JP6737035B2 - Metal electrodeposited cathode plate and method for producing the same - Google Patents

Description

The present invention relates to a metal electrodeposition cathode plate and a method for manufacturing the same.

BACKGROUND ART Conventionally, electric nickel used as an anode raw material for nickel plating is placed in a titanium basket serving as an anode holder and hung in a nickel plating tank for use. At this time, as the electric nickel used as the anode raw material, plate-shaped electric nickel electrodeposited on the cathode plate was cut into small pieces.

However, since small pieces of electric nickel have sharp corners, it is difficult to handle when they are put into a titanium basket. In addition, the small pieces of electric nickel that are thrown into the titanium basket cause the corners to catch on the mesh of the titanium basket and cause so-called hanging, which changes the filling state in the titanium basket and causes uneven plating. There were cases where

Therefore, it has been proposed to use rounded, rounded small lump (button-shaped) electric nickel. The small electric nickel is, for example, a cathode plate in which a plurality of circular conductive portions are arranged at equal intervals, and nickel is deposited on the conductive portion by electrolysis, and then nickel is electrodeposited from the conductive portion. It can be manufactured by peeling off. According to such a method, a plurality of small lumps of electric nickel can be efficiently produced from one cathode plate.

FIG. 5: is a figure which shows an example of the conventional cathode plate used for manufacture of a blob-shaped electric nickel. The cathode plate 11 is masked with the non-conductive film 13 on the flat metal plate 12 except for the portions to be the conductive portions 12a. The film 13 is a convex portion. By using such a cathode plate 11, nickel of an appropriate size is electrodeposited on the conductive portion 12a to produce a small lump of electric nickel.

As the method of forming the non-conductive film 13 on the metal plate 12 like the cathode plate 11, for example, as shown in FIG. 6A, a thermosetting epoxy resin or the like is formed on the flat metal plate 12. There is a method of forming a non-conductive film 13 having a desired pattern by applying a conductive non-conductive resin by a screen printing method and heating it (see Patent Documents 1 and 2). Note that FIG. 6B shows a state in which nickel (electric nickel) 14 is electrodeposited on the conductive portion 12a by using the cathode plate 11 on which the non-conductive film 13 is formed. In the cathode plate 11, nickel 14 begins to be electrodeposited from the conductive portion 12a, grows not only in the thickness (vertical) direction but also in the planar (horizontal) direction, and rises above the non-conductive film 13 as well. ..

Further, for example, as shown in FIG. 7A, a photosensitive non-conductive resin is applied on the metal plate 22, and the non-conductive resin in a portion corresponding to the conductive portion 22a is removed by exposure and development. Then, a method of forming the non-conductive film 23 having a desired pattern has also been proposed. Note that FIG. 7B shows a state in which nickel (electric nickel) 24 is electrodeposited on the conductive portion 22a by using the cathode plate 21 on which the non-conductive film 23 is formed. Also in the cathode plate 21, the nickel 24 starts to be electrodeposited from the conductive portion 22a and grows not only in the thickness direction but also in the plane direction.

Furthermore, by fixing the periphery of a metal structure in which a plurality of conductive studs are arranged at equal intervals with an insulative resin by an injection molding method, the cathode plate forming the non-conductive portion is formed. A manufacturing method has also been proposed (see Patent Document 3).

Japanese Patent Publication No. 51-036693 Japanese Patent Laid-Open No. 52-152832 Japanese Patent Publication No. 56-029960

By the way, in the case of producing small lumps of electric nickel using the cathode plate as described above, the non-conductive film (non-conductive portion) formed on the cathode plate has a long life, and the non-conductive film is missing (degraded). Even if it does, it is required that it can be easily maintained.

As shown in FIG. 6A, when the non-conductive resin is applied to the metal plate 12 by screen printing to form the non-conductive film 13, the thickness of the non-conductive film 13 approaches the conductive portion 12a. Therefore, since the thickness gradually decreases, the thickness becomes extremely thin at the boundary with the conductive portion 12a. Such a change in the film thickness of the non-conductive film 13 is caused by the coating amount of the non-conductive resin, the viscosity of the non-conductive resin and the temperature characteristic of the viscosity, the curing temperature of the non-conductive resin, the surface roughness of the metal surface and the free surface. Depends on energy etc. Therefore, the film thickness of the non-conductive film 13 becomes very thin at the boundary with the conductive portion 12a.

As described above, when small lump-shaped electric nickel is manufactured using the cathode plate 11 as shown in FIGS. 5 and 6, nickel 14 starts to be electrodeposited from the conductive portion 12a, and not only in the vertical direction but also in the horizontal direction. Since it also grows, it gradually rises on the non-conductive film 13. Therefore, in the portion of the thin non-conductive film 13 formed in the vicinity of the boundary with the conductive portion 12a, the adhesion with the metal plate 12 is likely to be lowered due to the permeation of the electrolytic solution, and the stress at the time of electrodeposition of the nickel 14 is reduced. It is easy to drop due to the impact when stripping the nickel or its electric nickel. In addition, once the non-conductive film 13 is lost, the non-conductive film 13 around the non-conductive film 13 is lifted from the surface of the metal plate 12, so that the electrolytic solution is more likely to enter the gap, and as a result, nickel is continuously charged. When it is attempted to be deposited, the electrolytic solution submerges in the gap of the non-conductive film 13 lifted from the surface of the metal plate 12, and the nickel 14 is electrodeposited. Then, if it is attempted to peel off the nickel 14 that has penetrated into the gap and electrodeposited, the non-conductive film 13 in which the nickel 14 is caught is further lost.

As described above, in the conventional cathode plate 11, the non-conductive film 13 is missing in a chained manner, and when the missing parts are spread, the nickels 14 grown from the adjacent conductive parts 12a are easily connected to each other. It is not possible to obtain electric nickel in the shape of, and it becomes a defective product. Therefore, it becomes necessary to peel off all the non-conductive films 13 and form the non-conductive film 3 again to maintain the cathode plate 11 before the loss of the non-conductive film 13 occurs. However, in practice, the cathode plate 11 needs to be serviced at the stage where nickel has been electrodeposited several times to less than 10 times, which not only lowers productivity but also increases service cost.

On the other hand, as shown in FIG. 7A, in the cathode plate 21 in which the non-conductive film 23 is formed by exposure and development using a photosensitive non-conductive resin, the non-conductive film 23 is formed with a uniform thickness. can do. However, when the nickel 24 is peeled off after electrodeposition, the nickel 24 is caught in the step of the non-conductive film 23 forming the convex portion, and a large impact is easily applied to the non-conductive film 23. Will be lost.

However, for the non-conductive films 13 and 23 of the cathode plates 11 and 21 described above, an epoxy resin is often used for reasons such as high dimensional stability, chemical resistance, and high insulation. Therefore, as described above, when the non-conductive films 13 and 23 made of epoxy resin are stripped for the maintenance of the cathode plates 11 and 21, it is necessary to use a dangerous chemical such as hot concentrated sulfuric acid. Become. The non-conductive films 13 and 23 made of an epoxy resin can be mechanically peeled off by sandblasting or water jet, but a long peeling time is required. For this reason, it is not easy to maintain the cathode plates 11 and 21 even if the non-conductive films 13 and 23 are missing.

In the method of forming the non-conductive part by injection molding as in Patent Document 3, although the life of the non-conductive part formed is long, the manufacturing cost of the cathode plate itself is high and the non-conductive part is deteriorated. In this case, maintenance of the cathode plate is difficult.

The present invention has been made in view of such conventional circumstances, and an object thereof is to provide a metal electrodeposited cathode plate that can be repeatedly used with simple maintenance, and a manufacturing method thereof.

The present inventors have earnestly studied to solve the above-mentioned problem. As a result, a protrusion is provided on the metal plate to form a conductive portion, a non-conductive film is provided on the metal surface other than the protrusion, and the non-conductive film has a laminated structure of an insulating layer and a protective layer, which simplifies the process. They have found that they can be used repeatedly during maintenance, and have completed the present invention.

(1) A first invention of the present invention is a metal plate having a plurality of disk-shaped projections arranged on at least one surface thereof, and a non-conductive film formed on a surface other than the projections of the metal plate. And the non-conductive film is a metal electrodeposition cathode plate including an insulating layer having a thickness of 60 μm or more and a protective layer for protecting the insulating layer.

(2) The second invention of the present invention is the cathode plate for producing electric nickel according to the first invention, wherein the protective layer of the non-conductive film is made of a resist resin that can be stripped with an alkaline aqueous solution.

(3) The third invention of the present invention is the first or second invention, wherein the non-conductive film has a minimum film thickness at a position passing between the centers of the adjacent protrusions equal to the height of the protrusions. The above is the cathode plate for metal electrodeposition.

(4) A fourth invention of the present invention is the cathode plate for metal electrodeposition according to any one of the first to third inventions, wherein the insulating layer of the non-conductive film is made of an epoxy resin.

(5) The fifth invention of the present invention is the metal electrodeposition cathode plate according to any one of the first to fourth inventions, wherein the height of the protrusion is 100 μm or more and 1000 μm or less.

(6) A sixth invention of the present invention is the invention of any one of the first to fifth inventions, wherein the minimum film thickness of the non-conductive film at a position passing between the centers of the adjacent protrusions and the protrusion It is a metal electrodeposited cathode plate having a height difference of 200 μm or less.

(7) A seventh invention of the present invention is the metal electrodeposition cathode plate according to any one of the first to sixth inventions, wherein the metal plate is made of titanium or stainless steel.

(8) The eighth invention of the present invention is the cathode plate for metal electrodeposition according to any one of the first to seventh inventions, which is used for the production of electrolytic nickel for plating.

(9) A ninth invention of the present invention is a method for manufacturing a metal electrodeposition cathode plate, comprising a first step of forming a plurality of disk-shaped projections on at least one surface of the metal plate, and the metal. A second step of forming an insulating layer on the surface of the plate other than the projecting portion, and a third step of forming a protective layer on the insulating layer and forming a non-conductive film composed of the insulating layer and the protective layer. And a manufacturing method.

According to the present invention, it is an object of the present invention to provide a metal electrodeposition cathode plate that can be repeatedly used with simple maintenance and a method for manufacturing the same.

It is a top view which shows the structure of a cathode plate. It is an important section enlarged sectional view showing composition of a cathode plate, (a) is an important section enlarged sectional view explaining a state of a cathode plate before nickel electrodeposition, (b) shows a state of a cathode plate after nickel electrodeposition. It is a principal part expanded sectional view explaining. FIG. 6 is an enlarged cross-sectional view of an essential part showing a configuration of a cathode plate in the case where the thickness of a non-conductive film is small, (a) is an enlarged cross-sectional view of an essential part illustrating a state of the cathode plate before nickel electrodeposition, and (b) is It is a principal part expanded sectional view explaining the state of the cathode plate after nickel electrodeposition. It is a principal part enlarged sectional view explaining the manufacturing method of a cathode plate, (a) is a principal part enlarged sectional view explaining a 1st process, (b) is a principal part enlarged sectional view explaining a 2nd process, (c) [Fig. 8] is an enlarged cross-sectional view of a main part for explaining Otei, the third ward. It is a top view which shows the structure of the conventional cathode plate. It is a principal part expanded sectional view which shows the structure of the conventional cathode plate, (a) is a principal part enlarged sectional view explaining the state of the cathode plate before nickel electrodeposition, (b) is a cathode after nickel electrodeposition It is a principal part expanded sectional view explaining the state of a board. It is a principal part expanded sectional view which shows the structure of the conventional cathode plate, (a) is a principal part enlarged sectional view explaining the state of the cathode plate before nickel electrodeposition, (b) is a cathode after nickel electrodeposition It is a principal part expanded sectional view explaining the state of a board.

Hereinafter, an embodiment (hereinafter, referred to as “this embodiment”) in which the metal electrodeposition cathode plate of the present invention is applied to a metal electrodeposition cathode plate used for producing electric nickel will be described in detail. It should be noted that the present invention is not limited to the following embodiments, but can be modified as appropriate without departing from the scope of the invention.

<1. Metal electrodeposited cathode plate>
(1) Configuration of Cathode Plate As shown in FIG. 1, the cathode plate 1 according to the present embodiment has a metal plate 2 in which a plurality of disc-shaped protrusions 2a are arranged, and a protrusion 2a of the metal plate 2. Other than the non-conductive film 3 formed on the surface. As will be described later, the cathode plate 1 is used by being suspended by a suspending member 5 in an electrolytic bath containing an electrolytic solution containing nickel and an anode, and nickel having a desired shape is electrodeposited on the surface thereof. Let

[Metal plate]
As shown in FIGS. 1 and 2A, the metal plate 2 is a flat metal plate and has a plurality of disk-shaped protrusions 2a. Here, in the metal plate 2, the surface other than the protruding portion 2a is referred to as a "flat portion 2b" with respect to the protruding portion 2a. The “height X of the protrusion” is the height of protrusion from the surface of the flat portion 2b of the metal plate 2.

Although FIG. 2 shows an example in which the protrusion 2a is provided on one surface of the metal plate 2, the metal plate 2 may have the protrusion 2a on both surfaces.

The size of the metal plate 2 is not particularly limited and may be appropriately selected according to the size and number of desired electric nickel. For example, the size may be a rectangular size having a side of 100 mm or more and 2000 mm or less. .. The thickness of the metal plate 2 is preferably, for example, 1.5 mm or more and 5 mm or less when the protrusion 2a is provided on one surface, and when the protrusion 2a is provided on both surfaces. Is preferably, for example, about 3 mm or more and 10 mm or less. If the thickness of the metal plate 2 is too small, the protrusion 2a and the flat portion 2b tend to warp. Further, if the thickness of the metal plate 2 is too large, the weight of the metal plate 2 increases and it becomes difficult to handle.

The material of the metal plate 2 is not particularly limited as long as it is a metal that is less corroded by the electrolytic solution used and forms only a loose bond with an electrodeposit such as nickel, but titanium and stainless steel are preferred.

In the metal plate 2, the plurality of disc-shaped protrusions 2a have their surfaces exposed from a non-conductive film 3 described later to function as a conductive portion, and the non-conductive film 3 is formed with a predetermined thickness. Therefore, a concave step is formed by the adjacent protrusions 2a. Hereinafter, the surface of the protrusion 2a exposed from the non-conductive film 3 may be referred to as a "conductive portion 2c". In the conductive portion 2c, nickel 4 is electrodeposited by electrolytic treatment.

The size of the disk-shaped protrusion 2a may be appropriately set according to the desired size of electric nickel, and the diameter thereof can be, for example, 5 mm or more and 30 mm or less. The height X of the protrusion 2a is preferably 50 μm or more and 1000 μm or less, and more preferably 100 μm or more and 500 μm or less. If the height X of the protrusion 2a is too small, the film thickness of the non-conductive film 3 formed on the flat portion 2b of the metal plate 2 becomes insufficient, and the stress at the time of electrodeposition of the nickel 4 and its nickel It is easy to fall off due to the impact of peeling. On the other hand, if the height X of the protrusions 2a is too large, for example, when the non-conductive film is formed by screen printing, the number of times of application increases and the productivity decreases. If the height X is too large, the metal plate 2 is likely to be distorted when the protrusion 2a is processed, and the metal plate 2 is likely to warp, which makes it difficult to form the non-conductive film 3. It is possible to increase the thickness of the metal plate 2 in order to reduce the influence of the distortion of the metal plate 2, but the weight of the metal plate 2 increases and handling becomes difficult.

Further, fine irregularities may be provided on the surface of the metal plate 2, that is, the surface of the disk-shaped protrusion 2a of the metal plate 2 by sandblasting or etching. As a result, the nickel 4 electrodeposited on the protrusions 2a can be peeled off with an appropriate impact without dropping off during the electrolytic treatment. In this case, it is preferable that the film thickness of the non-conductive film 3 described later is twice or more the maximum surface roughness Rz of the metal plate 2. If the film thickness of the non-conductive film 3 is smaller than twice the maximum surface roughness Rz of the metal plate 2, there is a concern that pinholes or insulation failure parts of the non-conductive film 3 may occur.

[Non-conductive film]
As shown in FIG. 2, the non-conductive film 3 is formed on the flat portion 2b which is a surface of the metal plate 2 other than the protrusions 2a, whereby the plurality of protrusions 2a arranged on the metal plate 2 are arranged. The surface, that is, the conductive portion 2c is exposed. Then, the nickel 4 is electrodeposited and deposited on the conductive portion 2c of the metal plate 2 as described above, so that the nickel 4 is individually divided into a small lump shape.

By the way, as shown in FIG. 2A, the non-conductive film 3 has a laminated structure including an insulating layer 3a having a thickness of 60 μm or more and a protective layer 3b for protecting the insulating layer 3a. The layer 3b is the outermost surface. It should be noted that any other layer may be included between the insulating layer 3a and the protective layer 3b. The insulating layer 3a and the protective layer 3b will be described below.

(Insulating layer)
The insulating layer 3a is a layer having an insulating property. The material forming the insulating layer 3a is not particularly limited as long as it has an insulating property, but a material that is less corroded by the electrolytic solution used and has high adhesion to the metal plate 2 is preferable. For example, from the viewpoint of easier film formation, it is preferable to use a thermosetting resin or a photo-curing (ultraviolet curing) resin, and specifically, an epoxy resin, a phenol resin, a polyamide resin, a polyimide. An insulating resin such as a system resin may be used.

Since the insulating layer 3a is formed on the flat portion 2b having the concave step formed by the adjacent protrusions 2a, it is formed with a predetermined thickness. The thickness of the insulating layer 3a is 60 μm or more. Further, the thickness of the insulating layer 3a is preferably 100 μm or more, and more preferably 200 μm or more. When the thickness of the insulating layer 3a is less than 60 μm, pinholes are generated in the insulating layer 3a, which tends to make it difficult to secure the insulating property. On the other hand, if the thickness of the insulating layer 3a is too large, the height X of the protrusion 2a is exceeded, and it becomes difficult to form the protective layer 3b. The upper limit of the thickness of the insulating layer 3a is preferably set appropriately in relation to the thickness of the protective layer 3b described later, but is preferably 800 μm or less, for example.

(Protective layer)
The protective layer 3b is formed on the insulating layer 3a, and has a function of protecting the insulating layer 3a from the stress when the nickel 4 is electrodeposited and the impact when the electric nickel is stripped off.

The protective layer 3b is a layer laminated on the insulating layer 3a in the non-conductive film 3, and is in contact with the nickel 4 exposed on the surface of the cathode plate 1 and electrodeposited. Therefore, it is expected that the protective layer 3b is likely to be deteriorated or chipped due to the stress at the time of electrodeposition of the nickel 14 and the impact at the time of stripping the electric nickel. Therefore, in the protective layer 3b, it is preferable to re-apply before the exposure of the lower insulating layer 3a becomes large, and in this respect, the material forming the protective layer 3b is, if necessary, from the insulating layer 3a. It is preferable to use a material that can be easily peeled off.

Specifically, the protective layer 3b is preferably made of a resist material that can be stripped with an alkaline aqueous solution. A resist material that can be peeled off with an alkaline aqueous solution is easy to form a film by heat curing or photo-curing (such as UV curing), and peeling is easy if necessary, so that maintenance of the cathode plate 1 is easy. ..

As the resist material which can be stripped off with an alkaline aqueous solution, those commercially available as plating resists can be used, and examples thereof include PLAS FINE PER-3000 manufactured by Kao Kagaku Kogyo KK and SD2149SIT-HS manufactured by PETERS.

The thickness of the protective layer 3b is not particularly limited, but is preferably 30 μm or more. Further, it is more preferably 50 μm or more and 400 μm or less, and particularly preferably 60 μm or more and 200 μm or less. If the thickness of the protective layer 3b is too small, the insulating layer 3a cannot be protected, and the insulating layer 3a needs to be maintained, which makes repeated use of the cathode plate 1 difficult. On the other hand, if the thickness of the protective layer 3b is too large, the non-conductive film 3 composed of the protective layer 3b must be formed to greatly exceed the height X of the protrusion 2a, which is not practical. Absent.

Here, it is preferable that the minimum film thickness Y of the non-conductive film 3 including the insulating layer 3a and the protective layer 3b is equal to or greater than the height X of the protrusion 2a.

The "minimum film thickness Y of the non-conductive film" is defined as the minimum film thickness of the non-conductive film 3 at a position passing between the centers of the adjacent protrusions 2a. As shown in FIG. 2A, the non-conductive film 3 is formed such that the central portion of the non-conductive film 3 rises due to the surface tension between the adjacent protrusions 2 a. In this case, the minimum film thickness Y of the non-conductive film 3 is the film thickness of the end portion that comes into contact with the side surface of the protrusion 2a. In addition, the non-conductive film 3 may be formed on the surface of the protrusion 2a when the film thickness is large. The minimum film thickness Y of the non-conductive film 3 at this time is not the film thickness of the non-conductive film 3 formed on the surface of the protrusion 2a, but the film of the non-conductive film 3 formed at the position on the flat portion 2b. The minimum value of the thickness. In the cathode plate 1, although the film thickness varies depending on the position of the protruding portion 2a to be selected, the minimum value of them is the minimum film thickness Y.

Since the minimum film thickness Y of the non-conductive film 3 is equal to or greater than the height X of the protrusion 2a, when the nickel 4 is stripped from the cathode plate 1, the nickel 4 is stripped without being caught on the peripheral edge of the protrusion 2a. You can On the other hand, as shown in FIG. 3, when the minimum film thickness Y of the non-conductive film 3 is less than the height X of the protrusion 2a, when the electrodeposited nickel 4 is stripped from the cathode plate 1, for example, as shown in FIG. At the portion indicated by "A" in the inside, it is caught on the peripheral portion of the protrusion 2a and is difficult to peel off.

The upper limit of the minimum film thickness Y of the non-conductive film 3 is not particularly limited, but the difference between the minimum film thickness Y and the height X of the protrusion 2a is preferably 200 μm or less, and 5 μm or more and 100 μm or less. Is more preferable. Here, as described above, the minimum film thickness Y of the non-conductive film 3 is not particularly limited as long as it is equal to or higher than the height X of the protrusion 2a, but it is not necessary to make it thicker than necessary. For example, it is difficult to apply the non-conductive film 3 by screen printing so that the height X of the protrusion 2a exceeds 200 μm. When it is attempted to form the non-conductive film 3 having a film thickness of more than 200 μm from the height X of the protrusion 2a by screen printing, it is necessary to finely adjust the size of the pattern on the screen plate a plurality of times, Adjustment is difficult and productivity is reduced.

When the non-conductive film 3 is formed on the flat portion 2b on the metal plate 2 by the screen printing method, the material of the non-conductive film 3 is also applied to the surface of the protrusion 2a, so that the surface area of the conductive portion 2c is reduced. The initial current density may increase, but there is no problem as long as the characteristic of the electrodeposited nickel 4 does not occur. Further, the non-conductive film 3 attached on the surface of the protrusion 2a is apt to be lost because the film thickness is very thin, but the non-conductive film 3 formed on the flat portion 2b is thick and the removal is suppressed. There is no problem because it is done.

(2) Production of Electric Nickel Using Cathode Plate In the cathode plate 1 having the above-described configuration, as shown in FIG. 2B, the surface of the protrusion 2a exposed from the non-conductive film 3 becomes the conductive part 2c. Then, nickel 4 is electrodeposited. In the cathode plate 1, the nickel 4 grows not only in the thickness direction but also in the plane direction, so that the nickel 4 is swelled above the non-conductive film 3. From this, it is preferable to finish the electrodeposition before the nickel 4 grown from the conductive portion 2c of the adjacent protruding portion 2a comes into contact with each other. Then, after the electrodeposition of nickel 4 is completed, the nickel 4 is stripped off from the cathode plate 1, so that a plurality of small lumps of electric nickel can be obtained from one cathode plate 1.

As described above, in the cathode plate 1, the non-conductive film 3 has a laminated structure including the insulating layer 3a and the protective layer 3b that protects the insulating layer 3a. Therefore, the insulating layer 3a protected by the protective layer 3b is not easily deteriorated or chipped even by the stress and stripping during the nickel 4 electrodeposition. On the other hand, the protective layer 3b is likely to be deteriorated or chipped due to peeling off of the nickel 4, but a simple maintenance such as replacement (peeling, re-application) of only the protective layer 3b is required. Therefore, the cathode plate 1 can be repeatedly used while performing simple maintenance, and the maintenance cost can be reduced and the productivity can be improved as compared with the case where the non-conductive film including only the insulating layer is exchanged for maintenance. You can

Although the cathode plate 1 according to the present embodiment is electrodeposited with nickel 4, it is not limited to nickel, and silver, gold, zinc, tin, chromium, cobalt, or alloys thereof may be electrodeposited. ..

<2. Manufacturing method of metal electrodeposited cathode plate>
In the method for manufacturing the cathode plate 1 according to the present embodiment, as shown in FIG. 4, a first step of forming a plurality of disc-shaped protrusions 2a on at least one surface of the metal plate 2 (FIG. 4A). ), a second step of forming the insulating layer 3a on the surface of the metal plate 2 other than the protrusions 2a (FIG. 4B), and a third step of forming the protective layer 3b on the insulating layer 3a (FIG. c)) and.

[First step]
In the first step, a plurality of disc-shaped protrusions 2a are formed on the surface of the metal plate 2. For example, with respect to the flat metal plate 2, the flat portion 2b is formed by cutting away the portion other than the protruding portion 2a and leaving the protruding portion 2a having the height X. The processing method is not particularly limited, and for example, wet etching processing, end mill processing, laser processing or the like can be performed.

For example, when processing a flat plate-shaped stainless steel plate by wet etching, a photosensitive etching resist is applied to the surface of the stainless steel plate, and subsequently, a portion to be exposed through a film or glass on which a desired pattern is drawn and etched. The etching resist is removed by a developing process. Then, the developed stainless steel plate is applied to an etching solution (for example, ferric chloride solution), a part of the stainless steel plate from which the etching resist is removed is removed, and finally the etching resist is peeled off to obtain a desired It is possible to form a plurality of disk-shaped protrusions 2a corresponding to the pattern.

The protrusions 2 a may be formed on only one surface of the metal plate 2, or may be formed on both surfaces of the metal plate 2.

[Second step]
In the second step, the insulating layer 3a is formed on the flat portion 2b which is the surface of the metal plate 2 other than the protruding portion 2a. The method for forming the insulating layer 3a is not particularly limited, and it can be performed by screen printing. When the material of the insulating layer 3a is a thermosetting resin or a photocuring resin, thermosetting or photocuring may be performed as necessary.

[Third step]
In the third step, the protective layer 3b is formed on the insulating layer 3a, and the non-conductive film 3 including the insulating layer 3a and the protective layer 3b is formed. The method of forming the protective layer 3b is not particularly limited, and it can be performed by screen printing, like the insulating layer 3a. When the material of the protective layer 3b is a thermosetting resin or a photocurable resin, heat curing or photocuring may be performed as necessary.

According to the method for manufacturing a cathode plate according to the present embodiment, it is possible to obtain the cathode plate 1 that can be repeatedly used with simple maintenance by the above-described simple method.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. For convenience, members having the same functions as those shown in FIGS. 1 to 6 will be described with the same reference numerals.

<Production of cathode plate>
[Example 1]
A cathode plate 1 as shown in FIGS. 1 and 2 was prepared. Specifically, first, a metal plate 2 made of stainless steel having a size of 200 mm×100 mm×4 mm was wet-etched to form disk-shaped protrusions 2 a (18 pieces). At this time, the size of the protrusion 2a was 14 mm in diameter and the height X was 300 μm, and the distance between the centers of the adjacent protrusions 2a was 21 mm.

Next, a thermosetting epoxy resin was applied onto the flat portion 2b of the metal plate 2 by screen printing and cured by heating at 150° C. for 60 minutes to form an insulating layer 3a having a thickness of about 250 μm. Then, a thermosetting resist (SD2149SIT-HS manufactured by PETERS, Inc.) that can be peeled off with an alkaline aqueous solution is applied to the insulating layer 3a by a screen printing method, and is cured by heating at 130° C. for 30 minutes to have a thickness of about 60 μm. Was formed on the protective layer 3b. In the cathode plate 1 thus manufactured, the difference between the minimum film thickness Y of the non-conductive film 3 and the height X of the protrusion 2a at a position passing between the centers of the adjacent protrusions 2a is determined by a laser displacement meter. Was measured at 10 locations, the range was 10 to 20 μm, and therefore the minimum film thickness Y of the non-conductive film 3 was 310 μm.

[Example 2]
Example 1 except that the height X of the protrusion 2a of the metal plate 2 was 400 μm and the non-conductive film 3 formed by laminating the insulating layer 3a and the protective layer 3b was formed on the flat portion 2b with a predetermined thickness. A cathode plate 1 was prepared in the same manner as in. In the cathode plate 1 thus manufactured, the difference between the minimum film thickness Y of the non-conductive film 3 and the height X of the protrusion 2a was measured at 10 arbitrary positions by a laser displacement meter, and was 10 to 30 μm. Therefore, the minimum film thickness Y of the non-conductive film 3 was 410 μm.

[Example 3]
Example 1 except that the height X of the protrusion 2a of the metal plate 2 was 100 μm and the non-conductive film 3 formed by laminating the insulating layer 3a and the protective layer 3b was formed on the flat portion 2b with a predetermined thickness. A cathode plate 1 was prepared in the same manner as in. In the thus manufactured cathode plate 1, the difference between the minimum film thickness Y of the non-conductive film 3 and the height X of the protrusion 2a was measured by a laser displacement meter at arbitrary 10 points, and it was 100 to 140 μm. Therefore, the minimum film thickness Y of the non-conductive film 3 was 200 μm.

[Example 4]
Example 1 except that the height X of the protrusion 2a of the metal plate 2 was set to 500 μm and the non-conductive film 3 formed by laminating the insulating layer 3a and the protective layer 3b was formed on the flat portion 2b with a predetermined thickness. A cathode plate 1 was prepared in the same manner as in. In the thus manufactured cathode plate 1, the difference between the minimum film thickness Y of the non-conductive film 3 and the height X of the protrusion 2a was measured at 10 arbitrary positions by a laser displacement meter. It was in the range of −100 μm, so the minimum film thickness Y of the non-conductive film 3 was 350 μm.

[Comparative Example 1]
In Comparative Example 1, a conventional cathode plate 11 as shown in FIGS. 5 and 6 was produced. Specifically, a thermosetting epoxy resin is applied to a 200 mm×100 mm×4 mm flat plate-shaped metal plate 12 made of stainless steel by a screen printing method while leaving the conductive portions 12 a (18 pieces) having a diameter of 14 mm. Then, it was cured by heating at 150° C. for 60 minutes to form the non-conductive film 13, and the cathode plate 11 was manufactured. In the thus manufactured cathode plate 11, the film thickness of the insulating layer 3a was measured at 10 arbitrary positions with a laser displacement meter, and it was in the range of 90 to 110 μm.

[Comparative example 2]
A thermosetting resist (made by PETERS, SD2149SIT, which can be stripped by an alkaline aqueous solution by a screen printing method, leaving a conductive portion 12a having a diameter of 14 mm on a flat metal plate 12 made of stainless steel of 200 mm×100 mm×4 mm. -HS) was applied and cured by heating at 130° C. for 40 minutes to form a protective layer, and the cathode plate 11 was manufactured. In the thus manufactured cathode plate 1, the film thickness of the non-conductive film 13 (protective layer 3b) was measured at 10 arbitrary positions by a laser displacement meter, and it was 30 μm.

[Comparative Example 3]
The metal electrodeposition was performed in the same manner as in Example 1 except that the height X of the protrusions of the metal plate was 100 μm and the non-conductive film formed by laminating the insulating layer and the protective layer on the flat portion had a predetermined thickness. A cathode plate was created. In the thus manufactured cathode plate 1, the difference between the minimum film thickness Y of the non-conductive film and the height X of the protrusions 2a was measured by a laser displacement meter at 10 arbitrary positions. Therefore, the minimum film thickness Y of the non-conductive film was 110 μm.

[Comparative Example 4]
A 200 mm×100 mm×4 mm stainless steel metal plate was wet-etched to form protrusions (18) having a height of 2000 μm. However, the warp of the metal plate was large, and it was difficult to form the non-conductive film by screen printing.

<Manufacture of electric nickel>
Electrolytic nickel was produced by electrolytic treatment using the cathode plates produced in the respective examples and comparative examples. Specifically, a cathode plate and an anode plate made of 200 mm×100 mm×10 mm electric nickel were immersed in an electrolytic cell containing a nickel chloride electrolytic solution so as to face each other. Then, nickel was electrodeposited on the surface of the cathode plate under the conditions of an initial current density of 710 A/m ² and an electrolysis time of 3 days. After electrolysis, the electric nickel deposited on the cathode plate was peeled off to obtain a small lump of electric nickel for plating.

<Evaluation>
The number of times the cathode plate used for the electrolytic treatment could be repeatedly used as it was was evaluated. In the cathode plate 1 having the protective layer 3b, every time the electrodeposition and stripping of the nickel 4 were repeated twice, the protective layer 3b was stripped with an alkaline aqueous solution to form the protective layer 3b again. If the loss of the non-conductive film spreads, nickel that has been electrodeposited in the adjacent conductive portions will be connected to each other, and electric nickel having a desired shape cannot be obtained. Therefore, when the non-conductive portion was missing from the boundary with the conductive portion in the flat portion direction by 1 mm or more, the use was stopped and the number of repetitions up to this point was evaluated. Further, even when the non-conductive film was missing and the diameter of the conductive part was expanded by 1 mm or more, the use was stopped and the number of repetitions up to this point was evaluated.

Table 1 below shows the evaluation results together with the constitution of the cathode plate.

As shown in Table 1, in Examples 1 to 3 using the cathode plate 1 in which the non-conductive film 3 including the insulating layer 3a and the protective layer 3b was formed on the flat portion 2b of the metal plate 2, the protective layer 3b was used. Although the electrodeposition and stripping of nickel 4 were repeated 20 times while replacing the above, it was possible to reuse the nickel 4 without stopping the use and to efficiently obtain electric nickel.

In addition, in Example 4, although it could be used repeatedly, nickel 4 was caught at the peripheral edge of protrusion 2a, and it was slightly difficult to strip nickel 4. From this, from the viewpoint of stripping off the nickel 4, it is understood that the minimum film thickness Y of the non-conductive film 3 including the insulating layer 3a and the protective layer 3b is preferably equal to or higher than the height X of the protrusion 2a.

On the other hand, in Comparative Example 1 in which the cathode plate in which the non-conductive film 13 (insulating layer) is formed on the flat metal plate 12 is used, the insulating layer begins to be lost after about 7 times of use, and the repeated use is sufficiently repeated. I couldn't. Further, in Comparative Example 2 in which the cathode plate in which only the protective layer was formed on the flat metal plate 12 was used, pinholes were generated, insulation was not sufficient, and electric nickel having a desired shape could not be obtained. Further, also in Comparative Example 3 in which a cathode plate having a small insulating layer thickness of 50 μm was used, pinholes were generated, insulation was not sufficient, and electric nickel having a desired shape could not be obtained.

DESCRIPTION OF SYMBOLS 1 Cathode plate 2 Metal plate 2a Projection part 2b Flat part 2c Conductive part 3 Non-conductive film 3a Insulating layer 3b Protective layer 4 Nickel

Claims (9)

A metal plate having a plurality of disk-shaped protrusions arranged on at least one surface,
A non-conductive film formed on the surface of the metal plate other than the protrusions,
The non-conductive film includes an insulating layer having a thickness of 60 μm or more and a protective layer that protects the insulating layer.
Metallic electrodeposit cathode plate. The protective layer of the non-conductive film is composed of a resist resin that can be peeled off with an alkaline aqueous solution,
The cathode plate for producing electric nickel according to claim 1. In the non-conductive film, the minimum film thickness at a position passing between the centers of the adjacent protrusions is equal to or higher than the height of the protrusions.
The cathode plate for metal electrodeposition according to claim 1 or 2. The insulating layer of the non-conductive film is made of epoxy resin,
The metal electrodeposited cathode plate according to claim 1. The height of the protrusion is 100 μm or more and 1000 μm or less,
The cathode plate for metal electrodeposition according to any one of claims 1 to 4. The difference between the minimum film thickness of the non-conductive film at a position passing between the centers of the adjacent protrusions and the height of the protrusions is 200 μm or less.
The metal electrodeposited cathode plate according to any one of claims 1 to 5. The metal plate is made of titanium or stainless steel,
The cathode plate for metal electrodeposition according to any one of claims 1 to 6. Used in the production of electroplating nickel,
The metal electrodeposited cathode plate according to any one of claims 1 to 7. A method of manufacturing a metal electrodeposition cathode plate,
A first step of forming a plurality of disk-shaped protrusions arranged on at least one surface of the metal plate;
A second step of forming an insulating layer having a thickness of 60 μm or more on the surface of the metal plate other than the protrusions;
A third step of forming a protective layer on the insulating layer and forming a non-conductive film including the insulating layer and the protective layer.

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