JP2018012864A - Cathode plate for metal electro-deposition and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cathode plate for metal electro-deposition unlikely to separate a non-conductive film, allowing a repeated use, and a manufacturing method thereof.SOLUTION: A cathode plate 1 is composed of a metal plate 2 having a plurality of ring-shaped grooves 2b aligned thereon, and includes: a conductive part 2a formed by a surface on an inner side of a ring shape of a ring-shaped groove 2b, being a surface of the metal plate 2; and a non-conductive part 3 formed on a surface on an inside of the ring-shaped groove 2b and an outer side of the ring shape of the ring-shaped groove 2b, on the surface of the metal plate 2. A depth X of the ring-shaped groove 2b is preferably 50-1000 μm. A width Y of the ring-shaped groove 2b is preferably 100 μm or more.SELECTED DRAWING: Figure 1

Description

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

  Conventionally, electric nickel provided as an anode raw material for nickel plating has been used in a titanium basket serving as an anode holder and suspended in a nickel plating tank. At this time, as the electric nickel as the anode raw material, a plate-like electric nickel electrodeposited on the cathode plate was cut into small pieces.

  However, since the small pieces of electro nickel have sharp corners, they are difficult to handle when throwing them into the titanium basket. In addition, when the small pieces of electro nickel are put into the titanium basket, the corners get caught in the mesh of the titanium basket and cause so-called shelf hanging, and the filling state in the titanium basket changes, causing the occurrence of uneven plating. There was sometimes.

  In view of this, it has been proposed to use round nickel (button-shaped) electric nickel with rounded corners. For example, a small lump of electric nickel is obtained by depositing nickel on the conductive part by electrolysis using a cathode plate in which a plurality of circular conductive parts are arranged at equal intervals, and then electrodepositing from the conductive part. It can be manufactured by stripping off. According to such a method, it is possible to efficiently produce a plurality of small blocks of electro nickel from one cathode plate.

  FIG. 5 is a diagram showing an example of a conventional cathode plate used for producing a small lump of electronickel. The cathode plate 11 is masked with a non-conductive film 13 on a flat metal plate 12 except for a portion to be a conductive portion 12a. In the cathode plate 11, the conductive portion 12a becomes a concave portion and is non-conductive. The film 13 is a convex portion. By using such a cathode plate 11, nickel having an appropriate size is electrodeposited on the conductive portion 12 a to produce a small lump of electric nickel.

  As a method of forming the nonconductive film 13 on the metal plate 12 like the cathode plate 11, for example, as shown in FIG. 6A, thermosetting such as epoxy resin 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 (see Patent Documents 1 and 2). FIG. 6B shows a state in which nickel (electric nickel) 14 is electrodeposited on the conductive portion 12a 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 12 a, grows not only in the thickness (longitudinal) direction but also in the plane (lateral) direction, and rises above the non-conductive film 13. Become.

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

  Further, the cathode plate constituting the non-conductive portion is formed by solidifying the periphery of the metal structure incorporated so that a plurality of studs serving as the conductive portion are arranged at equal intervals with an insulating resin by an injection molding method. A manufacturing method has also been proposed (see Patent Document 3).

Japanese Patent Publication No. 51-036693 JP 52-152832 A Japanese Examined Patent Publication No. 56-029960

  Now, when manufacturing a small lump of electronickel using the cathode plate as described above, the non-conductive film (non-conductive part) formed on the cathode plate has a long life, and the non-conductive film is missing (deteriorated). Even in such a case, it is required to be easily maintainable.

  As shown in FIG. 6A, when the nonconductive film 13 is formed by applying a nonconductive resin to the metal plate 12 by screen printing, the film thickness of the nonconductive film 13 approaches the conductive portion 12a. Therefore, since it becomes thin gradually, it becomes very thin at the boundary with the conductive part 12a. Such a change in the film thickness of the non-conductive film 13 depends on the coating amount of the non-conductive resin, the viscosity and viscosity temperature characteristics of the non-conductive resin, the curing temperature of the non-conductive resin, the surface roughness of the metal surface and the surface freedom. Depends on energy etc. Therefore, the film thickness of the non-conductive film 13 becomes very thin at the boundary with the conductive part 12a.

  As described above, when small-sized electronickel is manufactured using the cathode plate 11 as shown in FIGS. 5 and 6, the nickel 14 begins to be electrodeposited from the conductive portion 12a, and not only in the vertical direction but also in the horizontal direction. Therefore, it gradually rises on the non-conductive film 13 as well. 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 liable to decrease due to the penetration of the electrolytic solution, and the stress during the electrodeposition of the nickel 14 And it tends to be lost due to the impact when stripping the electric nickel. In addition, once the non-conductive film 13 is lost, the surrounding non-conductive film 13 is lifted from the surface of the metal plate 12, so that the electrolyte is more likely to enter the gap. When trying to deposit, the electrolyte sinks into the gap between the non-conductive film 13 floating from the surface of the metal plate 12, and the nickel 14 is electrodeposited. Then, if the nickel 14 that has entered the gap and is electrodeposited is peeled off, the non-conductive film 13 in which the nickel 14 is biting is further lost.

  Thus, in the conventional cathode plate 11, the non-conductive film 13 is lost in a chain, and the nickel 14 grown from the adjacent conductive parts 12 a is easily connected to each other as the missing part expands. The electric nickel having the shape cannot be obtained, resulting in a defective product. Accordingly, before the non-conductive film 13 is lost, it is necessary to remove all the non-conductive film 13 and form the non-conductive film 3 again to prepare the cathode plate 11. However, in practice, it becomes necessary to maintain the cathode plate 11 at a stage where nickel electrodeposition treatment is performed from several times to at most less than 10 times, which not only reduces productivity but also maintenance costs. Increase.

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

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

  In view of such conventional circumstances, an object of the present invention is to provide a metal electrodeposition cathode plate that can be used repeatedly, and a method for manufacturing the same, in which a non-conductive film on a metal plate is hardly lost.

  The present inventors have intensively studied to solve the above-mentioned problem. As a result, a plurality of ring-shaped grooves are arranged on the metal plate, and a conductive portion formed by the inner surface of the ring-shaped groove of the metal plate and a non-conductive formed on the inner surface of the ring-shaped groove of the metal plate. It was found that the non-conductive film is less likely to be lost by using the cathode plate provided with a film, and the present invention has been completed.

  (1) A first invention of the present invention is a metal plate in which a plurality of ring-shaped grooves are arranged on at least one surface, and is a surface of the metal plate, and is inside the ring shape of the groove. And a non-conductive portion formed on the surface of the metal plate and on the outer surface of the ring-shaped outer surface of the groove. It is a wearing cathode plate.

  (2) The second aspect of the present invention is the metal electrodeposition cathode plate according to the first aspect, wherein the groove has a depth of 50 μm or more and 1000 μm or less.

  (3) A third invention of the present invention is the metal electrodeposition cathode plate according to the first or second invention, wherein the groove has a width of 100 μm or more.

  (4) According to a fourth aspect of the present invention, in the first to third aspects, the metal plate is a metal electrodeposition cathode plate made of titanium or stainless steel.

  (5) The fifth invention of the present invention is a metal electrodeposition cathode plate used in the production of electroplating nickel in the first to fourth inventions.

  (6) A sixth invention of the present invention is a method for manufacturing a metal electrodeposition cathode plate, wherein a first step of forming a plurality of ring-shaped grooves on at least one surface of the metal plate; The manufacturing method includes a second step of forming a non-conductive portion on the surface of the groove and on the outer surface of the ring shape of the groove.

  According to the present invention, it is possible to provide a metal electrodeposition cathode plate that can be used repeatedly, and a method for manufacturing the same, in which a non-conductive film is not easily lost.

It is a top view which shows the structure of a cathode plate. It is a principal part expanded sectional view which shows the structure of a cathode plate, (a) is a principal part expanded sectional view explaining the state of the cathode plate before nickel electrodeposition, (b) is the cathode plate after nickel electrodeposition It is a principal part expanded sectional view explaining a state. It is a principal part expanded sectional view which shows the structure of another cathode plate. It is a principal part expanded sectional view explaining the manufacturing method of a cathode plate, (a) is a principal part expanded sectional view explaining a 1st process, (b) is a principal part expanded sectional view explaining a 2nd process. is there. 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 expanded sectional view explaining the state of the cathode plate before nickel electrodeposition, (b) is the 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 expanded sectional view explaining the state of the cathode plate before nickel electrodeposition, (b) is the cathode after nickel electrodeposition. It is a principal part expanded sectional view explaining the state of a board.

  Hereinafter, an embodiment in which the metal electrodeposition cathode plate of the present invention is applied to a metal electrodeposition cathode plate used for the production of electric nickel (hereinafter referred to as “this embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, In the range which does not change the summary of this invention, it can change suitably.

<1. Metal electrodeposition cathode plate>
(1) Configuration of Cathode Plate Cathode plate 1 according to the present embodiment is formed on a surface other than metal plate 2 having conductive portion 2a and conductive portion 2a of metal plate 2, as shown in FIG. And a non-conductive film 3 which is a non-conductive part. As will be described later, the cathode plate 1 is used by being suspended by a suspension member 5 in an electrolytic cell containing an electrolytic solution containing nickel or an anode, for example. As a result, nickel is electrodeposited on the conductive portion 2a, and electric nickel formed by being divided into small blocks can be obtained.

[Metal plate]
As shown in FIGS. 1 and 2, the metal plate 2 is a substantially flat metal plate, and a plurality of ring-shaped grooves (hereinafter referred to as “ring-shaped grooves”) 2b are arranged on one surface. ing. In the metal plate 2, the ring-shaped inner surface of the ring-shaped groove 2 b is exposed from the non-conductive film 3 and becomes a conductive portion 2 a.

  The magnitude | size of the metal plate 2 is not specifically limited, What is necessary is just to set suitably according to the desired magnitude | size and number of electrical nickel to manufacture. For example, it can be a rectangular size with one side being 100 mm or more and 2000 mm or less. The thickness of the metal plate 2 is preferably about 1.5 mm or more and 5 mm or less, for example, when the ring-shaped groove 2b is provided on one surface, and the ring-shaped groove 2b is provided on both surfaces. In such a case, for example, it is preferably about 3 mm or more and 10 mm or less. If the thickness of the metal plate 2 is too small, the warp tends to occur easily during the processing of the metal plate. On the other hand, if the thickness of the metal plate 2 is excessive, the weight of the metal plate 2 increases and handling becomes difficult.

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

  Further, the surface of the metal plate 2, that is, the conductive portion 2a of the metal plate 2, may be provided with fine irregularities by sandblasting or etching. Thereby, the nickel 4 electrodeposited on the conductive portion 2a can be peeled off with an appropriate impact without dropping off during the electrolytic treatment. In this case, the film thickness of the non-conductive film 3 described later is preferably at least twice 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 and defective insulation portions of the non-conductive film 3 are generated.

(Ring groove)
As described above, a plurality of ring-shaped grooves 2b are formed on the surface of the metal plate 2 at regular intervals. On the surface of the metal plate 2, the ring-shaped inner surface of the ring-shaped groove 2b constitutes the conductive portion 2a. In addition, in FIG. 2, although the example which has the ring-shaped groove | channel 2b in the one surface of the metal plate 2 is shown, you may have the ring-shaped groove | channel 2b in the both surfaces.

  The inner diameter of the ring shape of the ring-shaped groove 2b, that is, the diameter of the conductive portion 2a may be appropriately set according to the desired size of the nickel, but can be set to, for example, 5 mm or more and 30 mm or less. .

  Further, the depth X of the ring-shaped groove 2b is preferably 50 μm or more and 1000 μm or less, and more preferably 100 μm or more and 600 μm or less. If the depth of the ring-shaped groove 2b is too small, as will be described later, the thickness of the non-conductive film 3 inside the ring-shaped groove 2b becomes insufficient, and the non-conductive film 3 is likely to be deteriorated or missing. On the other hand, if the depth of the ring-shaped groove 2b is excessive, distortion is increased during the process of forming the ring-shaped groove 2b in the metal plate 2, and the formation of the non-conductive film 3 becomes difficult.

  Further, the width Y of the ring-shaped groove 2b is preferably 100 μm or more, and more preferably 500 μm or more. If the width of the ring-shaped groove 2b is too small, it becomes difficult to fill the non-conductive film 3 into the ring-shaped groove 2b, and the non-conductive film 3 formed inside the ring-shaped groove 2b is deteriorated or missing. It becomes easy. The upper limit value of the width of the ring-shaped groove 2b is not particularly limited, but may be determined according to the interval between the adjacent ring-shaped grooves 2b.

[Non-conductive film]
As shown in FIG. 2, the non-conductive film 3 is a surface of the metal plate 2 and includes an inner surface of the ring-shaped groove 2b and an outer surface of the ring-shaped groove 2b (hereinafter referred to as “ring-shaped groove”). "Outside surface") formed on 2c. Here, the inside of the ring-shaped groove 2b is not limited to the range within the depth X of the ring-shaped groove 2b. Therefore, the non-conductive film 3 formed in the ring-shaped groove 2b. May be formed to have a film thickness equal to or greater than the depth X of the ring-shaped groove 2b.

  The non-conductive film 3 formed in this way has an end portion in the ring-shaped groove 2b. Therefore, the film thickness of the end portion of the non-conductive film 3 is equal to the depth X of the ring-shaped groove 2b than the film thickness of the non-conductive film 3 formed on the outer surface 2c of the ring-shaped groove 2b of the metal plate 2. Only thickly formed. Therefore, as shown in FIG. 6, the non-conductive film 3 is unlikely to have a thin film thickness at the end portion, unlike the conventional non-conductive film 13 formed on the flat metal plate 12. It is hard to be lost due to stress at the time of wearing and impact at the time of peeling after electrodeposition. Further, the non-conductive film 3 does not protrude in a convex shape unlike the conventional non-conductive film 23 shown in FIG. 7, and its end is in the ring-shaped groove 2b. Therefore, when the nickel 4 is peeled off from the cathode plate 1, the impact of the nickel 4 on the end portion of the non-conductive film 3 is small and the non-conductive film 3 is not easily lost. Thus, since the non-conductive film 3 is not easily lost in the cathode plate 1, it can be used repeatedly for electrodeposition without replacing the non-conductive film 3, reducing maintenance costs and productivity. It is possible to improve.

  The film thickness of the non-conductive film 3 is not particularly limited as long as it can cover the inside of the ring-shaped groove 2b and the outer surface 2c of the ring-shaped groove 2b. For example, the non-conductive film on the outer surface 2c of the ring-shaped groove 2b The thickness of No. 3 is preferably 60 μm or more, and more preferably 100 μm or more.

  The film thickness of the non-conductive film 3 inside the ring-shaped groove 2b is preferably equal to or greater than the depth X of the ring-shaped groove 2b. If the film thickness of the non-conductive film 3 inside the ring-shaped groove 2b is greater than or equal to the depth X of the ring-shaped groove 2b, the inner peripheral edge of the ring-shaped groove 2b is exposed from the non-conductive film 3 as a step. There is nothing to do. Accordingly, even when the nickel 4 is peeled off from the cathode plate 1, the nickel 4 is not caught on the peripheral edge of the ring-shaped groove 2b.

  The upper limit of the film thickness of the non-conductive film 3 is not particularly limited, but it is not necessary to make it thicker than necessary. For example, the film thickness on the outer surface 2c of the ring-shaped groove 2b is preferably 500 μm or less, and more preferably 300 μm or less. For example, it is difficult to apply over 500 μm on the outer surface 2c of the ring-shaped groove 2b of the metal plate 2 by screen printing. When trying to form the non-conductive film 3 having a film thickness of more than 500 μm on the outer surface 2c of the ring-shaped groove 2b by screen printing, it becomes necessary to carry out while finely adjusting the size of the screen plate pattern over a plurality of times. The adjustment is difficult and productivity is lowered.

  When the non-conductive film 3 is formed in the ring-shaped groove 2b of the metal plate 2 by screen printing, the material of the non-conductive film 3 is the inner surface of the ring-shaped groove 2b, that is, the conductive portion 2a. The surface area of the conductive portion 2a may be reduced and the initial current density may be increased, but there is no problem if the characteristics of the electrodeposited nickel 4 do not cause a problem. In addition, the non-conductive film 3 attached on the surface of the conductive portion 2a is easily lost due to its very thin film thickness, but the non-conductive film 3 formed on the ring-shaped groove 2b has a large film thickness and lacks. There is no problem because it is suppressed.

  The non-conductive film 3 is non-conductive and is not particularly limited as long as it is made of a material that is less corroded by the electrolyte used. For example, the material of the non-conductive film 3 includes a thermosetting resin or a photo-curing (ultraviolet curing) resin from the viewpoint of easy film formation. Specific examples include insulating resins such as epoxy resins, phenol resins, polyamide resins, and polyimide resins.

  In addition, you may comprise a nonelectroconductive part by multiple layers. For example, as shown in FIG. 3, the non-conductive film 3 ′, which is a non-conductive part, includes a first non-conductive layer 3a formed in the ring-shaped groove 2b, a ring shape on the first non-conductive layer 3a, and the like. You may comprise from the 2nd nonelectroconductive layer 3b formed on the outer surface 2c of the groove | channel 2b. Specifically, for example, an inorganic material such as ceramics is used as the first nonconductive layer 3a, and an epoxy resin, a phenol resin, a polyamide resin, a polyimide resin, or the like is used as the second nonconductive layer 3b. An insulating resin can be used. Further, different insulating resins may be used for the first non-conductive layer 3a and the second non-conductive layer 3b. An insulating resin is preferably used for the outermost layer of the non-conductive portion, that is, the non-conductive layer 3b on which the nickel 4 is electrodeposited, from the viewpoint that it is not easily broken by an impact when the nickel 4 is peeled off. When the non-conductive portion is composed of a plurality of layers, for example, an expensive material is used for the first non-conductive layer 3a, but an inexpensive material is used for the second non-conductive layer 3b. May be used.

(2) Manufacture of electric nickel using cathode plate In the cathode plate 1 having the above-described configuration, the surface of the metal plate 2 exposed from the non-conductive film 3 becomes the conductive portion 2a as shown in FIG. 2 (b). Then, nickel 4 is electrodeposited. In the cathode plate 1, the nickel 4 grows not only in the thickness direction but also in the planar direction, so that it rises above the non-conductive film 3. For this reason, it is preferable to finish the electrodeposition before the nickels 4 grown from the adjacent conductive portions 2a come into contact with each other.

  Then, after the nickel electrodeposition is completed, the nickel 4 is peeled off from the cathode plate 1, whereby a plurality of small blocks of electric nickel can be obtained from one cathode plate 1. As described above, in the cathode plate 1 according to the present embodiment, since the non-conductive film 3 is not easily lost, the non-conductive film 3 can be used repeatedly without replacement, reducing maintenance costs and producing. It is possible to improve the performance.

  In addition, although the cathode plate 1 which concerns on this Embodiment electrodeposited nickel 4, it is not limited to nickel, You may electrodeposit silver, gold | metal | money, zinc, tin, chromium, cobalt, or these alloys. .

<2. Method for producing metal electrodeposition cathode plate>
As shown in FIG. 4, the manufacturing method of the cathode plate 1 according to the present embodiment includes a first step (FIG. 4A) for forming a plurality of ring-shaped grooves 2b on at least one surface of the metal plate 2. And a second step (FIG. 4B) for forming the non-conductive film 3 on the surface of the metal plate 2 other than the ring-shaped groove 2b.

[First step]
In the first step, a plurality of ring-shaped grooves 2 b are formed on the surface of the metal plate 2. It does not specifically limit as a processing method, For example, it can carry out by wet etching processing, end mill processing, laser processing, etc.

  For example, when processing a flat stainless steel plate by wet etching, a photosensitive etching resist is applied to the surface of the stainless steel plate, and then exposed through a film or glass on which a desired pattern is drawn and etched. The etching resist is removed by development processing. Then, the developed stainless steel plate is attached 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 A plurality of ring-shaped grooves 2b corresponding to the pattern can be formed.

  The ring-shaped groove 2b may be formed only on 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 non-conductive film 3 is formed inside the ring-shaped groove 2b and on the outer surface 2c of the ring-shaped groove 2b, that is, on the surface of the metal plate 2 other than the conductive portion 2a. The method for forming the non-conductive film 3 is not particularly limited, and can be performed by screen printing. In the case where the material of the non-conductive film 3 is a thermosetting resin or a photo-curing resin, heat curing or photo-curing may be performed as necessary.

  When the non-conductive film is formed in a two-layer structure, after the first non-conductive layer 3a is formed inside the ring-shaped groove 2b, the first non-conductive layer 3a and the outside of the ring-shaped groove 2b are formed. A second non-conductive layer 3b is formed on the surface 2c. As a method for forming the first non-conductive layer 3a, for example, a portion other than the ring-shaped groove 2b is masked, a ceramic coating agent is applied to the ring-shaped groove 2b, and the masking is removed and then fired. The first nonconductive layer 3a made of ceramics may be formed in 2b. Alternatively, after applying and firing a ceramic coating agent on the entire surface of the metal plate 2, unnecessary ceramics formed other than the ring-shaped groove 2b are polished and removed, whereby the first groove made of ceramics is formed in the ring-shaped groove 2b. The nonconductive layer 3a may be formed. As a method for forming the second non-conductive layer 3b, an epoxy resin is applied by screen printing on the first non-conductive layer 3a and the outer surface 2c of the ring-shaped groove 2b, and then heat curing or light curing is performed. The second non-conductive layer 3b made of an epoxy resin may be formed.

  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 used repeatedly, with the non-conductive films 3 and 3 ′ on the metal plate 2 being less likely to be lost by the simple method described above. it can.

  Hereinafter, the present invention will be described more specifically 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.

<Preparation of cathode plate>
[Example 1]
A cathode plate 1 as shown in FIGS. 1 and 2 was produced. Specifically, first, wet etching was performed on a metal plate 2 made of stainless steel of 200 mm × 100 mm × 4 mm to form ring-shaped grooves 2b (18 pieces). At this time, the size of the ring-shaped groove 2a was 14 mm in inner diameter, depth X 300 μm, and width Y 1000 μm, and the minimum distance between adjacent conductive portions 2 a was 21 mm. Next, a thermosetting epoxy resin is applied to the inside of the ring-shaped groove 2b and the outer surface 2c of the ring-shaped groove 2b in the metal plate 2 by screen printing, and is cured by heating at 150 ° C. for 60 minutes to make it non-conductive Film 3 was formed.

[Examples 2 to 6]
A cathode plate 1 was produced in the same manner as in Example 1 except that the depth X and the width Y of the ring-shaped groove 2b of the metal plate 2 were changed to the values shown in Table 1.

[Comparative Example 1]
In Comparative Example 1, a conventional cathode plate 11 as shown in FIG. Specifically, a thermosetting epoxy resin is applied by a screen printing method, leaving a conductive portion 12a (18 pieces) having a diameter of 14 mm on a flat metal plate 12 made of stainless steel of 200 mm × 100 mm × 4 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 produced.

[Comparative Example 2]
Wet etching was performed on a 200 mm x 100 mm x 4 mm stainless steel metal plate to form ring-shaped grooves (18 pieces) with an inner diameter of 14 mm, a depth of 2000 μm, and a width of 2000 μm. It was difficult to form a non-conductive film.

<Manufacture of electrical nickel>
Using the cathode plate produced in each example and comparative example, electro nickel was produced by electrolytic treatment. Specifically, a cathode plate and an anode plate made of electric nickel of 200 mm × 100 mm × 10 mm were immersed facing each other in an electrolytic cell containing a nickel chloride electrolyte. 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 electronickel deposited on the cathode plate was peeled off to obtain a small lump of electronickel for plating.

<Evaluation>
The number of times that the cathode plate used for the electrolytic treatment can be repeatedly used as it was was evaluated. When the lack of the non-conductive film spreads, nickel electrodeposited at adjacent conductive portions may be connected to each other, so that electric nickel having a desired shape may not be obtained. Therefore, when the non-conductive film is missing and the non-conductive film is missing over 1 mm in the direction away from the conductive portion from the initial predetermined position, the use was stopped and the number of repetitions up to that point was evaluated. .

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

  As shown in Table 1, in Examples 1 to 6 using the cathode plate 1 made of the metal plate 2 formed with the ring-shaped groove 2b, Comparative Example 1 using the cathode plate 11 made of the flat metal plate 12 was used. In comparison with the above, the loss of the non-conductive film 3 is suppressed, and the number of times of repeated use is increased. In particular, in Examples 1 to 4 using the cathode plate 1 in which the groove depth X of the ring-shaped groove 2b was 50 μm or more and the width Y was 100 μm or more, the ring-shaped groove 2b could be used repeatedly a sufficient number of times.

DESCRIPTION OF SYMBOLS 1 Cathode plate 2 Metal plate 2a Conductive part 2b Ring-shaped groove 2c Outer surface of ring-shaped groove 3 Non-conductive film 4 Nickel

Claims (6)

A metal plate having a plurality of ring-shaped grooves arranged on at least one surface,
A conductive portion that is a surface of the metal plate and is configured by an inner surface of the ring shape of the groove;
A non-conductive portion formed on the surface of the metal plate and on the inner surface of the groove and the outer surface of the ring shape of the groove;
Cathode plate for metal electrodeposition. The depth of the groove is 50 μm or more and 1000 μm or less.
The cathode plate for metal electrodeposition according to claim 1. The width of the groove is 100 μm or more.
The cathode plate for metal electrodeposition according to claim 1 or 2. The metal plate is made of titanium or stainless steel.
The metal electrodeposition cathode plate according to any one of claims 1 to 3. Used in the production of electro nickel for plating,
The metal electrodeposition cathode plate according to any one of claims 1 to 4. A method for producing a metal electrodeposition cathode plate,
A first step of forming a plurality of ring-shaped grooves on at least one surface of the metal plate;
A manufacturing method comprising a second step of forming a non-conductive portion on the metal surface and on the ring-shaped outer surface of the groove and the ring-shaped outer surface of the groove.

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