JP2656107B2 - Dialysis electrode device - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a simple dialysis electrode device for removing unnecessary ionic substances from a solution, for example, in electrodeposition coating and electroplating. In particular, the present invention relates to a dialysis electrode device useful as an electrode other than an electrode of an object to be coated, which is separated from a solution by a tubular ion exchanger and is useful in electrodeposition coating.

[Problems to be solved by the prior art and the invention]

Electrodeposition coating is roughly divided into anionic type and cationic type.
Generally, an anionic paint and a cationic paint containing a resin as a main component are used as an aqueous solution, and at the same time, an acid and an alkali are respectively added as a neutralizing agent to adjust the electric conductivity of the solution. However, in the implementation of electrodeposition coating, since the paint solution is replenished in accordance with the decrease in paint components, the acid or alkali in the solution gradually accumulates as it is, resulting in changes in conditions such as conductivity. This has a negative effect on the uniform and good formation of the coating. Therefore, in general, a control method is employed in which the other electrode with respect to the electrode to be coated is isolated from the solution by an ion exchange membrane, and the acid or alkali in the solution is dialyzed and removed through the membrane.

Conventionally, in the electrodeposition coating as described above, as an electrode separated by an ion exchange membrane, as described in Japanese Patent Publication No. 45-2231, the electrode itself was installed using an ion exchange membrane as a diaphragm. It consists of a box-shaped hollow container,
It is an electrode unit that can be removed from the solution. However, in such a box-shaped diaphragm electrode device using an ion exchange membrane, even if the membrane is held by a non-conductive wire mesh or a perforated structure, it is accompanied by the loading and unloading of an object to be coated in a solution. Due to water pressure fluctuations, deformation of the membrane is unavoidable, so it does not have long-term durability and breaks, and requires periodic replacement. However, there is a problem that the efficiency is low and the cost is high.

On the other hand, Japanese Patent Publication No. 57-27955 has been proposed as a diaphragm electrode device for electrodeposition coating which aims to improve the durability of the ion exchange membrane and the efficiency of the electrodeposition coating, as well as to reduce the size and weight. That is, the membrane device for electrodeposition coating described in Japanese Patent Publication No. 57-27955 is held with good durability because the ion exchange membrane is laminated on the surface of the electrode via a support having a liquid flow structure, and Water is forcibly circulated from the outside through the support material to eliminate bubbles adhering to the electrodes and polarized impurity molecules. Specifically, a tubular electrode device for electrodeposition coating is shown in which an ion exchange membrane is wound and laminated around the outer periphery of a tubular electrode via a mesh spacer or the like. However, Japanese Patent Publication No. 57-
In the membrane electrode device for electrodeposition coating proposed in 27955 and the like, it is essential to laminate the ion exchange membrane on the surface of the electrode via a support material, so the ion exchange membrane is wound, laminated and joined. It takes time and effort to produce the configuration. In addition, the dimensions of the ion exchange membrane generally extend in the electrodeposition coating solution and shrink when it comes out of the solution, but in the above electrodeposition membrane electrode device for electrodeposition coating, the ion exchange membrane is fixed to the electrode together with the membrane support. Therefore, there is a problem that expansion and contraction of the ion exchange membrane is not absorbed, and wrinkles and the like are generated and easily broken.

[Means for solving the problem]

In view of the above problems, the present inventors have conducted intensive studies with the aim of developing an electrode device which is easy to manufacture and does not cause wrinkles or the like of an ion exchange membrane. As a result, the above object was successfully achieved, and the present invention was provided.

That is, the present invention comprises a tubular ion exchanger having one or both ends opened, an electrode inserted in the tube, and a lid fitted to the open end of the tubular ion exchanger, and one end of the tubular ion exchanger. One end of an electrode is supported on the fitted lid, and the other end of the tubular ion exchanger is movable in the axial direction according to expansion and contraction of the tubular ion exchanger. This is a dialysis electrode device provided with a supply port and a discharge port of the polar solution for flowing the polar solution from one end to the other end.

FIG. 1 is a sectional view of the dialysis electrode device of the present invention cut along a plane parallel to a vertical direction. In FIG. 1, a cylindrical electrode 2 is inserted into a tube of a tubular ion exchanger 1 whose both ends are open. At the upper and lower ends of the tubular ion exchanger 1, upper and lower lids 4 and 3
Are fitted. The lower end of the tubular ion exchanger 1 is a lower lid 3
, But the upper end is a tubular ion exchanger 1
The upper lid 4 is open for inserting the electrode 2 therein. The lower end of the electrode 2 is pushed down by the lower lid 3 fitted to the lower end of the tubular ion exchanger 1.
In order to prevent breakage of the electrode 2, the electrode 2 is suspended by supporting a flange 7 provided near the upper end of the electrode 2 with the upper lid 4. And the tubular ion exchanger 1 itself also has an upper lid 4.
The lower end of the tubular ion exchanger 1 is not fixed to the electrode 2 but forms a free end, and can move in the axial direction (vertical direction) according to the expansion and contraction of the tubular ion exchanger 1. Has become. Further, the lower lid 3 and the upper lid 4 are respectively provided with a supply port 6 and a discharge port 5 for the polar liquid for flowing the polar liquid from one end to the other end in the tube of the tubular ion exchanger 1.

FIG. 2 is a sectional view showing another embodiment of the dialysis electrode device of the present invention. In FIG. 2, joining members 8 are fixed to both ends of a tubular ion exchanger having three open ends by any means such as adhesion or fusion with an adhesive. The joining member 8 is threaded, and the tubular ion exchanger 1
They can be easily connected via the packing 9. In addition, three electrodes 2 are connected by screws, and can be divided according to the flow of each tubular ion exchanger 1. By doing so, the dialysis electrode device can be easily assembled, and when the tubular ion exchanger is damaged, it can be easily repaired by replacing only the damaged portion.

In FIG. 2, an anolyte supply pipe 10 made of a rigid material is connected to the anolyte supply port 6 provided in the lower lid 3 at the lower end of the tubular ion exchanger 1. Is provided along the outer surface of the tubular ion exchanger 1 in the axial direction. The polar liquid supply pipe 10 is fixed to the lower lid 3 at the lower end, passes through a guide pipe 11 fixed to the upper lid 4 at the upper end, and is fixed by a nut 12 above it. nut
The distance between the upper lid 4 and the lower lid 3, that is, the length of the tubular ion exchanger 1 can be adjusted by moving the electrode 12 in the axial direction of the supply pipe 10 for the polar liquid. For this reason, when the electrode device for dialysis of the present invention is immersed in the electrodeposition coating solution, the nut 12 is moved in the axial direction of the supply pipe 10 for the polar solution by the extension of the tubular ion exchanger, thereby forming the tubular ion exchanger. By increasing the length, wrinkles of the tubular ion exchanger can be prevented. For transport of the dialysis electrode device, the supply line
Therefore, it is possible to prevent the tubular ion exchanger from being damaged.

The above-mentioned polar liquid supply pipe has three functions of supplying the polar liquid, adjusting the distance between the upper lid and the lower lid, and reinforcing the bending. These three functions are performed by separate parts. May be. For example, a hose for supplying a flexible polar liquid may be connected to the polar liquid supply port of the lower lid, and separately from this, the upper lid and the lower lid may be connected by a rigid rod or a cylinder. it can.

In the electrode device for dialysis of the present invention, a tubular ion exchanger is selected according to its use.For example, a cation exchanger for anionic electrodeposition coating and an anion exchanger for cation electrodeposition coating. Used. Such a tubular ion exchanger used in the present invention is required to have a tensile strength sufficient to support its own weight, for example, an inner diameter of 44 mm
The tensile strength of a tubular ion exchanger with a thickness of 3 mm and a length of 1000 mm is 0.1
It is preferably at least Kg / cm ² . In addition, it has durability against water pressure fluctuation in the solution to be performed such as electrodeposition coating,
For example, it is preferable to have a mechanical strength that hardly deforms when a pressure of 0.1 kg / cm ² is applied from the inside of a tubular ion exchanger having an inner diameter of 44 mm, a thickness of 3 mm, and a length of 1000 mm. The method for producing such a tubular ion exchanger is not particularly limited, but as already proposed by the present inventors in Japanese Patent Application No. 63-238913, at least (A) ion is added to a tubular polyethylene porous body. A method of impregnating a monomer mixture containing a polymerizable monomer having a functional group suitable for introducing an exchange group, (B) a cross-linking agent and (C) a radical polymerization initiator, and then polymerizing, followed by introducing an ion-exchange group Thus, an integral tubular ion exchanger having a good mechanical height can be obtained. The tubular polyethylene porous body used in this manufacturing method is generally 5 to 300 mm in diameter, 0.5 to 5 mm in thickness,
It is appropriately selected from shapes having a length of 20 mm to 5 m. The average pore diameter of the porous body is 1 to 500 μm, particularly 10 to 200 μm, and the porosity is 10 to
It is preferably 80%, especially 30 to 60%, since the impregnation and polymerization of the monomer mixture can be sufficiently achieved and a desired tubular ion exchanger can be obtained. Further, the monomer mixture is the same composition as the conventionally known ion exchange resin membrane,
For example, the component (A) such as styrene and chloromethylstyrene, the component (B) such as divinylbenzene, and the component (C) such as benzoyl peroxide are used. It is prepared using molecules, plasticizers, solvents and the like.

Further, the tubular ion exchanger that can be suitably used in the present invention can also be produced by the following method. That is, this is a method in which a mixture of an ion exchange resin powder and a polyethylene resin is formed into a tube by extrusion. Here, as the ion-exchange resin powder, known ones are used without any limitation, but usually, it is preferable to use a powder having an average particle diameter smaller than 100 μm. As the polyethylene resin, any of a high density and a low density can be used, but a resin having a melt index of 2 g / 10 minutes or less is preferable because a reduction in ion exchange capacity due to extrusion can be prevented. The mixing ratio of the above-mentioned ion exchange resin powder and polyethylene resin is generally from ion exchange resin powder: polyethylene resin = 7: 3 to 5: 5 from the viewpoint of mechanical strength and ion exchange capacity of the obtained tubular ion exchanger. (Weight ratio). As a method of forming the mixture into a tube by extrusion, a normal extrusion method is employed without any limitation. However, as the molding temperature, a value that does not decompose the ion exchange group is adopted, and the molding time is preferably short. In this way, a tubular ion exchanger having the same size as that produced by the above-described method is obtained.

The tubular ion exchanger shown in FIG. 1 and FIG.
Although both ends are open, a tubular ion exchanger having one end closed as shown in FIG. 3 can be obtained depending on the manufacturing method, and such a tubular ion exchanger can also be used in the present invention.

The electrode used in the present invention is selected according to the type of the tubular ion exchanger. The tubular cation exchanger is a cathode, and the tubular anion exchanger is an anode. Such electrodes are
Conventionally known cathodes or anodes are employed, and are not particularly limited as long as they have a predetermined shape that can be installed in the tube of the tubular ion exchanger, and are generally rod-shaped, flat, cylindrical, and the like. An acid-resistant metal anode of a platinum group metal is used. Such an electrode is installed in the tube of the tubular ion exchanger while maintaining the distance from the tubular ion exchanger generally at 0.5 to 50 mm. In particular, when a vertical electrode device is used, the gas increases in the upper part of the tubular ion exchanger and the current distribution in the lower part becomes non-uniform. A lath-like or punched porous electrode for removing slag is preferably used. Furthermore, the current-carrying surface side of the electrode in the upper part of the electrode in the tube of the tubular ion exchanger is closer to the counter electrode,
It is preferable to dispose the gas at a lower part in order to facilitate the accumulation of the generated gas on the back side of the current-carrying surface.

In the present invention, one end of the electrode 2 is connected to the tubular ion exchanger 1.
Is supported by a lid fitted to one end of the. As a supporting method, a method of supporting the collar 7 provided at one end of the electrode 2 with the upper lid 4 as shown in FIGS. 1 and 2, and bonding one end of the tubular ion exchanger 1 as shown in FIG. When the lid is formed by potting with an agent, a method of fixing the electrode 2 so that the electrode 2 penetrates the lid made of an adhesive from outside the tube of the tubular ion exchanger to the inside of the tube may be used.

In general, the dialysis electrode device of the present invention is used by immersing the lower part from the upper end of the tubular ion exchanger in the electrodeposition coating liquid in a vertical state so that the axis of the tubular ion exchanger is substantially vertical. Is done. In this case, the open end of the lower end of the tubular ion exchanger is closed by the lower lid 3 so as not to mix the polar solution in the tube of the tubular ion exchanger with the electrodeposition coating solution, but the upper end is open. Good. When the entire dialysis electrode device of the present invention is used by immersing it in an electrodeposition coating solution, it is necessary to seal the open end of the tubular ion exchanger with a lid.

The upper and lower lids may be attached directly to the ends of the tubular ion exchanger by mechanical bonding using an adhesive or an O-ring, or may be joined to the ends of the tubular ion exchanger. The member 8 may be fixed by the above means, and the joining member 8 may be connected to the upper lid and the lower lid. The connection between the joining member 8 and the upper and lower lids is preferably a detachable method such as a screw as shown in FIG. 2 in order to easily replace the tubular ion exchanger.

The upper lid and the lower lid are not particularly limited as long as they are electrically insulating materials, but generally, plastic materials such as hard PVC, polypropylene, and polyethylene are preferable. Further, as shown in FIG. 3, the lid may be formed by potting with an adhesive. In addition, since the tubular ion exchanger undergoes dimensional change due to lubrication shrinkage between the dry state and the wet state, a relatively soft adhesive rubber-based adhesive may be used when joining the upper and lower lids. Preferably, a method of decomposing ion exchange groups on the bonding surface of the tubular ion exchanger with an oxidizing agent or the like and inactivating them in advance to perform bonding is also desirable.

The supply and discharge ports of the polar solution provided in the dialysis electrode device of the present invention may be provided so that the polar solution can flow from one end to the other end in the tube of the tubular ion exchanger. For example, as shown in FIG. 1 and FIG.
It is preferable that each of the upper lids 4 is provided with a discharge port 5 for the polar liquid, and the polar liquid is discharged from the discharge port 5 by overflow. Further, as shown in FIG. 3, a tubular electrode is used as the electrode, and the polar liquid is supplied from the upper end of the electrode into the tube.
The polar solution is supplied from the polar solution supply port 6 provided at the lower end of the electrode into the tube of the tubular ion exchanger, and is passed from the lower end to the upper end of the tubular ion exchanger. A mode in which the liquid is discharged from the discharge port 5 can also be adopted.

The following method is preferably employed as a method for discharging the polar solution supplied into the tubular ion exchanger after the completion of the electrodeposition coating. As shown in FIG. 4, a polar liquid supply pipe 10 is connected to a polar liquid discharge pipe 13 having one end opened.
, Valves 14 and 15 are provided at two locations with the connecting position of the discharge pipe 13 for the polar solution therebetween, and a valve 16 is also provided on the discharge pipe 13 for the polar solution. When the dialysis electrode device is pulled up from the electrodeposition coating liquid or when the electrodeposition coating liquid is removed from the bath, the valve 15 is closed, the valves 14 and 16 are opened, and the inside of the discharge pipe 13 for the electrode is discharged. The liquid is filled, then the valve 14 is closed and the valve 15 is opened so that the polar liquid in the tubular ion exchanger can be easily discharged by the siphon principle.

As the polar solution, water may be used. However, in order to efficiently and uniformly remove acid or alkali, an external tank or the like is provided and the dialyzed acid or alkali polar solution is reduced with water to a certain level. A method of circulating while controlling the concentration is preferred.

According to the dialysis electrode device of the present invention, as shown in FIG. 2, two or more tubular ion exchangers are coated with an appropriate adhesive in a large bathtub, for example, for electrodeposition coating of an automobile body. Flange Joined by screw-in type etc.
It is also possible to configure a long device.

Further, as shown in FIG. 5, by connecting two tubular ion exchangers via a flexible cylinder 17, the dialysis electrode device can be bent at the position of the flexible cylinder 17. It is possible. According to FIG. 5, a joining member 8 fitted to the tubular ion exchanger is fixed to the ends of the two tubular ion exchangers 1 by bonding with an adhesive or by fusion. The joining member 8 is threaded. On the other hand, a threaded joining member 8 'is also fixed to both ends of the flexible cylindrical body 17, and the joining member 8' is connected to the joining member 8 of the tubular ion exchanger.

The electrodes 2 in the two tubular ion exchangers are connected to each other by a flexible conductor 18.

Further, in order to prevent breakage during handling of the dialysis electrode device of the present invention, in particular, the tubular ion exchanger, the device has many openings so as not to obstruct the flow of a solution used for electrodeposition coating or the like. It is preferable to attach the mesh frame 19 as a cover to the outer surface of the tubular ion exchanger as shown in FIG. In this case, it is preferable that the lower end of the frame 19 be fixed to the dialysis electrode device so as to be located below the lower lid 3. By doing so, even if the dialysis electrode device is placed on the bottom of the battery case or on the floor, the lower lid of the dialysis electrode device does not contact the bottom of the battery case or on the floor. Body damage can be prevented. The frame 19 also has a function as a guide for movement of the lower lid accompanying extension of the tubular ion exchanger when the dialysis electrode device of the present invention is immersed in the electrodeposition coating solution.

The dialysis electrode device of the present invention is generally installed in the electrodeposition coating liquid such that the axis of the tubular ion exchanger is substantially vertical as described above, as shown in FIG. By providing such a bent portion, the tubular ion exchanger can be installed so that its axis is horizontal. Also, 2
Two dialysis electrode devices may be installed in a V-shape, and the lower ends of both may be connected by a polar liquid supply pipe.

(Effect)

In the dialysis electrode device of the present invention, the lower end of the tubular ion exchanger can freely move up and down in accordance with the elongation of the tubular ion exchanger when immersed in the electrodeposition coating solution. For this reason, the tubular ion exchanger does not wrinkle due to the extension of the exchange ion exchanger, and there is almost no possibility of damage due to the wrinkle.

In addition, the dialysis electrode device of the present invention has a tubular ion exchanger used as a diaphragm, which has higher durability than the conventional ion exchange membrane, and has a simple structure without any support material (reinforcing material). Is also easy. Further, in the apparatus of the present invention, since there is no support material between the tubular ion exchanger and the electrode, the acid or alkali to be dialyzed,
For example, impurities such as heavy metals contained in the electrodeposition coating liquid, gas generated in the electrodes, and the like do not stay and are quickly eliminated by the flow of the polar liquid. Therefore, according to the apparatus of the present invention, since the retention of gas and the deposition of heavy metals and the like in the tubular ion exchanger are extremely small, the increase in electric resistance over time and the unevenness of current distribution are eliminated, resulting in consumption. The power consumption is reduced, and dialysis of acid or alkali is efficiently achieved, and thus a uniform coating film can be obtained, for example, in electrodeposition coating. In the present invention, the electrode device is mainly described as an electrode device for electrodeposition coating. However, the present invention is not limited to this, and may be used as an electrode device for dialysis in other electroplating and the like.

〔Example〕

Hereinafter, although an example of the present invention is shown, the present invention is not limited to this.

Example 1 [Production of Tubular Ion Exchanger] 50 mm outside diameter × 44 mm inside diameter × 1 m length made of a polyethylene porous body having an average pore diameter of about 100 μm and a porosity of about 50%
A tubular mixture of polyethylene powder (having an average diameter of about 30 μm or less), chloromethylstyrene, and a paste mixture prepared from divinylbenzene, styrene-butadiene rubber, and benzoyl peroxide is injected and impregnated in a mold. After depressurizing and defoaming, heat polymerization was performed to obtain a tubular polymer molded article. Next, this tubular molded body was immersed in an amino solution to be aminated to form a tubular anion exchanger.

This tubular anion exchanger had an electrical resistance of about 25 Ω-cm ^{2 in} a 0.1 N NaCl solution (25 ° C.) and an exchange capacity of 2.5 meq / g. Also, seal both ends of the tube and put 0.5 kg / cm ²
However, almost no deformation was observed. Further, the tensile strength was 20 kg / cm ² .

[Configuration of electrode device for electrodeposition coating]

As shown in FIG. 2, three cylindrical anodes made of SUS304 having an outer diameter of about 38 mm, an inner diameter of 33 mm, and a length of 1 m were placed in a tube in which three of the above tubular anion exchangers (1 m) were connected as shown in FIG. The tube was connected and inserted, the lower end of the tube was sealed with a lower lid, and an open upper lid was provided at the upper end. In addition, the supply port of the polar liquid is connected to the bottom of the lower lid provided at the lower end of the pipe, the outlet of the polar liquid is provided on the side of the upper lid provided at the upper end, and a tank is provided outside the pipe,
Pure water was automatically added based on the specific conductivity to control the concentration of the polar solution and circulated. The connection of the tubular anion exchanger and the installation of the upper and lower lids at the upper and lower ends and the supply and discharge ports of the polar liquid were all made of hard vinyl chloride resin and fixed with an adhesive.

A bisphenol-type epoxy resin-based cationic paint is used as a main component, and in a solution for electrodeposition coating using acetic acid as a neutralizing agent, a degreased iron-made article is used as a cathode, and the above-described composition is sandwiched between the articles. Two of the thus-obtained diaphragm anode devices were installed, and a direct current was supplied. As a result, at the start of energization, the voltage gradually decreased with time at a voltage of 250 V and a current of about 25 A. However, a coating having a good coating state was obtained by energizing for 5 minutes. The paint in the solution was maintained at a constant concentration while being replenished with time, and the anolyte of the anode device was circulated by adding water in an external tank to a controlled concentration.

Next, a new material to be coated was put into the solution, and the test was performed under the same electrodeposition conditions as described above. As a result, the current showed the same time-dependent change after 5 minutes of energization, and a good coated product was obtained. Was.
Such electrodeposition coating was repeated 20 times, and a good coated product could be obtained under almost the same electrodeposition conditions, and the neutralizing agent (acid) removal rate during this period was 92%. The tubular ion exchanger grew 5%, but no wrinkles occurred.

Example 2 An electrode device as shown in FIG. 1 was constructed using one of the tubular ion exchangers (1 m) produced in Example 1. For comparison, a similar electrode device was constructed by filling a gap between the tubular anion exchanger and the electrode with a tubular porous plastic mesh.

Using the body of the object to be coated as a cathode, two pieces of electrode devices (for a total of four pieces) of the above-described examples and the comparative example were placed in a cationic electrodeposition coating solution having the same composition as in Example 1. ) Were installed near the same distance from the car body, and operation tests were performed. The energization was performed in the same manner as in Example 1 by providing a constant-voltage DC power supply device, wiring the four electrode devices in parallel, and preparing ammeters for each.

As a result, at the beginning of operation, the voltage was constant at 270 V, about 15 A in the electrode device for the example, and about 1 A in the electrode device for the comparative example.
Although the current was 3 A, it decreased with time, and the continuous operation for about 3 months resulted in about 14 A for the example and about 8 A for the comparative example.
Down to Table 1 shows the results of measuring the removal rate of the neutralizing agent (acid) at the beginning of operation and after continuous operation for about three months for each electrode device.

Further, after three months of operation, each electrode device was disassembled, and the exchange capacity of the tubular anion exchanger was measured. The results are shown in Table 2 together with the initial exchange capacity.

As a result of measuring the fluorescent X-ray intensity on the inner surface of the tubular anion exchanger after the operation for about three months, for both the examples and the comparative examples, heavy metals such as Fe, Cr, Pb, Ni, and Sn were used. However, the strength was particularly strong in the tubular anion exchanger for the comparative example, and was strongly observed up to the inside.

From the above measurements, in the electrode device for the comparative example in which a mesh is interposed between the tubular anion exchanger and the electrode, the liquid and gas are likely to stay due to the presence of the mesh, It is more susceptible to oxidation, which is reflected in a decrease in exchange capacity and a decrease in neutralizing agent (acid) removal efficiency as compared with the examples, and the deposition of heavy metals on the tubular anion exchanger, It is presumed that this causes an increase in electric resistance and a decrease in current over time.

Further, the tubular ion exchanger expanded about 10 cm in the electrodeposition coating solution, but the shape was not changed in the electrode device of this embodiment.
On the other hand, in the electrode device of the comparative example, since the tubular ion exchanger is bonded at both ends together with the porous plastic mesh, the elongation of the tubular ion exchanger is not absorbed and is large. Was generated, and breakage was broken, so it was repaired with an adhesive before use.

Example 3 [Production of Tubular Ion Exchanger] Pulverized anion exchange resin (average particle size of 100 μm or less) having a styrene-divinylbenzene copolymer as a skeleton and a quaternary ammonium base as an exchange group, having a melt index of 0.4 g / 10 minutes of low-density polyethylene powder and stearic acid are mixed, and the powder
A pipe-shaped tubular anion exchanger having a size of mm × 44 mm inner diameter × 1 m length was formed.

This tubular anion exchanger has an electric resistance of about 50 Ω-cm ^{2 in} a 0.1N-NaCl solution (25 ° C.), an exchange capacity of 2.2 meq / g, and seals both ends of the tube to form 0.5 kg of gas inside the tube. A water pressure of / cm ² was applied, but almost no deformation was observed. Further, the tensile strength was 21 kg / cm ² .

[Configuration of electrode device for electrodeposition coating]

In a tube of the above-mentioned tubular anion exchanger (1 m), a Ti substrate was plated with a 5 μm-thick Pt layer as an anode.
A lath-like flat plate having a length of 120 cm was inserted, the lower end was closed with a lower lid as in Example 2, and an open upper lid was provided at the upper end. In addition, the supply port of the polar liquid is connected to the bottom of the lower lid provided at the lower end of the pipe, the outlet of the polar liquid is provided on the side of the upper lid provided at the upper end, and a tank is provided outside the pipe, The system was configured such that pure water was automatically added according to the specific conductivity to control the concentration of the polar solution and circulated. The upper lid, the lower lid, and the supply and discharge ports of the polar liquid were made of hard vinyl chloride resin, and were connected by an adhesive.

A bisphenol-based epoxy resin-based cationic paint as a main component, in a solution of electrodeposition coating using lactic acid as a neutralizing agent, a degreased iron-made article is used as a cathode, and the anode is used as an anode so as to sandwich the article. Were installed, and a direct current was applied in the same manner as in the previous example.

As a result, at the start of operation, a constant voltage of 300 V and a current of about 27 A
However, it decreased with time, and after 4 minutes, the energization was stopped, and a coated product having a good coated surface state was obtained. The same energization treatment was repeated 20 times using a new article to be coated, and the change with time of the current showed almost the same tendency. During this time, the removal rate of the neutralizing agent was 90.5%. The elongation of the tubular ion exchanger was 8%, but no wrinkles occurred.

[Brief description of the drawings]

FIGS. 1, 2, 3, and 5 are cross-sectional views of the dialysis electrode device of the present invention cut along a plane parallel to the vertical direction, and FIG. FIG. 6 is a schematic diagram showing an example of the connection of FIG. 6, and FIG. 6 is a schematic diagram showing the dialysis electrode device of the present invention. In the figure, 1 is a tubular ion exchanger, 2 is an electrode, 3 is a lower lid, 4 is an upper lid, 5 is an outlet for polar liquid, 6 is a supply port for polar liquid, 7 is a collar of the electrode, and 8 and 8 ′ are electrodes. Joining member, 9 is an O-ring, 10 is an anolyte supply pipe, 11 is a guide pipe, 12 is a nut, 13 is an anolyte discharge pipe, 14, 1
5 and 16 are valves, 17 is a flexible cylinder, 18 is a flexible conductor, and 19 is a frame.

Claims (1)

(57) [Claims] 1. A tubular ion exchanger having one end or both ends open, an electrode inserted into a tube thereof, and a lid fitted to an open end of the tubular ion exchanger, and fitted to one end of the tubular ion exchanger. One end of an electrode is supported on the combined lid, and the other end of the tubular ion exchanger is movable in the axial direction in accordance with expansion and contraction of the tubular ion exchanger. An electrode device for dialysis, comprising a supply port and a discharge port for the polar solution for flowing the polar solution from one end to the other end.