JP6500937B2 - Negative electrode plate for metal electrodeposition and method of manufacturing the same - Google Patents

Description

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

  2. Description of the Related Art Conventionally, electric nickel provided as an anode material for nickel plating is put in a titanium basket serving as an anode holder, and is suspended and used in a nickel plating tank. At this time, as the electric nickel which is an anode raw material, a small piece of plate-like electric nickel electrodeposited on a cathode plate was used.

  However, small pieces of electric nickel are difficult to handle when introduced into a titanium basket because the corners are sharp. In addition, the small pieces of electric nickel are caught in the mesh of the titanium basket after being inserted into the titanium basket and cause so-called shelf suspension, and the filling state in the titanium basket changes, causing uneven plating It could have been

  Therefore, it has been proposed to use rounded small lumps (button-like) of electric nickel having sharp corners. The small block of electric nickel is formed, for example, by depositing nickel on the conductive portion by electrolysis using a cathode plate in which a plurality of circular conductive portions are arranged at equal intervals, and then electrodepositing nickel 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 view showing an example of a conventional cathode plate used for the production of small chunks of electric nickel. The cathode plate 11 is masked with a non-conductive film 13 on the flat metal plate 12 except for the portion to be the conductive portion 12 a. In this cathode plate 11, the conductive portion 12 a becomes a recess and the non-conductive layer The film 13 is a convex portion. By using such a cathode plate 11, nickel of a suitable size is electrodeposited on the conductive portion 12a to produce small lumps of electrolytic 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, a thermosetting resin such as epoxy resin is formed on the flat metal plate 12. There is a method of forming a nonconductive film 13 having a desired pattern by applying a conductive nonconductive resin by a screen printing method and heating it (see Patent Documents 1 and 2). 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 nonconductive film 13 is formed. In the cathode plate 11, nickel 14 starts electrodeposition deposition from the conductive portion 12 a and grows not only in the thickness (longitudinal) direction but also in the planar (horizontal) direction and also rises in the upper portion of the nonconductive film 13. Become.

  For example, as shown in FIG. 7A, a photosensitive nonconductive resin is applied on the metal plate 22, and the nonconductive resin corresponding to the conductive portion 22a is removed by exposure and development. A method of forming the nonconductive 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 22 a using the cathode plate 21 on which the nonconductive film 23 is formed. Also in the cathode plate 21, nickel 24 starts electrodeposition deposition from the conductive portion 22a, and grows not only in the thickness direction but also in the planar direction.

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

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

  Now, in the case of producing small chunks of electric nickel using the cathode plate as described above, the life of the non-conductive film (non-conductive portion) formed on the cathode plate is long, and the non-conductive film is missing (deterioration) It is required that they can be easily maintained even if they

  As shown in FIG. 6A, when the nonconductive resin is applied to the metal plate 12 by screen printing to form the nonconductive film 13, 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 changes in the thickness of the nonconductive film 13 may be caused by the coating amount of the nonconductive resin, the viscosity and temperature characteristics of the nonconductive resin, the curing temperature of the nonconductive resin, the surface roughness of the metal surface, and the surface freedom. It depends on energy etc. Therefore, the film thickness of the nonconductive film 13 becomes very thin at the boundary with the conductive portion 12a.

  As described above, when a small block of electric nickel is produced using the cathode plate 11 as shown in FIGS. 5 and 6, the nickel 14 starts electrodeposition deposition from the conductive portion 12a, and not only in the longitudinal direction but also in the lateral direction. In order to grow as well, the nonconductive film 13 gradually rises. Therefore, in the portion of the thin nonconductive film 13 formed in the vicinity of the boundary with the conductive portion 12a, the adhesion with the metal plate 12 is likely to deteriorate due to the penetration of the electrolytic solution, and the stress at the time of electrodeposition of the nickel 14 And the impact at the time of the stripping of the electric nickel becomes easy to be missing. In addition, once the nonconductive film 13 is missing, the nonconductive film 13 in the periphery thereof rises from the surface of the metal plate 12 so that the electrolyte is more likely to penetrate into the gap, and as a result, nickel is continuously electroplated. When it is attempted to deposit, the electrolyte penetrates into the gap of the nonconductive film 13 lifted up from the surface of the metal plate 12 and the nickel 14 is electrodeposited. Then, if it is attempted to peel off the electrodeposited nickel 14 that has penetrated the gap, the nonconductive film 13 in which the nickel 14 is bitten is further lost.

  As described above, in the conventional cathode plate 11, the nonconductive film 13 is missing in a chained manner, and when the missing portion spreads, the nickels 14 grown from the adjacent conductive portions 12a are easily connected, which is desirable. It is not possible to obtain electric nickel of the shape of the above, and it becomes a defective product. Therefore, it is necessary to strip off all the nonconductive film 13 and form the nonconductive film 13 again to prepare the cathode plate 11 before the nonconductive film 13 is missing. However, in practice, it is necessary to perform maintenance of the cathode plate 11 at a stage where electrodeposition treatment of nickel is performed several times to at most less than 10 times, and not only the productivity is lowered but also the maintenance cost is Increase.

  On the other hand, as shown in FIG. 7A, in the cathode plate 21 on which the nonconductive film 23 is formed by exposure and development using a photosensitive nonconductive resin, the nonconductive film 23 is formed to a uniform thickness. can do. However, when the nickel 24 is peeled off after electrodeposition, the nickel 24 is caught on the step of the nonconductive film 23 forming the convex portion, and the nonconductive film 23 is likely to be subjected to a large impact. Lack of will occur.

  In the method of forming the nonconductive portion by injection molding as in Patent Document 3, although the life of the formed nonconductive portion is extended, the manufacturing cost of the cathode plate itself is increased and the nonconductive portion is deteriorated. It is difficult to maintain the cathode plate in the case.

  SUMMARY OF THE INVENTION In view of such conventional circumstances, the present invention is a cathode for metal electrodeposition in which a nonconductive film on a metal plate is unlikely to be missing, which can be repeatedly used and which can be easily maintained even when the nonconductive film is missing. It aims at providing a board and its manufacturing method.

  The present inventors diligently studied to solve the above-mentioned problems. As a result, it has been found that the nonconductive film is less likely to be missing by providing the protrusion on the metal plate to form the conductive portion and providing the nonconductive film on the metal surface other than the protrusion. Furthermore, by setting the shape of the side surface of the projection to a predetermined shape, it is possible to prevent the nonconductive film more effectively from falling off, and it is necessary to perform maintenance by reforming the nonconductive film, It has been found that when the nonconductive film is peeled off, maintenance becomes easy without the nonconductive film remaining, and the present invention has been completed.

  (1) According to a first aspect of the present invention, there is provided a metal plate in which a plurality of disk-shaped protrusions are arranged on at least one surface, and a nonconductive film formed on the surface of the metal plate other than the protrusions. The side surface of the protrusion is a shape having a substantially vertical portion and an inclined portion, and the height L1 of the protrusion is 50 μm or more and 1000 μm or less, and the outer side from the outer peripheral edge of the protrusion When the point of intersection between a perpendicular drawn down from a position X separated by 20 μm and the side surface is Y, the length L 2 from X to Y is 40 μm or more and 0.8 × L 1 μm or less. It is.

  (2) A second invention of the present invention is the cathode plate for metal electrodeposition according to the first invention, wherein the metal plate is made of titanium or stainless steel.

  (3) A third invention of the present invention is a cathode plate for metal electrodeposition, which is used for producing electroplated nickel in the first or second invention.

  (4) A fourth invention of the present invention is a method of manufacturing a cathode plate for metal electrodeposition according to any one of the first to third inventions, wherein at least one surface of the metal plate is wet-etched or an end mill It is a manufacturing method of the cathode plate for metal electrodeposition which forms two or more said disk-shaped projection parts by processing.

  (5) A fifth aspect of the present invention is the method according to the fourth aspect, wherein a radius end mill is used in the end milling.

  According to the present invention, it is possible to provide a negative electrode plate for metal electrodeposition which is resistant to omission of a nonconductive film, which can be repeatedly used, and which can be easily maintained even when the nonconductive film is absent, and a manufacturing method thereof. it can.

It is a top view which shows the structure of a cathode plate. It is a principal part expanded sectional view showing the composition of a cathode plate, (a) is an important part expanded sectional view explaining the state of the cathode plate before nickel electrodeposition, (b) is a cathode plate after nickel electrodeposition It is a principal part expanded sectional view explaining a state. It is the principal part expanded sectional view which expanded the A section in FIG. 2, and is a principal part expanded sectional view explaining the side shape of the projection part of a metal 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 showing the composition of the conventional cathode plate, (a) is an important part expanded 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 showing the composition of the conventional cathode plate, (a) is an important part expanded 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 in which the metal electrodeposition negative electrode plate of the present invention is applied to a metal electrodeposition negative electrode plate used for producing electric nickel (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can change suitably in the range which does not change the summary of this invention.

<1. Negative electrode plate for metal electrodeposition>
(1) Configuration of Cathode Plate The cathode plate 1 according to the present embodiment is, as shown in FIG. 1, a metal plate 2 in which a plurality of disk-shaped protrusions 2a are arrayed, and a protrusion 2a of the metal plate 2 And a nonconductive film 3 formed on the other surface. The cathode plate 1 is used by being suspended by a suspending member 5 in an electrolytic cell containing, for example, an electrolytic solution containing nickel and an anode as described later, and nickel of a desired shape is electrodeposited on its surface Let

[Metal plate]
The metal plate 2 is a flat metal plate as shown in FIG. 1 and FIG. 2 (a), and has a plurality of disk-shaped protrusions 2a. Here, in the metal plate 2, surfaces other than the protrusion 2a are referred to as "flat portions 2b" with respect to the protrusion 2a. Further, “the height L 1 of the protrusion” is the height of protrusion of the metal plate 2 from the surface of the flat portion 2 b.

  In addition, although the example which has the projection part 2a in one side of the metal plate 2 is shown in FIG. 2, you may have the projection part 2a in the both surfaces.

  The size of the metal plate 2 is not particularly limited, and may be appropriately set according to the desired size and number of the electric nickel to be manufactured. For example, it can be made into the rectangular size of 100 mm or more and 2000 mm or less per side. Moreover, as thickness of the metal plate 2, when providing the projection part 2a in one surface, it is preferable that it is about 1.5 mm or more and 5 mm or less, for example, and when providing the projection part 2a in both surfaces. For example, it is preferable that it is 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 cause warpage. On the other hand, when 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 which is less corroded by the electrolyte used and which only forms a loose bond with an electrodeposit such as nickel, but titanium and stainless steel are preferably mentioned.

  In the metal plate 2, the plurality of disk-shaped protrusions 2 a are exposed from the non-conductive film 3, the upper surface of which will be described later, to function as a conductive portion, and the non-conductive film 3 is formed with a predetermined thickness. As a result, a concave step is formed by the adjacent projections 2a. Hereinafter, the upper surface of the protrusion 2 a exposed from the nonconductive film 3 may be referred to as “conductive portion 2 c”. In the conductive portion 2c, nickel 4 is electrodeposited by electrolytic treatment.

  The size of the disk-like protrusion 2a may be appropriately set according to the desired size of the electric nickel, but the diameter can be, for example, 5 mm or more and 30 mm or less. The height L1 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 L1 of the protruding portion 2a is too small, the film thickness of the nonconductive 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 It becomes easy to drop off by the impact at the time of peeling off. On the other hand, if the height L1 of the protrusion 2a is too large, for example, when forming a nonconductive film by screen printing, the number of times of application increases and productivity decreases. Further, if the height L1 is too large, distortion of the metal plate 2 is easily generated at the time of processing the protrusion 2a, and the metal plate 2 is easily warped, so that formation of the nonconductive film 3 becomes difficult. In addition, in order to make the influence by distortion of the metal plate 2 small, it is also possible to thicken the thickness of the metal plate 2, but the weight of the metal plate 2 increases and handling becomes difficult.

  Here, FIG. 3 is an enlarged cross-sectional view of the main part in which the portion A in FIG. As shown in FIG. 3, in the metal plate 2, the side surface of the protrusion 2 a has a shape including a substantially vertical portion 2 d and an inclined portion 2 e. Specifically, the substantially vertical portion 2 d is a portion formed substantially perpendicularly to the upper surface of the protrusion 2 a to be the conductive portion 2 c. The inclined portion 2e is a portion formed to be inclined from the substantially vertical portion 2d toward the flat portion 2c.

  As described above, the side surface of the protrusion 2a is configured to be formed of the substantially vertical portion 2d and the sloped portion 2e, so that the nonconductive film 3 is more effectively removed even when the electrodeposition process is repeated. Can be prevented and allow repeated use. In addition, even when maintenance by re-formation of the non-conductive film 3 is necessary due to deterioration such as loss of the non-conductive film 3, when peeling the non-conductive film 3 from the metal plate 2, A so-called peeling residue in which the nonconductive film 3 remains hardly occurs, and maintenance becomes easy.

  For example, in the case where the side surface of the protrusion is formed only by the substantially vertical portion and the inclined portion does not exist, even if it is attempted to peel off the nonconductive film from the metal plate, The nonconductive film tends to remain at the corners to be formed. On the other hand, in the case where the side surface of the protrusion is formed with only the sloped portion and the substantially vertical portion does not exist, the nonconductive film in the vicinity of the conductive portion becomes thinner and the nonconductive film is electrodeposited. Deterioration of the non-conductive film is quickened, for example, it is easy to drop off.

  More specifically, as shown in FIG. 3, the shape of the side surface of the protrusion 2a is a point of intersection of a line vertically lowered from a position X spaced 20 .mu.m outward from the outer peripheral edge of the protrusion 2a and the side surface of the protrusion 2a. When Y is Y, the length L2 from X to Y is 40 μm or more, and preferably 100 μm or more. When the length L2 is 40 μm or more, the non-conductive film 3 formed on the metal plate 2 (flat portion 2b) is unlikely to be missing even if the electrolytic treatment is repeated. Here, the outer peripheral edge of the protrusion 2a is the outer peripheral edge (edge portion) of the upper surface to be the conductive portion 2c of the protrusion 2a.

  Further, the length L2 is equal to or less than 0.8 times (L1 × 0.8 μm) the height L1 of the protrusion 2a. When the length L2 is L1 × 0.8 μm or less, the inclined portion 2e can be effectively secured, and as described above, the side surface of the protrusion 2a when the nonconductive film 3 is peeled from the metal plate 2 It becomes difficult for the non-conductive film 3 to remain in the peeling residue.

  Although the length L2 from X to Y corresponds to the height of the substantially vertical portion 2d, the intersection point Y clearly divides the shape of the side surface of the protrusion 2a into the substantially vertical portion 2d and the inclined portion 2e. It does not have to be a turning point. Hereinafter, the length L2 may be referred to as "the height L2 of the substantially vertical portion 2d".

  Moreover, 10 micrometers or more are preferable and, as for length L3 which is the difference of height L1 of projection part 2a and length L2, 25 micrometers or more and 0.7xL1 micrometer or less are more preferable. Hereinafter, the length L3 may be referred to as "the height of the inclined portion 2e". Furthermore, let Y 'be the point of intersection of a line vertically lowered from the intersection point Y and a virtual surface extending horizontally in the surface of the flat portion 2b, let Y' be the boundary position between the projection 2a and the flat portion 2b, Z ' When the length up to Z is L4, L3 / L4 is preferably 0.2 or more and 1 or less. Hereinafter, the length L4 may be referred to as "the length L4 of the inclined portion 2e". L3 / L4 corresponds to the inclination angle of the inclined portion 2e.

  When the nonconductive film 3 is peeled from the metal plate 2 even when maintenance by re-formation of the nonconductive film 3 is required because the lengths L3 and L3 / L4 are in the above range, the protrusion 2a It is hard to produce the peeling residue which the nonelectroconductive film 3 remains on the side surface, and maintenance is easy.

  In addition, on the surface of the metal plate 2, that is, the upper surface of the disk-like protrusion 2 a of the metal plate 2, fine unevenness may be provided by sand blasting or etching. As a result, the nickel 4 electrodeposited on the projection 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 twice or more the maximum surface roughness Rz of the metal plate 2. If the film thickness of the nonconductive film 3 is smaller than twice the maximum surface roughness Rz of the metal plate 2, generation of pinholes and insulation failure portions of the nonconductive film 3 may be concerned.

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

  The nonconductive film 3 is formed on the flat portion 2b having a concave step formed by the adjacent protruding portions 2a. Therefore, as in the case of the conventional non-conductive film 13 shown in FIG. 6, the non-conductive film 3 hardly has a thin film thickness at the end, and the stress at the time of electrodeposition of nickel 4 and the impact at the time of stripping after electrodeposition It also makes it difficult to get lost. Further, the nonconductive film 3 does not protrude in a convex shape as in the conventional nonconductive film 23 shown in FIG. 7, and its end is protected by a concave step. Therefore, even when the nickel 4 is peeled off from the cathode plate 1, the impact of the nickel 4 on the end of the nonconductive film 3 is small, and the nonconductive film 3 is less likely to be missing. As described above, in the cathode plate 1, since the nonconductive film 3 is hard to be missing, it is possible to use the nonconductive film 3 for repeated electrodeposition without replacing the nonconductive film 3. Thus, the maintenance cost is reduced and the productivity is improved. Can be improved.

  When the nonconductive film 3 is formed on the flat portion 2b on the metal plate 2 by the screen printing method, the material of the nonconductive film 3 is also applied to the upper surface of the protrusion 2a to reduce the surface area of the conductive portion 2c. Although the initial current density may increase, there is no problem if the characteristics of the electrodeposited nickel 4 do not fail. In addition, the nonconductive film 3 attached on the upper surface of the protrusion 2a is likely to be dropped because the film thickness is very thin, but the nonconductive film 3 formed on the flat portion 2b is thick and the drop is suppressed There is no problem because

  The nonconductive film 3 is not particularly limited as long as it is nonconductive and is made of a material that is less likely to be corroded by the electrolyte used. For example, from the viewpoint of easy film formation, it is preferable to use a thermosetting resin or a light curing (ultraviolet curing etc.) resin. Specifically, insulating resins such as epoxy resins, phenol resins, polyamide resins, polyimide resins and the like can be mentioned.

(2) Production of electric nickel using a cathode plate In the cathode plate 1 having the above-described structure, as shown in FIG. 2B, the upper surface of the projection 2a exposed from the nonconductive film 3 is the conductive portion 2c. To deposit nickel 4 by electrodeposition. In the cathode plate 1, the nickel 4 grows not only in the thickness direction but also in the planar direction, and therefore, is in a state of being raised above the nonconductive film 3. From this, it is preferable to finish the electrodeposition before the nickels 4 grown from the conductive portion 2c in the adjacent protrusion 2a come in contact with each other.

  Then, after the electrodeposition of the nickel 4 is completed, the nickel 4 is peeled off from the cathode plate 1 to obtain a plurality of small lumps of electronickel from the cathode plate 1 of one sheet. As described above, in the cathode plate 1 according to the present embodiment, since the nonconductive film 3 is unlikely to be missing, the nonconductive film 3 can be repeatedly used for electrodeposition without replacing it, and maintenance costs can be reduced. Reduction and improvement of productivity can be achieved.

  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 of Manufacturing Negative Electrode Plate for Metal Electrodeposition>
In the method of manufacturing the cathode plate 1 according to the present embodiment, as shown in FIG. 4, a first step of forming a plurality of disk-shaped protrusions 2 a on at least one surface of the metal plate 2 (FIG. 4 (a)) And a second step (FIG. 4B) of forming the nonconductive film 3 on the surface of the metal plate 2 other than the protrusion 2a.

[First step]
In the first step, a plurality of disk-shaped protrusions 2 a are formed on the surface of the metal plate 2. For example, the flat metal plate 2 is ground at a portion other than the protrusion 2a to leave the protrusion 2a having a height L1 and form the flat portion 2b. As a processing method, wet etching or end milling is preferable, and in order to process a large area, wet etching is more preferable.

  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 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 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 has been removed is removed, and finally the etching resist is peeled off. A plurality of disk-shaped protrusions 2a corresponding to the pattern can be formed. In the case of wet etching, the stainless steel in the vicinity of the resist has a slower etching rate than the portion distant from the resist end, so the cross-sectional shape of the projection 2a is formed by the substantially vertical portion 2d and the inclined portion 2e Become. Moreover, since a large area can be processed at once, it can manufacture in a short time.

  On the other hand, in the case of end milling, the substantially vertical portion 2 d and the inclined portion 2 e can be formed more precisely by processing the metal plate 2 with a radius end mill having a desired rounded shape at the tip of the drill blade. it can.

  The protrusion 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 nonconductive film 3 is formed on the flat portion 2 b which is the surface of the metal plate 2 other than the protrusion 2 a. The method of forming the nonconductive film 3 is not particularly limited, and the nonconductive film 3 can be formed by screen printing. When the material of the nonconductive film 3 is a thermosetting resin or a photocuring resin, thermosetting or photocuring may be performed as necessary.

  According to the method for manufacturing a cathode plate according to the present embodiment, the non-conductive film 3 on the metal plate 2 is unlikely to be missing by the simple method described above, and the cathode plate 1 that can be used repeatedly can be obtained. In addition, even when maintenance due to re-formation of the non-conductive film 3 is necessary due to deterioration due to lack of the non-conductive film 3 or the like, the non-conductive film 3 is on the side surface of the protrusion 2 a when peeling off the non-conductive film 3. Remaining peeling residue is unlikely to occur and maintenance is easy.

  Examples of the present invention will be more specifically described below, but the present invention is not limited by 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.

<Fabrication 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 200 mm × 100 mm × 4 mm stainless steel (cold-rolled) metal plate 2 to form disk-shaped protrusions 2 a (18 pieces). At this time, the size of the protrusion 2a was 14 mm in diameter, 300 μm in height L1, and 21 mm in the minimum distance between adjacent protrusions 2a. When the shape was measured by a laser displacement meter, the height L2 of the substantially vertical portion 2d was 120 μm on average, the height L3 of the inclined portion 2e was 180 μm on average, and the length L4 of the inclined portion 2e was 420 μm on average.

  Next, a thermosetting epoxy resin was applied onto the flat portion 2b of the metal plate 2 by screen printing, and was cured by heating at 150 ° C. for 60 minutes to form the nonconductive film 3.

Example 2
A cathode plate 1 was produced in the same manner as in Example 1 except that the height L1 of the protrusions 2a of the metal plate 2 was 500 μm. In the cathode plate 1 thus produced, when the height L2 of the substantially vertical portion 2d is measured by a laser displacement meter, the average is 200 μm, the average height L3 of the inclined portion 2e is 300 μm, and the length L4 of the inclined portion 2e The average was 650 μm.

[Example 3]
A cathode plate 1 was produced in the same manner as in Example 1 except that the height L1 of the protrusions 2a of the metal plate 2 was 60 μm. In the cathode plate 1 thus manufactured, when the height L2 of the substantially vertical portion 2d is measured by a laser displacement meter, the average is 45 μm, the average height L3 of the inclined portion 2e is 15 μm, and the length L4 of the inclined portion 2e The average was 20 μm.

Example 4
A cathode plate 1 was produced in the same manner as in Example 1 except that the height L1 of the protrusions 2a of the metal plate 2 was 200 μm. In the cathode plate 1 thus manufactured, when the height L2 of the substantially vertical portion 2d is measured by a laser displacement meter, the average is 90 μm, the height L3 of the inclined portion 2e is 110 μm on average, and the length L4 of the inclined portion 2e The average was 240 μm.

[Example 5]
A cathode plate 1 was produced in the same manner as in Example 1 except that a disk-like projection was formed using a radius end mill drill. In the cathode plate 1 thus produced, when the height L2 of the substantially vertical portion 2d is measured by a laser displacement meter, the average is 100 μm, the average height L3 of the inclined portion 2e is 200 μm, and the length L4 of the inclined portion 2e The average was 220 μm.

Comparative Example 1
In Comparative Example 1, a conventional cathode plate 11 as shown in FIGS. 5 and 6 was manufactured. Specifically, the conductive portions 12a (18 pieces) each having a diameter of 14 mm are left on a flat plate-like metal plate 12 made of stainless steel (cold-rolled material) of 200 mm × 100 mm × 4 mm, and thermally processed by screen printing. A curable epoxy resin was applied and cured by heating at 150 ° C. for 60 minutes to form a non-conductive film 13, thereby producing a cathode plate 11.

Comparative Example 2
A cathode plate 1 was produced in the same manner as in Example 1 except that the height L1 of the protrusions 2a of the metal plate 2 was 40 μm. In the cathode plate 1 thus manufactured, when the height L2 of the substantially vertical portion 2d is measured by a laser displacement meter, the average is 30 μm, the height L3 of the inclined portion 2e is 10 μm on average, and the length L4 of the inclined portion 2e The average was 50 μm.

Comparative Example 3
A cathode plate 1 was produced in the same manner as in Example 4 except that the 200 mm × 100 mm × 4 mm stainless steel (hot rolled material) metal plate 2 was used. When the height L2 of the substantially vertical portion 2d was measured by the laser displacement meter in the cathode plate 1 manufactured in this manner, a part thereof was about 20 μm, the height L3 of the inclined portion 2e was 180 μm on average, and the inclined portion 2e The length L4 was 300 μm on average. A portion where the height L2 of the substantially vertical portion 2d is low is formed by a concave portion of the surface asperity formed in the manufacturing process of the hot-rolled material.

Comparative Example 4
A cathode plate 1 was produced in the same manner as in Example 4 except that a disk-like protrusion 2a was formed using a flat end mill drill. In the cathode plate 1 thus produced, the height L2 of the substantially vertical portion 2d was measured by a laser displacement meter, and it was 200 μm, and there was no inclined portion.

Comparative Example 5
The metal plate was wet-etched in the same manner as in Example 1 to form a projection having a height L1 of 2000 μm. However, the warp of the metal plate is large, and it is difficult to form a nonconductive film by screen printing.

<Production of electric nickel>
Electronickel was manufactured by electrolytic processing using the cathode plate produced in each Example and the comparative example. Specifically, a cathode plate and an anode plate made of 200 mm × 100 mm × 10 mm of electric nickel were opposed to each other and immersed in an electrolytic cell containing a nickel chloride electrolytic solution. Then, nickel was electrodeposited on the surface of the cathode plate under conditions of an initial current density of 710 A / m ² and an electrolysis time of 3 days. After the electrolysis, the electrodeposited nickel deposited on the cathode plate was peeled off to obtain small lumps of electroplated nickel.

<Evaluation>
The number of times the cathode plate used for the electrolytic treatment could be repeatedly used as it was was evaluated. When the loss of the non-conductive film is increased, the nickel deposited in the adjacent projections and conductive portions may be connected to each other, and it may not be possible to obtain electric nickel having a desired shape. Therefore, when the nonconductive film was missing from the boundary with the protrusion in the direction of the flat portion by 1 mm or more, the use was stopped and the number of repetitions up to that point was evaluated. Also, electrodeposition and stripping of nickel were repeated up to 20 times. Moreover, also when the nonconductive film was missing and the diameter of the conductive part was enlarged by 1 mm or more, the use was stopped and the number of repetitions up to this point was evaluated.

  The nonconductive film of the cathode plate whose number of repetitions was evaluated was peeled off by a water jet, and the peelability of the nonconductive film was evaluated. Specifically, using a water jet, using a rotary nozzle with a hole diameter of 0.4 mm and 3 holes, the water pressure is 200 MPa, the water amount is 10 L / min, the effective width is 30 mm, and the nozzle is moved at 2 m / min. Peeling of the nonconductive film was performed. Regarding the removability of the nonconductive film, the case where the nonconductive film can be almost completely removed within about 20 seconds (200 mm × 100 mm) per cathode plate is regarded as “good”, and the nonconductive film takes over 20 seconds. The case where it could not be removed was evaluated as "peeling remaining occurrence".

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

  As shown in Table 1, in Examples 1 to 5 using the cathode plate 1 in which the nonconductive film 3 is formed on the flat portion 2b of the metal plate 2 and the height L1 of the projection 2a is 60 μm to 500 μm, The omission of the nonconductive film 3 was suppressed, and the film could be used sufficiently repeatedly. In particular, in Examples 1, 2, 4, and 5 in which the height L1 of the protrusion 2a is 100 μm or more, the number of times of repeated use exceeds 20 times. Further, in Examples 1 to 5 in which the height L2 of the substantially vertical portion 2d is 40 μm or more and 0.8 × L1 μm or less, when the nonconductive film 3 is peeled by water jet, peeling residuals and the like do not occur. It could be peeled off well.

  On the other hand, in Comparative Example 1 in which the nonconductive film 13 was formed on the flat metal plate 12, the nonconductive film 14 was missing, and it was not possible to use the film sufficiently repeatedly. Further, even in Comparative Example 2 in which the height L1 of the projection 2a was low, the nonconductive film 3 was missing, and the film could not be used sufficiently repeatedly. Further, in Comparative Example 3, the nonconductive film 3 was missing from a portion where the height L2 of the substantially vertical portion 2d was as low as 20 μm in the shape of the side surface of the protrusion 2a, and could not be used sufficiently repeatedly. In Comparative Example 4, since there is no inclined portion in the shape of the side surface of the protrusion 2a, when the non-conductive film 3 is peeled with water jet, peeling residue occurs at the corner formed substantially at right angles to the side surface of the protrusion 2a. did. Furthermore, in Comparative Example 5, since the height L1 of the protrusions 2a is too high, the warpage of the metal plate 2 becomes large, the application of the non-conductive film becomes difficult, and the cathode plate can not be configured.

1 cathode plate 2 metal plate 2a protrusion 2b flat portion 2c conductive portion 2d substantially vertical portion 2e inclined portion 3 nonconductive film 4 nickel

Claims (5)

A metal plate having a thickness of 3 mm or more and 10 mm or less, and a plurality of disk-shaped protrusions arranged on at least one surface;
And a nonconductive film formed on the surface of the metal plate other than the protrusions.
The projection has a shape in which the side surface is composed of a substantially vertical portion and a sloped portion,
The height L1 of the protrusion is 50 μm to 500 μm,
Assuming that the point of intersection between the side surface and a perpendicular drawn vertically from a position X spaced 20 μm outward from the outer peripheral edge of the protrusion is Y, the length L2 from X to Y is 40 μm or more and 0.8 × L1 μm or less The cathode plate for metal electrodeposition. The metal plate is made of titanium or stainless steel.
A cathode plate for metal electrodeposition according to claim 1. Used in the production of electric nickel for plating
The cathode plate for metal electrodeposition of Claim 1 or 2. A method of manufacturing a cathode plate for metal electrodeposition according to any one of claims 1 to 3, wherein
A manufacturing method of a cathode plate for metal electrodeposition which forms a plurality of disk shaped projections by wet etching or end milling on at least one surface of a metal plate. In the above end milling, a radius end mill is used.
The manufacturing method of the negative electrode plate for metal electrodeposition of Claim 4.

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