by the following equation (4).

M + H ₂ O → M−OH + H ⁺ + e ⁻ (1)
M−OH → M−O + H ⁺ + e ⁻ (2)
M−O + Cl ⁻ + H ⁺ → M + HClO (3)
H ₂ O + Cl ⁻ → HClO + H ⁺ + 2e ⁻ (4)

In the anode chamber S2, a side reaction represented by the following formula (5) may occur. In the side reaction, oxygen is generated. From the formulas (1), (2), and (5), the side reaction in the entire anode chamber S2 is represented by the following formula (6).

2M−O → 2M + O ₂ (5)
2H ₂ O → O ₂ + 2H ⁺ + 2e ⁻ (6)

On the other hand, in the cathode chamber S3, a reaction represented by the following formula (7) occurs.

2H ₂ O + 2e ⁻ → H ₂ + 2OH ⁻ (7)

The total reaction including the anode and the cathode is expressed by the following formula (8).

2NaCl + 3H ₂ O → HClO + HCl + 2NaOH + H ₂ (8)

The acidic water generated in the anode chamber S2 is discharged from the drain port 114 leading to the anode chamber S2. Further, the alkaline water generated in the cathode chamber S3 is discharged from the drain 116 that leads to the cathode chamber S3. As mentioned above, in the electrolyzed water generating apparatus 10, acidic water and alkaline water are generated.

FIG. 2 is a diagram schematically showing the porous membranes 21 and 22 and the electrodes 23 and 24. As shown in FIG. 2, the porous membranes 21 and 22 and the electrodes 23 and 24 are disposed via a spacer 35. The spacer 35 is, for example, a casing that constitutes the intermediate chamber S1. In the present embodiment, the porous films 21 and 22, the electrodes 23 and 24, and the spacer 35 constitute the electrode unit 100.

<Electrode unit>
FIG. 3 is a perspective view of the electrode unit 100. FIG. 4 is a developed perspective view of the electrode unit 100. As can be seen with reference to FIGS. 3 and 4, the electrode unit 100 has the porous film 21 and the electrode 23 arranged on the upper surface (the surface on the + Z side) of the spacer 35, and the lower surface (the −Z side on the −Z side). Formed on the surface) by disposing the porous membrane 22 and the electrode 24.

"Spacer"
The spacer 35 is a rectangular frame-shaped member whose longitudinal direction is the X-axis direction and whose inside is hollow. The spacer 35 is made of, for example, resin or stainless steel. The spacer 35 is formed with a water supply port 111 and a water discharge port 112 that communicate with the internal space. The salt water circulates inside the spacer 35 through the water supply port 111 and the drain port 112.

In the internal space of the spacer 35, for example, a porous body that holds salt water may be disposed. In addition, a meandering flow path, a flow path that branches into a plurality, and the like may be formed in the internal space of the spacer 35.

<Porous membrane>
The porous membranes 21 and 22 are shaped to be approximately the same size as the spacer 35. FIG. 5 is a partially enlarged view showing the porous membranes 21 and 22. As shown in FIG. 5, a plurality of pores 200 are formed in the porous films 21 and 22. The surfaces of the porous membranes 21 and 22 are preferably covered with an inorganic oxide. The porous films 21 and 22 preferably contain an inorganic oxide inside.

For the porous films 21 and 22, chemically stable polytetrafluoroethylene, polyethylene, polyvinylidene fluoride, polyvinylidene chloride, or the like is used as a base material.

The porous membrane 21 that partitions the anode chamber S2 is preferably covered with an inorganic oxide that makes the zeta potential positive in a region where the pH is 2 to 6. A porous membrane satisfying this condition is chemically stable and has high transport performance for anions in a weakly acidic region.

As this kind of inorganic oxide, for example, zirconium oxide, titanium oxide, aluminum oxide, tin oxide, zircon, copper oxide, iron oxide, and mixed oxides thereof can be used. In particular, zirconium oxide, aluminum oxide, titanium oxide, and zircon can be used as the inorganic oxide having good chemical stability. Among these, the inorganic oxide having good bending resistance is zirconium oxide.

The inorganic oxide may contain a hydroxide, an alkoxide, an oxyhalide, or a hydrate. When an inorganic oxide is produced through hydrolysis of a metal halide or metal alkoxide, a mixture of these may be formed depending on the post-treatment temperature. The abundance ratio of the inorganic oxide in the porous film may be varied depending on the location. For example, the presence ratio of the inorganic oxide around the pores or on the surface may be increased.

As the inorganic oxide, a composite oxide such as zircon or a mixture of different inorganic oxides can be used. The porous film may be covered with two or more different oxides, and the abundance ratio of each oxide may be made different depending on the position of the porous film. For example, the surface of the porous film may be coated with zirconium oxide having a large bending strength, and the inside may be coated with titanium oxide having a large positive potential absolute value.

The zeta potential on the surface of the porous membrane is preferably greater than −30 mV at pH 4. When the zeta potential on the surface of the porous membrane is smaller than −30 mV, chloride ions tend to hardly penetrate even when a voltage is applied to the porous membrane. The zeta potential on the surface of the porous membrane is preferably larger than −15 mV.

The porous membrane 22 that partitions the cathode chamber S3 is preferably covered with an inorganic oxide that has a negative zeta potential in the region where the pH is 8 to 10. A porous membrane that satisfies this condition has high transport performance for cations in the weakly alkaline region.

As this kind of inorganic oxide, for example, zirconium oxide, titanium oxide, aluminum oxide, tungsten oxide, zircon, silicon oxide, and zeolite can be used. A mixture of the above oxides may be used as the inorganic oxide. Further, the abundance ratio and type of inorganic oxide in the porous film may be changed depending on the location. For example, the surface of the porous film may be coated with zirconium oxide having a high bending strength, and the inside may be coated with silicon oxide having a negative potential in a wide pH range.

A porous film coated with an inorganic oxide can be formed by applying nanoparticles to a porous substrate. Further, by using the sol-gel method, a porous film having pores that are irregularly arranged two-dimensionally or three-dimensionally can be formed. Such a porous film is resistant to bending and the like. The inorganic oxide may have dispersed particles, or the particles may form an aggregate to form a network.

The pore diameters of the pores formed in the porous membranes 21 and 22 may be different from one side of the porous membranes 21 and 22 to the other side. For example, in the porous membrane 21, the pore diameter on the electrode 23 side may be smaller than the pore diameter on the electrode 24 side. Anions such as chloride ion Cl 2 ⁻ can easily move toward the electrode 23 even if the pore diameter on the electrode 23 side is small. On the contrary, in the porous membrane 21, when the pore diameter of the pores on the electrode 23 side is larger than the pore diameter of the pores on the electrode 24 side, chlorine easily diffuses in the vicinity of the porous membrane. The pore diameter of the pores of the porous membrane can be measured using, for example, a scanning electron microscope (SEM).

"electrode"
6 and 7 are perspective views of the electrode 23. FIG. The electrode 23 has a thickness of about 1 mm and is shaped into a rectangular plate having the X-axis direction as the longitudinal direction. The electrode 23 includes a frame-shaped frame portion 201, a plurality of lattice portions 202 having a longitudinal direction in the X-axis direction, and a beam portion 203 having a longitudinal direction in the Y-axis direction.

The lattice unit 202 and the beam unit 203 are provided in a space defined by the frame unit 201 so as to cross each other. The lattice unit 202 is stretched across a space defined by the frame unit 201 so as to be parallel to the X axis. Further, the beam portion 203 is stretched in a space defined by the frame portion 201 so as to be parallel to the Y axis.

FIG. 8 is a diagram showing an AA cross section in FIG. As shown in FIG. 8, the lattice portions 202 are arranged at equal intervals along the Y axis so that the pitch P1 is 0.5 mm. The lattice portion 202 is shaped so that the thickness D1 is 0.1 to 0.2 mm and the cross section is a trapezoid. For this reason, in the opening sandwiched between the lattice portions 202, the dimension W1 in the Y-axis direction on the + Z side is 0.4 mm, and the dimension W2 in the Y-axis direction on the −Z side is 0.2 mm.

FIG. 9 is a diagram showing a BB cross section in FIG. As shown in FIG. 9, the beam portions 203 are arranged at equal intervals along the X-axis so that the pitch P2 is 2.4 mm. The beam portion 203 is shaped so that the thickness D2 is 0.3 to 0.4 mm and the cross section is a trapezoid. For this reason, in the opening sandwiched between the beam portions 203, the dimension W3 in the X-axis direction on the −Z side is 1.6 mm, and the dimension W4 in the X-axis direction on the + Z side is 1.2 mm.

The electrode 23 configured as described above can be manufactured, for example, by performing etching treatment on both surfaces of a metal plate made of stainless steel or titanium having a thickness of about 0.5 to 1 mm. Therefore, the + Z side surface of the frame portion 201 and the + Z side surface of the lattice portion 202 are located in the same plane, and the −Z side surface of the frame portion 201 and the −Z side surface of the beam portion 203 are the same. Located in the plane. The four corners of the rectangular opening are rounded.

In FIG. 6 and FIG. 7, ten lattice parts 202 are drawn, but tens to hundreds of lattice parts 202 are formed on an actual electrode. Accordingly, the ratio of the area A1 of the region sandwiched on the −Z side of the lattice portion 202 to the area A0 of the + Z side surface of the electrode 23 is about 40%. The electrode 23 is disposed such that the longitudinal direction is the vertical direction and the surface on the + Z side faces the porous film.

6 and 7, three beam portions 203 are drawn, but several tens of beam portions 203 are formed on an actual electrode. For this reason, the area A2 of the opening that penetrates the electrode 23 is about 20% of the area A0 of the + Z side surface of the electrode 23. In the electrode 23, the ratio of the area A2 to the area A0 is preferably 50% or less.

Also, the electrode 24 is configured similarly to the electrode 23.

In addition, the shape of the opening part of the electrodes 23 and 24 can be arbitrarily determined, such as a circle, an ellipse, or a polygon. When the shape of the opening is a polygon such as a quadrangle or a rhombus, the corner is preferably rounded. By rounding the corner portion, stress concentration can be made difficult to occur.

When the concentration of chloride ions at the electrode 23 as the anode is low, the reaction represented by the formula (5) tends to occur. Therefore, in order to efficiently generate hypochlorous acid, it is necessary to increase the concentration of chloride ions. Chloride ions are supplied from the porous membrane side to the electrode. Chloride ions passing through the porous membrane do not flow out from the place where the porous membrane and the electrode are in contact, but flow out from the opening through which the electrode 23 penetrates. For this reason, in order to increase the concentration of chloride ions at the electrode 23, it is important to prevent the outflow of chloride ions from the opening of the electrode 23.

Therefore, the opening area of the openings of the electrodes 23 and 24 is 0.01 mm ² to 4 mm ² . When the opening area is smaller than 0.01 mm ² , it becomes difficult to discharge reaction products such as gas and hypochlorous acid to the outside. For this reason, the electrodes 23 and 24 are likely to deteriorate. On the other hand, if the opening area is larger than 4 mm ² , chloride ions are likely to flow out, the electric resistance of the electrodes 23 and 24 is increased, and the electrolysis efficiency is lowered. The opening area is preferably 0.1 mm ^{2 to} 1.5 mm ² . The opening area is more preferably 0.2 mm ^{2 to} 1 mm ² .

"Production method"
Next, the manufacturing method of the electrolyzed water generating apparatus 10 provided with the electrode unit 100 comprised as mentioned above is demonstrated based on the flowchart of FIG.

When manufacturing the electrode unit 100, first, the porous material is shaped to prepare the porous films 21 and 22 shown in FIG. 4 (step S101). Next, preprocessing is performed on the porous films 21 and 22 (step S102).

The pretreatment is a treatment for improving the affinity of the porous membranes 21 and 22 to the liquid by modifying the surfaces of the porous membranes 21 and 22. As preprocessing, plasma processing, electron beam processing, UV ozone processing, etc. are performed, for example.

The plasma treatment is a treatment in which the surfaces of the porous films 21 and 22 are irradiated with, for example, oxygen plasma. The electron beam treatment is a treatment for irradiating the surfaces of the porous films 21 and 22 with an electron beam. The UV ozone treatment is a treatment for irradiating the surfaces of the porous films 21 and 22 with ultraviolet rays. By these treatments, the surfaces of the porous membranes 21 and 22 are modified, and the affinity for the liquid is improved.

Next, as shown in FIG. 11, the porous membranes 21 and 22 are immersed in the liquid 51 (step S103). The liquid 51 is a liquid having a property that is compatible with water and having a surface tension of 35 mN / m or less. As the liquid 51, for example, as shown in FIG. 11, an ethanol aqueous solution having an ethanol concentration of 30% by weight or more can be considered. The concentration of ethanol is preferably 50% by weight or more, and particularly preferably 90% by weight or more. The liquid 51 may be 99.5% so-called absolute ethanol. Moreover, the aqueous solution of surfactant may be sufficient.

By immersing the porous membranes 21 and 22 in the liquid 51, the liquid 51 having a lower surface tension than water enters the pores of the porous membranes 21 and 22.

Next, as shown in FIG. 12, the porous membranes 21 and 22 are washed with water 52 such as tap water (step S104). The surfaces of the porous membranes 21 and 22 and the inside of the pores are in a state in which they are familiar with the liquid 51 having an affinity for water. For this reason, by washing the porous membranes 21 and 22 with water, the surface and the inside of the porous membranes 21 and 22 are in a state of being in contact with the water 52.

Next, the porous films 21 and 22 are taken out, and the porous film 21 and the electrode 23 are arranged on the upper surface side of the spacer 35 and the lower surface side of the spacer 35 as shown in FIG. The porous membrane 22 and the electrode 24 are disposed. Then, as shown in FIG. 3, the spacer 35, the porous films 21 and 22, and the electrodes 23 and 24 are assembled and integrated (step S105). The spacer 35, the porous films 21 and 22, and the electrodes 23 and 24 are integrated by, for example, fixing the electrodes 23 and 24 to the spacer 35. Thereby, the electrode unit 100 is assembled.

Next, as shown in FIG. 13, the electrode unit 100 is sandwiched between a resin casing 151 having an anode chamber S2 formed therein and a resin casing 152 having a cathode chamber S3 formed therein. 151 and 152 are fixed with screws or the like. Thereby, the electrolytic cell 11 is assembled (step S106).

As shown in FIG. 13, the spacer 151, the porous membranes 21 and 22, and the electrodes 23 and 24 are composed of a casing 151 having an anode chamber S 2 formed therein and a casing 152 having a cathode chamber S 3 formed therein. The spacers 35, the porous membranes 21 and 22, and the electrodes 23 and 24 may be integrated by fixing the casings 151 and 152 with screws or the like.

Next, auxiliaries such as the salt water tank 12, the circulation pump 31, the pressure adjustment valve 32, and the DC power source 33 are connected to the electrolytic cell 11 configured as described above (step S107). Thereby, the electrolyzed water generating apparatus 10 shown in FIG. 1 is assembled.

As described above, in the present embodiment, the porous membranes 21 and 22 are immersed in the liquid 51 during the manufacturing process of the electrode unit 100 (step S103). Next, the porous membranes 21 and 22 are washed with water 52 such as tap water (step S104). By passing through the above process, the surface of the porous membranes 21 and 22 and the inside of the pores are in a state of becoming familiar with the liquid 51 having affinity for water. Then, the porous membranes 21 and 22 are washed with water, so that the surfaces and the inside of the porous membranes 21 and 22 become familiar with the water 52.

Therefore, the porous membranes 21 and 22 are in a state of having a short time affinity with the salt water and tap water in the intermediate chamber S1, the anode chamber S2, and the cathode chamber S3. As a result, it is possible to shorten the rise time from when the electrolyzed water generating device 10 is started until the electrolysis is stably performed.

It should be noted that after the electrolyzed water generating device 10 is started up, ionic species remain on the surfaces and pores of the porous membranes 21 and 22 even if the electrolyzed water generating device 10 is dried. Therefore, even when the electrolyzed water generating apparatus 10 is started next time, electrolysis can be stably performed in a short time. For this reason, the electrolyzed water generating apparatus 10 may be preliminarily operated before operation. Even if the electrolyzed water generating device is dried after the preliminary operation, the electrolyzed water generating device can be started up in a short time.

The liquid 51 is preferably made of ethanol and water. Ethanol has low environmental impact and high safety. For this reason, the porous membranes 21 and 22 immersed in the liquid 51 can be safely washed with water.

In this embodiment, before the porous membranes 21 and 22 are immersed in the liquid 51, the porous membranes 21 and 22 are pretreated. For this reason, the hydrophilicity of the surface of the porous membranes 21 and 22 improves. Accordingly, the porous films 21 and 22 can be satisfactorily made compatible with the liquid 51 or the water 52 in the subsequent processing (steps S103 and S104).

In the above embodiment, the case where the liquid 51 contains ethanol has been described. However, the liquid 51 may contain alcohols such as methanol, propanol, and isopropanol.

In the above embodiment, the surface tension of the liquid 51 is 35 mN / m or less, but the surface tension of the liquid 51 is preferably 30 mN / m or less. In particular, the surface tension of the liquid 51 is preferably 25 mN / m or less. The surface tension of the liquid 51 can be measured by various methods. For example, the measurement can be performed using a Wilhelmy method, a ring method, a hanging drop method, a maximum bubble pressure method, or the like. The ring method is suitable for measuring the surface tension of alcohol or an aqueous alcohol solution. The hanging drop method is suitable for measuring the surface tension of an aqueous solution containing a surfactant.

In the above embodiment, the case where the porous membranes 21 and 22 are washed with water has been described. Not limited to this, the porous membranes 21 and 22 may be washed with water containing chloride ions. Thereby, after starting electrolyzed water production | generation apparatus 10, the starting time until electrolysis is performed stably can further be shortened.

The chloride ion source is preferably a chloride such as sodium chloride or potassium chloride. The concentration of chloride contained in water when the porous membranes 21 and 22 are washed is preferably 1% by weight saturation concentration. The chloride concentration is more preferably 3% by weight saturation, and particularly preferably 5% by weight saturation.

In the above embodiment, the porous membranes 21 and 22 are immersed in the liquid 51 after the pretreatment (step S102) (step S103). Not only this but after performing pre-processing, you may perform the process which makes the porous membranes 21 and 22 contact alkoxide solutions, such as aluminum, zirconium, and titanium. By performing this step, oxides or hydroxides such as aluminum, or intermediates thereof are generated on the surfaces of the porous films 21 and 22 and the surfaces of the pores. Thereby, the hydrophilicity of the porous membranes 21 and 22 is increased, and the liquid 51 is more easily immersed. Moreover, since affinity with a chloride ion increases, it is preferable.

As the alkoxide, methoxide, ethoxide, propoxide, isopropoxide and the like can be used. From the viewpoint of solubility and hydrolysis, it is preferable to use isopropoxide. These concentrations are preferably about 5% to 95% of the saturated concentration. Further, it is more preferably 20% to 90% of the saturated concentration, and particularly preferably 50% to 80% of the saturated concentration. If the concentration is less than 5% of the saturation concentration, the effect is small. At the saturated concentration, the stability of the liquid becomes poor.

The step of bringing the porous membranes 21 and 22 into contact with the alkoxide solution is preferably performed after the pretreatment (step S102). By performing the above steps after the pretreatment, when the porous membranes 21 and 22 come into contact with an alkoxide solution such as aluminum, zirconium, or titanium, the oxide as the reaction product is stably stabilized. 21 and 22 are fixed. When plasma treatment or electron beam treatment is performed as pretreatment, the oxide is particularly stably fixed to the porous films 21 and 22.

In the above embodiment, chemically stable polytetrafluoroethylene, polyethylene, polyvinylidene fluoride, polyvinylidene chloride, or the like is used as the base material of the porous membranes 21 and 22.

Porous polytetrafluoroethylene film, porous polyethylene film, etc. have a porous structure formed by stretching or the like, but it is generally difficult to control the size of the pores. In addition, since these films have low mechanical strength, they may be stretched by water pressure or the like to change the pore diameter. On the other hand, glass fiber is chemically stable, has high strength, and is hardly deformed by water pressure. Therefore, as the porous film, glass fiber and polytetrafluoroethylene or polyvinylidene fluoride may be mixed to form a composite film. Thereby, adjustment of a hole diameter becomes easy and a chemical strength and mechanical strength can be improved. Among the above materials, it is preferable to laminate a porous polytetrafluoroethylene film and glass fiber. The polyethylene porous membrane has a slight problem with heat resistance, but the polyvinylidene fluoride has a slight problem with alkali resistance.

<Modification>
Next, a modification of the manufacturing method according to the above embodiment will be described. In the above embodiment, the porous membranes 21 and 22 are immersed in the liquid 51 (step S103), and then the porous membranes 21 and 22 are washed with water (step S104). In the manufacturing method according to this modified example, first, as shown in FIG. 3, after the porous membranes 21, 22, the electrodes 23, 24 and the spacers 35 are integrated to assemble the electrode unit 100, as shown in FIG. As described above, the electrode unit 100 is immersed in the liquid 51. By dipping the electrode unit 100 in the liquid 51, the liquid 51 having a lower surface tension than water enters the pores of the porous films 21 and 22.

Next, as shown in FIG. 15, the electrode unit 100 is manufactured by washing the electrode unit 100 with water 52 such as tap water. The surfaces of the porous membranes 21 and 22 and the inside of the pores are in a state in which they are familiar with the liquid 51 having an affinity for water. For this reason, by washing the electrode unit 100 with water, the surface and the inside of the porous membranes 21 and 22 are in a state of being in contact with the water 52.

Next, as shown in FIG. 13, the electrode unit 100 is sandwiched between the casing 151 in which the anode chamber S2 is formed and the casing 152 in which the cathode chamber S3 is formed, and the casings 151 and 152 are screwed together. Fix with etc. Thereby, the electrolytic cell 11 is completed.

Next, auxiliary equipment such as the salt water tank 12, the circulation pump 31, the pressure adjustment valve 32, and the DC power source 33 is connected to the electrolytic cell 11 configured as described above. Thereby, the electrolyzed water generating apparatus 10 shown in FIG. 1 is completed.

As described above, in this modification, only the electrode unit 100 can be made in large quantities as replacement parts.

Next, examples showing the effects of this embodiment will be described.

Example 1
In the electrolyzed water generating apparatus 10 shown in FIG. 1, a polytetrafluoroethylene porous membrane (manufactured by Sumitomo Electric: Poreflon HPW-010-30) having a thickness of 30 μm and a glass cloth having a thickness of 75 μm (Nittobo: 3313) Is used as a raw material for the porous membranes 21 and 22. The polytetrafluoroethylene porous membrane and the glass cloth are integrated by heating and pressing to 100 ° C. in a state where both are stacked.

Next, a dispersion obtained by diluting a polytetrafluoroethylene fine particle dispersion (Mitsui / DuPont: Fluorochemical 31-JR) twice with respect to the glass cloth surface of the polytetrafluoroethylene porous membrane and glass cloth laminate. The solution is subjected to dip coating using a mixed solution containing 30% by weight of titania nanoparticles with respect to polytetrafluoroethylene. And a laminated body is heated to 200 degreeC and the porous membranes 21 and 22 are produced. The amount of polytetrafluoroethylene fine particles added is 16 mg / cm 2 and the heating time of the laminate is about 20 minutes.

Next, after dip coating using a 5% isopropanol solution of tetraisopropoxyzirconium (IV) is performed on the porous membranes 21 and 22, the porous membranes 21 and 22 are placed in the atmosphere at 200 ° C. Allow to dry for a while. The zeta potential on the surfaces of the porous membranes 21 and 22 thus completed is −10 mV at ph4. Further, it is −40 mV at pH 8-10.

For the electrode 23 as an anode, a flat titanium plate having a plate thickness of 0.5 mm is used as a substrate. The substrate has a length of 15 cm and a width of 10 cm. On the base material, through holes having a diameter of 1.5 mm are formed in a hexagonal lattice shape with a pitch of 2.2 mm by punching.

The electrode 23 is immersed in a 10 wt% oxalic acid aqueous solution at 80 ° C. for 1 hour. Next, a voltage of 10 V is applied for 2 hours while the electrode 23 is immersed in a mixed aqueous solution of 1M ammonium sulfate and 0.5M ammonium fluoride. Thus, the electrode 23 is anodized.

Next, a solution prepared by adding 1-butanol to 0.25 M (Ir) to iridium chloride (IrCl ₃ .nH ₂ O) is applied to both surfaces of the electrode 23. Thereafter, the electrode 23 is dried and baked to form a catalyst layer on the surface of the electrode 23. Drying is performed by placing the electrode 23 in an atmosphere of 80 ° C. for 10 minutes, and baking is performed by heating the electrode 23 to 450 ° C. and maintaining it for 10 minutes. In the present embodiment, the catalyst layer is formed on the surface of the electrode 23 by repeating the application, drying, and firing five times.

For the electrode 24 as a cathode, a flat SUS304S plate having a plate thickness of 0.5 mm is used as a substrate. The substrate has a length of 15 cm and a width of 10 cm. On the base material, through holes having a diameter of 1.5 mm are formed in a hexagonal lattice shape with a pitch of 2.2 mm by punching. The substrate of the electrode 24 is used as it is as the electrode 24 without forming a catalyst layer or the like on the surface.

In the spacer 35 having the intermediate chamber S1, porous polystyrene having a thickness of 5 mm is disposed as a holder for holding the electrolytic solution.

The porous membranes 21 and 22 are immersed in 90% ethanol (10% is almost water) having a surface tension at 20 ° C. of 24 mN / m for 1 minute. Thereafter, the porous membranes 21 and 22 are washed with water. Next, as can be seen with reference to FIGS. 3 and 4 without drying the porous membranes 21 and 22, the resin spacers 35, the porous membranes 21 and 22, and the electrodes 23 and 24 are screwed or packed. The electrode unit 100 is configured by assembling and integrating them. The resin electrolytic cell 11 is configured using the electrode unit 100.

Next, auxiliary equipment is connected to the electrolytic cell 11 to constitute the three-chamber electrolyzed water generating apparatus 10 shown in FIG. The electrolytic cell 11 is connected to a conduit for supplying water from a commercial water supply facility to the anode chamber S2 and the cathode chamber S3. The porous membranes 21 and 22 are not dried during this period after being washed with water. The brine tank 12 is supplied with saturated saline. A conductivity sensor is installed at the drain port 114 of the electrolytic cell 11 shown in FIG. 1, and a pH sensor is installed at the drain port 116.

The electrolyzed water generating apparatus 10 configured as described above is operated under the condition that the flow rate of salt water is 2 L / min and the voltage between electrodes is 6V. As a result, hypochlorous acid water is generated in the anode chamber S2, and hydrogen and sodium hydroxide water are generated in the cathode chamber S3. The electrolyzed water generating apparatus 10 is in a steady operation state in which electrolysis is stabilized within 2 minutes from the start of operation. Then, after draining water and salt water from the electrolyzed water production | generation apparatus 10, and making it dry, a driving | operation is started again. Also in this case, the electrolyzed water generating apparatus 10 is in a steady operation state in which electrolysis is stabilized within 3 minutes from the start of operation.

<< Comparative Example 1 >>
The porous membranes 21 and 22 are immersed in 90% ethanol having a surface tension at 20 ° C. of 24 mN / m for 1 minute. Thereafter, the porous membranes 21 and 22 are dried without washing with water. The porous units 21 and 22 constitute the electrode unit 100. Similarly, the electrolyzed water generating apparatus 10 including the electrode unit 100 is operated under the condition that the flow rate of the salt water is 2 L / min and the voltage between the electrodes is 6V. The electrolyzed water generating apparatus 10 according to Comparative Example 1 takes time for the rise of the interelectrode current, and enters a steady operation state in which electrolysis is stable after 30 minutes or more have elapsed from the start of operation.

<< Comparative Example 2 >>
The porous membranes 21 and 22 are immersed in a 20% aqueous ethanol solution having a surface tension of 38 mN / m at 20 ° C. for 1 minute. Thereafter, the porous membranes 21 and 22 are washed with water. Next, the electrode unit 100 is composed of the porous films 21 and 22 without drying the porous films 21 and 22. Similarly, the electrolyzed water generating apparatus 10 including the electrode unit 100 is operated under the condition that the flow rate of the salt water is 2 L / min and the voltage between the electrodes is 6V. The electrolyzed water generating apparatus 10 according to Comparative Example 2 takes time for the rise of the interelectrode current, and after 15 minutes or more have elapsed from the start of operation, the electrolyzed water generating apparatus 10 enters a steady operation state in which electrolysis is stable.

The results of Example 1 and Comparative Examples 1 and 2 show that the electrolyzed water generator 10 is obtained by immersing the porous membranes 21 and 22 in water-containing ethanol having a surface tension of 35 mN / m or less and then washing with water. It shows that the rise time of is reduced.

Example 2
In the electrolyzed water generating apparatus 10 configured in the same manner as in Example 1, the porous membranes 21 and 22 obtained in the same manner as in Example 1 are placed in 90% ethanol having a surface tension at 20 ° C. of 24 mN / m for 1 minute. Immerse. Thereafter, the porous membranes 21 and 22 are washed with an aqueous sodium chloride solution having a concentration of 10% instead of water. Then, after the porous membranes 21 and 22 are dried at room temperature overnight, the electrode units 100 are constituted by the porous membranes 21 and 22. Similarly, the electrolyzed water generating apparatus 10 including the electrode unit 100 is operated under the condition that the flow rate of the salt water is 2 L / min and the voltage between the electrodes is 6V. The electrolyzed water generating apparatus 10 according to Example 2 is in a steady operation state in which electrolysis is stabilized within 4 minutes from the start of operation.

The results of Example 2 and Comparative Examples 1 and 2 show that the porous membranes 21 and 22 are immersed in hydrous ethanol having a surface tension of 35 mN / m or less, and then washed with an aqueous sodium chloride solution having a concentration of 10%. Thus, even when the electrolyzed water generating apparatus 10 is dried, the rise time is shortened.

Example 3
The porous membranes 21 and 22 obtained in the same manner as in Example 1 are neither immersed in an aqueous ethanol solution nor washed with water, and are used in a dry state to constitute the electrode unit 100. Then, the electrode unit 100 is immersed in 90% ethanol having a surface tension at 20 ° C. of 24 mN / m for 1 minute. Thereafter, the electrode unit 100 is washed with water. Similarly, the electrolyzed water generating apparatus 10 including the electrode unit 100 is operated under the condition that the flow rate of the salt water is 2 L / min and the voltage between the electrodes is 6V. The electrolyzed water generating apparatus 10 according to Example 3 is in a steady operation state in which electrolysis is stabilized within 2 minutes from the start of operation.

Example 4
In the electrolyzed water generating apparatus according to Example 4, the anode chamber S2 is disposed so as to surround the intermediate chamber S1 and the cathode chamber S3, as shown in FIG. Moreover, this electrolyzed water production | generation apparatus is equipped with the batch-type electrolyzer 11A in which a water flow is formed by natural convection of salt water or water without a pump or piping. The capacity of the anode chamber S2 is 2L, and the capacity of the cathode chamber S3 is 0.1L. As the electrode unit, an electrode unit having the same configuration as in the first embodiment is used. The size of the electrode unit is small, and the size of the electrode is 4 cm in length and 3 cm in width.

Further, at the time of manufacturing the electrode unit, as in the case of Example 1, the porous membrane is immersed in 90% ethanol having a surface tension of 24 mN / m at 20 ° C. for 1 minute and washed with water. Next, the porous membrane is integrated with an electrode or the like without drying to constitute an electrode unit.

The electrolyzed water generating apparatus according to this example is operated under the condition where the interelectrode voltage is 7V. As a result, hypochlorous acid water is generated in the anode chamber S2, and hydrogen and sodium hydroxide water are generated in the cathode chamber S3. This electrolyzed water generating apparatus is in a steady operation state in which electrolysis is stabilized within 2 minutes from the start of operation.

Example 5
In the electrolyzed water generating apparatus 10 shown in FIG. 1, a polyethylene porous film having a thickness of 30 μm is used as the porous films 21 and 22. The configuration other than the porous membranes 21 and 22 is the same as the configuration of the electrolyzed water generating apparatus according to the first embodiment.

The porous membranes 21 and 22 are immersed in an aqueous solution of a SPAN20 surfactant having a surface tension at 20 ° C. of 32 mN / m. Thereafter, the porous membranes 21 and 22 are washed with an aqueous sodium chloride solution having a concentration of 10%. Next, the electrode unit 100 is configured using the porous membranes 21 and 22 without drying the porous membranes 21 and 22. Similarly, the electrolyzed water generating apparatus 10 including the electrode unit 100 is operated under the condition that the flow rate of the salt water is 2 L / min and the voltage between the electrodes is 6V. The electrolyzed water generating apparatus 10 according to Example 5 is in a steady operation state in which electrolysis is stabilized within 3 minutes from the start of operation.

<< Comparative Example 3 >>
In the electrolyzed water generating apparatus 10 configured in the same manner as in Example 5, the porous membranes 21 and 22 are immersed in an aqueous solution of a SPAN20 surfactant having a surface tension at 20 ° C. of 36 mN / m. Thereafter, the porous membranes 21 and 22 are washed with an aqueous sodium chloride solution having a concentration of 10%. Next, the electrode unit 100 is configured using the porous membranes 21 and 22 without drying the porous membranes 21 and 22.

Similarly, the electrolyzed water generating apparatus 10 including the electrode unit 100 is operated under the condition that the flow rate of the salt water is 2 L / min and the voltage between the electrodes is 6V. The electrolyzed water generating apparatus 10 according to Comparative Example 3 enters a steady operation state in which electrolysis is stable after 10 minutes or more have elapsed from the start of operation.

As a result of Example 5 and Comparative Example 3, the electrolyzed water generating device was obtained by immersing the porous membranes 21 and 22 in an aqueous solution having a surface tension of 35 mN / m or less and then washing with a sodium chloride aqueous solution. 10 shows that the rise time is shortened.

Example 6
In the electrolyzed water generating apparatus 10 shown in FIG. 1, a polyethylene porous film having a thickness of 30 μm is used as the porous films 21 and 22. Then, after the porous films 21 and 22 are subjected to plasma treatment, they are immersed for 1 minute in isopropyl alcohol of aluminum isopropoxide having a concentration of 5% by weight. Thereafter, the porous membranes 21 and 22 are dried by being placed in an atmosphere of 90 ° C. for 10 minutes. Next, the porous membranes 21 and 22 are immersed in an aqueous solution of a SPAN20 surfactant having a surface tension at 20 ° C. of 32 mN / m. Thereafter, the porous membranes 21 and 22 are washed with a saturated sodium chloride aqueous solution.

The electrode unit 100 is configured using the porous membranes 21 and 22 without drying the porous membranes 21 and 22. The electrolyzed water generating apparatus 10 including this electrode unit 100 is operated under the condition that the flow rate of salt water is 2 L / min and the voltage between electrodes is 6V. The electrolyzed water generating apparatus 10 according to Example 6 is in a steady operation state in which electrolysis is stabilized within 2 minutes from the start of operation.

Example 7
The electrode unit 100 is configured in the same manner as in Example 6 except that instead of using an aqueous solution of a SPAN20 surfactant having a surface tension of 32 mN / m, a 30% ethanol aqueous solution having a surface tension of 33 mN / m is used. The electrolyzed water generating apparatus 10 including this electrode unit 100 is operated under the condition that the flow rate of salt water is 2 L / min and the voltage between electrodes is 6V. The electrolyzed water generating apparatus according to Example 7 is in a steady operation state in which electrolysis is stabilized within 3 minutes from the start of operation.

Example 8
The electrode unit 100 is configured in the same manner as in Example 7 except that it is washed with water instead of washing with a saturated sodium chloride solution. The electrolyzed water generating apparatus 10 including this electrode unit 100 is operated under the condition that the flow rate of salt water is 2 L / min and the voltage between electrodes is 6V. The electrolyzed water generating apparatus according to Example 8 is in a steady operation state in which electrolysis is stabilized within 5 minutes from the start of operation.

<< Comparative Example 4 >>
An electrode unit is constructed in the same manner as in Example 7 except that a 20% aqueous ethanol solution having a surface tension of 38 mN / m is used instead of using an aqueous solution of a SPAN20 surfactant having a surface tension of 33 mN / m. The electrolyzed water generating apparatus 10 including this electrode unit 100 is operated under the condition that the flow rate of salt water is 2 L / min and the voltage between electrodes is 6V. The electrolyzed water generating apparatus according to Example 7 enters a steady operation state in which electrolysis is stabilized after 8 minutes or more have elapsed from the start of operation.

Example 9
In the electrolyzed water generating apparatus 10 shown in FIG. 1, a polyethylene porous film having a thickness of 30 μm is used as the porous films 21 and 22. The configuration other than the porous membranes 21 and 22 is the same as the configuration of the electrolyzed water generating apparatus according to the first embodiment.

The porous membranes 21 and 22 are immersed in 99.5% methanol having a surface tension at 20 ° C. of 23 mN / m. Thereafter, the porous membranes 21 and 22 are washed with water. Next, the electrode unit 100 is configured using the porous membranes 21 and 22 without drying the porous membranes 21 and 22. Similarly, the electrolyzed water generating apparatus 10 including the electrode unit 100 is operated under the condition that the flow rate of the salt water is 2 L / min and the voltage between the electrodes is 6V. The electrolyzed water generating apparatus 10 according to Example 9 is in a steady operation state in which electrolysis is stabilized within 2 minutes from the start of operation.

The table shown in FIG. 17 is a table showing the rise time of the electrolyzed water generating apparatus according to each example and comparative example. As shown in the table, the electrolyzed water generating apparatus according to the present example rises within 5 minutes, while the electrolyzed water generating apparatus according to the comparative example requires at least 8 minutes or more for rising.

As mentioned above, although embodiment of this invention was described, these embodiment is shown as an example and is not intending limiting the range of invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

That is, this embodiment presents an example of a method for manufacturing an electrode unit (steps S101 to S105) and a method for manufacturing an electrolyzed water generating device (steps S101 to S107), and thereby limits the scope of the invention. Not intended to do. What has the requirements of the present invention is included in the scope of the present invention regardless of the name. For example, although the name of the present invention is a manufacturing method of an electrode unit and a manufacturing method of an electrolyzed water generating device, the manufacturing method concerning the present invention includes various modifications, such as maintenance provided with the constituent features of the present invention.

DESCRIPTION OF SYMBOLS 10 Electrolyzed water production | generation apparatus 11,11A Electrolysis tank 12 Salt water tank 21,22 Porous membrane 23,24 Electrode 31 Circulation pump 32 Pressure adjustment valve 33 DC power supply 35 Spacer 51 Liquid 52 Water 100 Electrode unit 111,113,115 Water supply port 112 , 114, 116 Drainage port 121 Outflow port 122 Inflow port 151, 152 Casing 200 Pore 201 Frame portion 202 Lattice portion 203 Beam portion S1 Intermediate chamber S2 Anode chamber S3 Cathode chamber

Claims (18)

1. A method for producing an electrode unit comprising an electrode and a porous membrane, which is used in an electrolyzed water generating device that generates electrolyzed water by electrolyzing an electrolytic solution,
   An electrode unit manufacturing method comprising a step of immersing the porous membrane in a liquid having a property of being mixed with water and having a surface tension lower than that of water.
2. The method for producing an electrode unit according to claim 1, wherein the liquid has a surface tension of 35 mN / m or less.
3. The method for manufacturing an electrode unit according to claim 1, wherein the liquid is an aqueous solution containing alcohol.
4. The method for producing an electrode unit according to claim 3, wherein the liquid is an aqueous solution containing 30% by weight or more of ethanol.
5. The method for manufacturing an electrode unit according to claim 1, wherein the liquid is ethanol having a purity of 90% or more.
6. The method for manufacturing an electrode unit according to claim 1, wherein the liquid is methanol having a purity of 90% or more.
7. The method for producing an electrode unit according to claim 1, wherein the liquid is an aqueous solution of a surfactant.
8. The method for manufacturing an electrode unit according to any one of claims 1 to 7, comprising a step of washing the porous film immersed in the liquid with water.
9. The method for manufacturing an electrode unit according to claim 8, wherein the porous membrane is washed with water containing chloride ions.
10. The method for manufacturing an electrode unit according to claim 7 or 9, wherein the porous membrane is washed with water containing chloride ions and then dried.
11. 11. The method according to claim 1, further comprising: performing at least one of plasma treatment, electron beam treatment, and UV ozone treatment on the porous membrane before immersing the porous membrane in the liquid. A method for manufacturing the electrode unit according to claim 1.
12. 12. The method according to claim 1, further comprising a step of contacting the porous film with an alkoxide solution of at least one of aluminum, zirconium, and titanium before immersing the porous film in the liquid. Of manufacturing the electrode unit.
13. The method for manufacturing an electrode unit according to any one of claims 1 to 12, wherein the porous film contains at least one of polyethylene, polyvinylidene fluoride, and polytetrafluoroethylene.
14. The method for manufacturing an electrode unit according to any one of claims 1 to 13, wherein the porous film contains at least one particle of titanium oxide, aluminum oxide, zirconium oxide, and zircon.
15. Disposing a set of the electrodes so as to oppose each other via a holding means for holding the electrolytic solution;
    Arranging a pair of diaphragms between the electrodes via a holding means for holding the electrolytic solution;
    The manufacturing method of the electrode unit as described in any one of Claims 1 thru | or 14 containing these
16. The method for manufacturing an electrode unit according to claim 15, wherein both of the pair of the diaphragms are the porous films.
17. A step of manufacturing an electrode unit by the method for manufacturing an electrode unit according to any one of claims 1 to 16,
    Installing the electrode unit in an electrolytic cell;
    The manufacturing method of the electrolyzed water generating apparatus containing this.
18. Preliminarily operating the electrolyzed water generating device;
    A step of drying the electrode unit after performing the preliminary operation;
    The manufacturing method of the electrolyzed water generating apparatus of Claim 17 containing this.

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