US20190233960A1 - Metal electrodeposition cathode plate and production method therefor - Google Patents
Metal electrodeposition cathode plate and production method therefor Download PDFInfo
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- US20190233960A1 US20190233960A1 US16/317,141 US201716317141A US2019233960A1 US 20190233960 A1 US20190233960 A1 US 20190233960A1 US 201716317141 A US201716317141 A US 201716317141A US 2019233960 A1 US2019233960 A1 US 2019233960A1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
- C25C7/08—Separating of deposited metals from the cathode
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/003—3D structures, e.g. superposed patterned layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/16—Apparatus for electrolytic coating of small objects in bulk
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Abstract
Description
- The present invention relates to a metal electrodeposition cathode plate and a production method therefor.
- Conventionally, electric nickel serving as an anode raw material for nickel plating has been used by being placed in a titanium basket to be an anode holding tool and hung in a nickel plating tank. At this time, as the electric nickel of an anode raw material, those obtained by cutting plate-shaped electric nickel electrodeposited on a cathode plate into small pieces have been used.
- However, the corner of the small pieces of electric nickel is sharp, and it has been thus difficult to handle the electric nickel when charging the electric nickel into a titanium basket. In addition, the small pieces of electric nickel cause so-called scaffold bridging as the corner thereof is caught by the mesh of the titanium basket after the electric nickel was charged in the titanium basket, the filling state of electric nickel in the titanium basket changes, and this causes plating unevenness in some cases.
- Hence, it has been proposed to use blobby (button-shaped) electric nickel with rounded corner. The blobby electric nickel can be produced, for example, by precipitating nickel on a conductive portion by using a cathode plate on which a plurality of circular conductive portions is disposed at regular intervals by electrolysis and then peeling off the electrodeposited nickel from the conductive portion. According to such a method, it is possible to efficiently produce a plurality of pieces of blobby electric nickel from one cathode plate.
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FIG. 5 is a view illustrating an example of a conventional cathode plate to be used in production of blobby electric nickel. Acathode plate 11 is masked with anon-conductive film 13 on a flat plate-shaped metal plate 12 except the place to be aconductive portion 12 a, and theconductive portion 12 a is a concave portion and thenon-conductive film 13 is a convex portion on thiscathode plate 11. Nickel having a proper size is electrodeposited on theconductive portion 12 a and blobby electric nickel is thus produced by using such acathode plate 11. - As a method for forming the
non-conductive film 13 on themetal plate 12 as thecathode plate 11, for example, there is a method for forming anon-conductive film 13 having a desired pattern by coating a thermosetting non-conductive resin such as an epoxy resin on the flat plate-shaped metal plate 12 by a screen printing method and heating the thermosetting non-conductive resin as illustrated inFIG. 6A (seePatent Documents 1 and 2). Incidentally,FIG. 6B illustrates a state in which nickel (electric nickel) 14 is electrodeposited and precipitated on theconductive portion 12 a by using thecathode plate 11 on which thenon-conductive film 13 is formed. In thecathode plate 11, thenickel 14 begins to be electrodeposited and precipitated from theconductive portion 12 a, grows not only in the thickness (longitudinal) direction but also in the planar (lateral) direction, and is in the state of being piled on the upper portion of thenon-conductive film 13 as well. - In addition, for example, there has also been proposed a method for forming a
non-conductive film 23 having a desired pattern by coating a photosensitive non-conductive resin on ametal plate 22 and removing the non-conductive resin at the place corresponding to aconductive portion 22 a by exposure and development as illustrated inFIG. 7A . Incidentally,FIG. 7B illustrates a state in which nickel (electric nickel) 24 is electrodeposited and precipitated on theconductive portion 22 a by using thecathode plate 21 on which thenon-conductive film 23 is formed. In thecathode plate 21 as well, thenickel 24 begins to be electrodeposited and precipitated from theconductive portion 22 a and grows not only in the thickness direction but also in the planar direction. - Furthermore, there has also been proposed a method for producing a cathode plate constituting a non-conductive portion by solidifying the periphery of a metal structure incorporated so that a plurality of studs to be a conductive portion is disposed at regular intervals with an insulating resin by an injection molding method (see Patent Document 3).
- Patent Document 1: Japanese Examined Patent Application Publication No. S51-036693
Patent Document 2: Japanese Unexamined Patent Application, Publication No. S52-152832
Patent Document 3: Japanese Examined Patent Application Publication No. S56-029960 - Meanwhile, in a case in which blobby electric nickel is produced using a cathode plate as described above, it is required that the non-conductive film (non-conductive portion) to be formed on the cathode plate has a long service life and can be easily maintained even in the case of being lost (deteriorated).
- The film thickness of the
non-conductive film 13 gradually decreases toward theconductive portion 12 a and is thus significantly thin at the boundary with theconductive portion 12 a in a case in which thenon-conductive film 13 is formed by coating a non-conductive resin on themetal plate 12 by screen printing as illustrated inFIG. 6A . Such a change in the film thickness of thenon-conductive film 13 depends on the amount of the non-conductive resin coated, the viscosity and temperature characteristics of viscosity of the non-conductive resin, the curing temperature of the non-conductive resin, the surface roughness and surface free energy of the metal surface, and the like. Hence, the film thickness of thenon-conductive film 13 is significantly thin at the boundary with theconductive portion 12 a. - As described above, the
nickel 14 begins to be electrodeposited and precipitated from theconductive portion 12 a, grows not only in the longitudinal direction but also in the lateral direction, and thus is in the state of gradually being piled on thenon-conductive film 13 as well when blobby electric nickel is produced by using thecathode plate 11 as illustrated inFIG. 5 andFIG. 6 . Hence, the part of the thinnon-conductive film 13 to be formed in the vicinity of the boundary with theconductive portion 12 a is likely to be lost by the stress at the time of electrodeposition of thenickel 14 and the impact at the time of peeling off of the electric nickel as well as the adhesive property of the part with themetal plate 12 is likely to diminish by penetration of the electrolytic solution. In addition, thenon-conductive film 13 in the vicinity of thenon-conductive film 13 lost rises from the surface of themetal plate 12 when loss of thenon-conductive film 13 once occurs, thus the electrolytic solution is more likely to enter the gap, and as a result, the electrolytic solution gets into the gap of thenon-conductive film 13 risen from the surface of themetal plate 12 and thenickel 14 is electrodeposited when it is attempted to continuously electrodeposit nickel. Thereafter, thenon-conductive film 13 in which thenickel 14 is bitten is further lost when it is attempted to peel off thenickel 14 electrodeposited by being gotten into the gap. - In this manner, in the
conventional cathode plate 11, when loss of thenon-conductive film 13 occurs and the lost part expands in a chain reaction, thenickel 14 grown from the adjacentconductive portions 12 a is likely to be connected to each other, electric nickel having a desired shape cannot be obtained, and a defective product is produced. Accordingly, it is required to peel off the entirenon-conductive films 13 before loss of thenon-conductive film 13 occurs, to form thenon-conductive film 3 again, and thus to maintain thecathode plate 11. However, in reality, it is required to perform maintenance of thecathode plate 11 at the stage at which the electrodeposition treatment of nickel is conducted about from several times to at most less than 10 times, and not only the productivity decreases but the maintenance cost also increases. - On the other hand, it is possible to form the
non-conductive film 23 having a uniform film thickness in thecathode plate 21 in which thenon-conductive film 23 is formed using a photosensitive non-conductive resin by exposure and development as illustrated inFIG. 7A . However, thenickel 24 is caught by the step of thenon-conductive film 23 constituting the convex portion when thenickel 24 is peeled off after the electrodeposition, a large impact is likely to be applied to thenon-conductive film 23, and thus loss of thenon-conductive film 23 occurs in this case as well. - Incidentally, in the method for forming a non-conductive portion by injection molding as in
Patent Document 3, the production cost of the cathode plate itself increases and it is difficult to maintain the cathode plate in a case in which the non-conductive portion is deteriorated although the service life of the non-conductive portion to be formed increases. - In view of such conventional circumstances, an object of the present invention is to provide a metal electrodeposition cathode plate in which a non-conductive film on a metal plate is hardly lost and which can be repeatedly used and a production method therefor.
- The inventors of the present invention have carried out intensive investigations in order to solve the problems described above. As a result, it has been found out that the non-conductive film is hardly lost as protrusions are provided on a metal plate to form a conductive portion and a non-conductive film is provided on the metal surface except the protrusions, whereby the present invention has been completed.
- (1) A first aspect of the present invention is a metal electrodeposition cathode plate, which includes a metal plate having a plurality of disc-shaped protrusions disposed on at least one surface of the metal plate and a non-conductive film formed on a surface of the metal plate except the protrusions, in which a minimum film thickness of the non-conductive film at a position between centers of the adjacent protrusions is the same as or greater than a height of the protrusion.
- (2) A second aspect of the present invention is the metal electrodeposition cathode plate according to the first aspect, in which the height of the protrusion is 50 μm or more and 1000 μm or less.
- (3) A third aspect of the present invention is the metal electrodeposition cathode plate according to the first or second aspect, in which a difference between the minimum film thickness of the non-conductive film at the position between centers of the adjacent protrusions and the height of the protrusion is 200 μm or less.
- (4) A fourth aspect of the present invention is the metal electrodeposition cathode plate according to any one of the first to third aspects, in which the metal plate is formed of titanium or stainless steel.
- (5) A fifth aspect of the present invention is the metal electrodeposition cathode plate according to any one of the first to fourth aspects, in which the metal electrodeposition cathode plate is used in production of electric nickel for plating.
- (6) A sixth aspect of the present invention is a method for producing a metal electrodeposition cathode plate, which includes a first step of forming a plurality of disc-shaped protrusions on at least one surface of a metal plate and a second step of forming a non-conductive film on a surface of the metal plate except the protrusions, in which a minimum film thickness of the non-conductive film at a position between centers of the adjacent protrusions is set to be the same as or greater than a height of the protrusion in the second step.
- According to the present invention, it is possible to provide a metal electrodeposition cathode plate in which a non-conductive film is hardly lost and which can be repeatedly used and a production method therefor.
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FIG. 1 is a plan view illustrating a configuration of a cathode plate. -
FIG. 2 is an enlarged cross-sectional view of a main part illustrating a configuration of a cathode plate,FIG. 2A is an enlarged cross-sectional view of a main part for describing the state of a cathode plate before nickel electrodeposition, andFIG. 2B is an enlarged cross-sectional view of a main part for describing the state of a cathode plate after nickel electrodeposition. -
FIG. 3 is an enlarged cross-sectional view of a main part illustrating a configuration of a cathode plate in a case in which the film thickness of the non-conductive film is thin,FIG. 3A is an enlarged cross-sectional view of a main part for describing the state of a cathode plate before nickel electrodeposition, andFIG. 3B is an enlarged cross-sectional view of a main part for describing the state of a cathode plate after nickel electrodeposition. -
FIG. 4 is an enlarged cross-sectional view of a main part for describing a method for producing a cathode plate,FIG. 4A is an enlarged cross-sectional view of a main part for describing a first step, andFIG. 4B is an enlarged cross-sectional view of a main part for describing a second step. -
FIG. 5 is a plan view illustrating a configuration of a conventional cathode plate. -
FIG. 6 is an enlarged cross-sectional view of a main part illustrating a configuration of a conventional cathode plate,FIG. 6A is an enlarged cross-sectional view of a main part for describing the state of a cathode plate before nickel electrodeposition, andFIG. 6B is an enlarged cross-sectional view of a main part for describing the state of a cathode plate after nickel electrodeposition. -
FIG. 7 is an enlarged cross-sectional view of a main part illustrating a configuration of a conventional cathode plate,FIG. 7A is an enlarged cross-sectional view of a main part for describing the state of a cathode plate before nickel electrodeposition, andFIG. 7B is an enlarged cross-sectional view of a main part for describing the state of a cathode plate after nickel electrodeposition. - Hereinafter, an embodiment (hereinafter referred to as the “present embodiment”) in which the metal electrodeposition cathode plate of the present invention is applied to a metal electrodeposition cathode plate to be used in the production of electric nickel will be described in detail. It should be noted that the present invention is not limited to the following embodiments and can be appropriately changed without changing the gist of the present invention.
- A
cathode plate 1 according to the present embodiment includes ametal plate 2 on which a plurality of disc-shapedprotrusions 2 a is disposed and anon-conductive film 3 formed on the surface of themetal plate 2 except theprotrusions 2 a as illustrated inFIG. 1 . Thecathode plate 1 is used, for example, by being hung in an electrolytic cell containing an electrolytic solution containing nickel and an anode by a hangingmember 5 and nickel having a desired shape is electrodeposited and precipitated on the surface of the cathode plate as to be described later. - The
metal plate 2 is a plate of a metal having a flat plate shape and has a plurality of disc-shapedprotrusions 2 a as illustrated inFIG. 1 andFIG. 2A . Here, the surface of themetal plate 2 except theprotrusion 2 a is referred to as a “flat area 2 b” with respect to theprotrusion 2 a. In addition, the “height X of the protrusion” is the protruding height from the surface of theflat area 2 b of themetal plate 2. - Incidentally, an example in which the
protrusion 2 a is provided on one surface of themetal plate 2 is illustrated inFIG. 2 , but theprotrusion 2 a may be provided on both surfaces of themetal plate 2. - The size of the
metal plate 2 is not particularly limited, and it may be set according to the desired size and number of electric nickel to be produced as appropriate. For example, the size can be set to a rectangular size of which one side is 100 mm or more and 2000 mm or less. In addition, the thickness of themetal plate 2 is preferably, for example, about 1.5 mm or more and about 5 mm or less in a case in which theprotrusion 2 a is provided on one surface, and it is preferably, for example, about 3 mm or more and about 10 mm or less in a case in which theprotrusion 2 a is provided on both surfaces. There is a tendency that warpage is likely to occur by theprotrusion 2 a and theflat area 2 b when the thickness of themetal plate 2 is too thin. On the other hand, the weight of themetal plate 2 increases and it is difficult to handle themetal plate 2 when the thickness of themetal plate 2 is too thick. - The material for the
metal plate 2 is not particularly limited as long as it is a metal which is less susceptible to corrosion by the electrolytic solution to be used and forms only loose bonding with an electrodeposit such as nickel, but preferred examples thereof may include titanium and stainless steel. - On the
metal plate 2, a concave step is formed by theadjacent protrusions 2 a in order to form thenon-conductive film 3 having a predetermined thickness as well as the surface of a plurality of disc-shapedprotrusions 2 a is exposed from thenon-conductive film 3 to be described later and functions as a conductive portion. Hereinafter, the surface of theprotrusions 2 a to be exposed from thenon-conductive film 3 is referred to as a “conductive portion 2 c” in some cases. Nickel 4 is electrodeposited and precipitated on theconductive portion 2 c by an electrolytic treatment. - The size of the disc-shaped
protrusion 2 a may be set according to the desired size of electric nickel as appropriate, but the diameter thereof can be set to, for example, 5 mm or more and 30 mm or less. In addition, the height X of theprotrusion 2 a is preferably 50 μm or more and 1000 μm or less and more preferably 100 μm or more and 500 μm or less. When the height X of theprotrusion 2 a is too low, the film thickness of thenon-conductive film 3 to be formed on theflat area 2 b of themetal plate 2 is insufficient and the non-conductive film is likely to be lost by the stress at the time of electrodeposition of the nickel 4 and the impact at the time of peeling off of the electric nickel. On the other hand, when the height X of theprotrusion 2 a is too high, for example, the number of coating increases and the productivity decreases when forming a non-conductive film by screen printing. In addition, when the height X is too high, distortion of themetal plate 2 is likely to occur at the time of processing of theprotrusion 2 a, themetal plate 2 is likely to warp, and it is thus difficult to form thenon-conductive film 3. Incidentally, it is also possible to increase the thickness of themetal plate 2 in order to diminish the influence of distortion of themetal plate 2, but the weight of themetal plate 2 increases and it is difficult to handle the metal plate. - In addition, fine concave and convex may be provided on the surface of the
metal plate 2, namely, on the surface of the disc-shapedprotrusion 2 a of themetal plate 2 by sand blasting or etching. This makes it possible to peel off the nickel 4 electrodeposited on theprotrusion 2 a with a proper impact without falling off the nickel 4 during the electrolytic treatment. In this case, it is preferable that the film thickness of thenon-conductive film 3 to be described later is two or more times the maximum surface roughness Rz of themetal plate 2. There is concern that pinholes and insulation failure portions are generated on thenon-conductive film 3 when the film thickness of thenon-conductive film 3 is thinner than two times the maximum surface roughness Rz of themetal plate 2. - The
non-conductive film 3 is formed on theflat area 2 b, which is the surface of themetal plate 2 except theprotrusion 2 a, as illustrated inFIG. 2 , and the surface of a plurality ofprotrusions 2 a disposed on themetal plate 2, namely, theconductive portion 2 c is put into a state of being exposed by this. Moreover, the nickel 4 is formed by being individually divided into a small blobby shape as the nickel 4 is electrodeposited and precipitated on such aconductive portion 2 c of themetal plate 2. - Here, in the
cathode plate 1, thenon-conductive film 3 is formed on theflat area 2 b having a concave step formed by theadjacent protrusions 2 a and thus thenon-conductive film 3 having a predetermined thickness is formed. In thecathode plate 1 according to the present embodiment, the minimum film thickness Y of thenon-conductive film 3 is the same as or greater than the height X of theprotrusion 2 a and it is preferably the same as the height X. - Incidentally, 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 between the centers of theadjacent protrusions 2 a. Thenon-conductive film 3 is formed as the central portion betweenadjacent protrusions 2 a is piled by the surface tension as illustrated inFIG. 2A . In this case, the minimum film thickness Y of thenon-conductive film 3 is the film thickness of the end portion in contact with the side face of theprotrusion 2 a. In addition, thenon-conductive film 3 may be formed on the surface of theprotrusion 2 a in a case in which the film thickness is thick. As the minimum film thickness Y of thenon-conductive film 3 at this time, not the film thickness of thenon-conductive film 3 formed on the surface of theprotrusion 2 a but the minimum value among the film thicknesses of thenon-conductive films 3 formed at the position on theflat areas 2 b is taken. Incidentally, in thecathode plate 1, the film thickness varies depending on the position of theprotrusion 2 a to be selected but the minimum value among the film thicknesses is taken as the minimum film thickness Y. - The
non-conductive film 3 is formed on theflat area 2 b which is formed by theadjacent protrusions 2 a and has a concave step. Hence, the film thickness of the end portion of thenon-conductive film 3 is hardly thinned and thenon-conductive film 3 is hardly lost even by the stress at the time of electrodeposition of the nickel 4 and the impact at the time of peeling off of the nickel 4 after electrodeposition as the conventionalnon-conductive film 13 illustrated inFIG. 6 . In addition, thenon-conductive film 3 does not protrude in a convex shape and the end portion thereof is protected by the concave step as the conventionalnon-conductive film 23 illustrated inFIG. 7 . Consequently, the impact to be applied to the end portion of thenon-conductive film 3 by the nickel 4 is minor and thenon-conductive film 3 is hardly lost even when the nickel 4 is peeled off from thecathode plate 1. In this manner, in thecathode plate 1, thenon-conductive film 3 is hardly lost and it is thus possible to repeatedly use thenon-conductive film 3 in electrodeposition without replacing thenon-conductive film 3, to decrease the maintenance cost, and to achieve improvement in the productivity. - Furthermore, the minimum film thickness Y of the
non-conductive film 3 is the same as or greater than the height X of theprotrusion 2 a, and the nickel 4 can be thus peeled off without being caught by the peripheral portion of theprotrusion 2 a when the nickel 4 is peeled off from thecathode plate 1. On the other hand, in a case in which the minimum film thickness Y of thenon-conductive film 3 is less than the height X of theprotrusion 2 a as illustrated inFIG. 3 , it is difficult to peel off the electrodeposited nickel 4 since the electrodeposited nickel 4 is caught by the peripheral portion of theprotrusion 2 a, for example, at the place denoted by “A” in the drawing when the electrodeposited nickel 4 is peeled off from thecathode plate 1. - The upper limit of the minimum film thickness Y of the
non-conductive film 3 is not particularly limited, but the difference (Y−X) between the minimum film thickness Y and the height X of theprotrusion 2 a is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, and particularly preferably 5 μm or less. Here, as described above, the minimum film thickness Y of thenon-conductive film 3 is not particularly limited as long as it is the same as or greater than the height X of theprotrusion 2 a, but it is not required to set the minimum film thickness Y thicker than necessary. For example, it is difficult to coat thenon-conductive film 3 so as to have a film thickness thicker than the height X of theprotrusion 2 a by more than 200 μm by screen printing. It is required to conduct coating while finely adjusting the size of the pattern of the screen plate plural times when it is attempted to form thenon-conductive film 3 having a film thickness thicker than the height X of theprotrusion 2 a by more than 200 μm by screen printing, and thus the adjustment is difficult and the productivity decreases. - Incidentally, in a case in which the
non-conductive film 3 is formed on theflat area 2 b on themetal plate 2 by the screen printing method, the material for thenon-conductive film 3 is coated on the surface of theprotrusion 2 a as well, thus the surface area of theconductive portion 2 c decreases and the initial current density increases in some cases, but there is no problem as long as troubles are not caused in the characteristics of the electrodeposited nickel 4. In addition, thenon-conductive film 3 attached on the surface of theprotrusion 2 a is likely to be lost since the film thickness thereof is extremely thin, but thenon-conductive film 3 to be formed on theflat area 2 b has no problem since the film thickness thereof is thick and the loss thereof is suppressed. - The
non-conductive film 3 is not particularly limited as long as it is formed from a material which is non-conductive and is less susceptible to corrosion by the electrolytic solution to be used. For example, it is preferable that thenon-conductive film 3 is composed of a thermosetting resin or a photocuring (ultraviolet curing and the like) resin from the viewpoint of being easy to form the film. Specific examples thereof may include an insulating resin such as an epoxy-based resin, a phenol-based resin, a polyamide-based resin, or a polyimide-based resin. - In the
cathode plate 1 having the configuration described above, the surface of theprotrusion 2 a to be exposed from thenon-conductive film 3 is theconductive portion 2 c and the nickel 4 is electrodeposited and precipitated thereon as illustrated inFIG. 2B . In thecathode plate 1, the nickel 4 grows not only in the thickness direction but also in the planar direction and is thus in the state of being piled on the upper part of thenon-conductive film 3. For this reason, it is preferable to terminate the electrodeposition before the nickel 4 grown from theconductive portion 2 c of the surface of theadjacent protrusion 2 a comes into contact with each other. - Thereafter, a plurality of pieces of blobby electric nickel can be obtained from one
cathode plate 1 by peeling off the nickel 4 from thecathode plate 1 after the electrodeposition of nickel is terminated. As described above, in thecathode plate 1 according to the present embodiment, thenon-conductive film 3 is hardly lost and it is thus possible to repeatedly use thenon-conductive film 3 without replacing thenon-conductive film 3, to decrease the maintenance cost, and to achieve improvement in the productivity. - Incidentally, in the
cathode plate 1 according to the present embodiment, the nickel 4 is electrodeposited but silver, gold, zinc, tin, chromium, cobalt, or any alloy thereof may be electrodeposited without being limited to nickel. - The method for producing a
cathode plate 1 according to the present embodiment includes a first step (FIG. 4A ) of forming a plurality of disc-shapedprotrusions 2 a on at least one surface of ametal plate 2 and a second step (FIG. 4B ) of forming anon-conductive film 3 on the surface of themetal plate 2 except theprotrusions 2 a as illustrated inFIG. 4 . - In the first step, a plurality of disc-shaped
protrusions 2 a is formed on the surface of themetal plate 2. For example, the parts of the flat plate-shapedmetal plate 2 except theprotrusions 2 a are scraped, theprotrusions 2 a having a height X are left, andflat areas 2 b are thus formed. The processing method is not particularly limited, and the formation offlat areas 2 b can be conducted by, for example, wet etching processing, end mill processing, and laser processing. - For example, in the case of processing a flat plate-shaped stainless steel plate by wet etching, a photosensitive etching resist is coated on the surface of a stainless steel plate and is then exposed by passing through a film or glass on which a desired pattern is drawn and the etching resist of the part to be etched is removed by a development treatment. Thereafter, the stainless steel plate developed is dipped in an etching solution (for example, a 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, whereby a plurality of disc-shaped
protrusions 2 a matching with a desired pattern can be formed. - Incidentally, the
protrusions 2 a may be formed only on one surface of themetal plate 2 or on both surfaces of themetal plate 2. - In the second step, the
non-conductive film 3 is formed on theflat areas 2 b to be the surface of themetal plate 2 except theprotrusions 2 a. The method for forming thenon-conductive film 3 is not particularly limited, and the formation of thenon-conductive film 3 can be conducted by screen printing. In a case in which the material for thenon-conductive film 3 is a thermosetting resin or a photocurable resin, heat curing or photocuring may be conducted if necessary. - At this time, the
non-conductive film 3 is formed so that the minimum film thickness Y of thenon-conductive film 3 at the position between the centers ofadjacent protrusions 2 a is the same as or greater than the height X of theprotrusion 2 a. In a case in which a desired film thickness cannot be obtained by one time of screen printing, the above-described screen printing and heat curing or photocuring may be repeated until the desired film thickness is obtained. - According to the method for producing a cathode plate according to the present embodiment, it is possible to obtain the
cathode plate 1 in which the non-conductive film on the metal plate is hardly lost and which can be repeatedly used. - Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited by these Examples at all. It should be noted that members having the same functions as the members illustrated in
FIG. 1 toFIG. 6 are denoted by the same reference numerals for the sake of convenience. - A
cathode plate 1 as illustrated inFIG. 1 andFIG. 2 was fabricated. Specifically, first, ametal plate 2 which was made of stainless steel and had a size of 200 mm×100 mm×4 mm was subjected to wet etching to form disc-shapedprotrusions 2 a (18 pieces). At this time, the size of theprotrusion 2 a was set to a diameter of 14 mm and a height X of 300 μm, and the minimum center-distance betweenadjacent protrusions 2 a was set to 21 mm. - Next, a thermosetting epoxy resin was coated on
flat areas 2 b of themetal plate 2 by a screen printing method and cured by heating at 150° C. for 60 minutes to form anon-conductive film 3. In thecathode plate 1 fabricated in this manner, the difference between the minimum film thickness Y of thenon-conductive film 3 and the height X of the protrusion at a position between the centers ofadjacent protrusions 2 a was measured at arbitrary 10 places by using a laser displacement meter, and the results were in a range of from 40 to 70 μm and the minimum film thickness Y of thenon-conductive film 3 was thus 340 μm. - A
cathode plate 1 was fabricated in the same manner as in Example 1 except that the height X of theprotrusion 2 a of themetal plate 2 was set to 500 μm and thenon-conductive film 3 was formed on theflat area 2 b so as to have a predetermined thickness. In thecathode plate 1 fabricated in this manner, the difference between the minimum film thickness Y of thenon-conductive film 3 and the height X of theprotrusion 2 a was measured at arbitrary 10 places by using a laser displacement meter, and the results were in a range of from 10 to 50 μm and the minimum film thickness Y of thenon-conductive film 3 was thus 510 μm. - A
cathode plate 1 was fabricated in the same manner as in Example 1 except that the height X of theprotrusion 2 a of themetal plate 2 was set to 60 μm and thenon-conductive film 3 was formed on theflat area 2 b so as to have a predetermined thickness. In thecathode plate 1 fabricated in this manner, the difference between the minimum film thickness Y of thenon-conductive film 3 and the height X of the protrusion was measured at arbitrary 10 places by using a laser displacement meter, and the results were in a range of from 60 to 90 μm and the minimum film thickness Y of thenon-conductive film 3 was thus 120 μm. - A
cathode plate 1 was fabricated in the same manner as in Example 1 except that the height X of theprotrusion 2 a of themetal plate 2 was set to 100 μm and thenon-conductive film 3 was formed on theflat area 2 b so as to have a predetermined thickness. In thecathode plate 1 fabricated in this manner, the difference between the minimum film thickness Y of thenon-conductive film 3 and the height X of the protrusion was measured at arbitrary 10 places by using a laser displacement meter, and the results were in a range of from 100 to 150 μm and the minimum film thickness Y of thenon-conductive film 3 was thus 200 μm. - A
cathode plate 1 was fabricated in the same manner as in Example 1 except that the height X of theprotrusion 2 a of themetal plate 2 was set to 40 μm and thenon-conductive film 3 was formed on theflat area 2 b so as to have a predetermined thickness. In thecathode plate 1 fabricated in this manner, the difference between the minimum film thickness Y of thenon-conductive film 3 and the height X of theprotrusion 2 a was measured at arbitrary 10 places by using a laser displacement meter, and the results were in a range of from 10 to 40 μm and the minimum film thickness Y of thenon-conductive film 3 was thus 50 μm. - In Comparative Example 1, a
conventional cathode plate 11 as illustrated inFIG. 5 andFIG. 6 was fabricated. - Specifically, a thermosetting epoxy resin was coated on a flat plate-shaped
metal plate 12 which was made of stainless steel and had a size of 200 mm×100 mm×4 mm exceptconductive portions 12 a (18 pieces) having a diameter of 14 mm by a screen printing method and cured by heating at 150° C. for 60 minutes to form anon-conductive film 13, whereby thecathode plate 11 was fabricated. In thecathode plate 11 fabricated in this manner, the maximum film thickness of thenon-conductive film 13 was measured at arbitrary 10 places by using a laser displacement meter, and the results were in a range of from 90 to 110 μm. - A cathode plate was fabricated in the same manner as in Example 1 except that the height X of the protrusion of the metal plate was set to 500 μm and the non-conductive film was formed on the flat area so as to have a predetermined thickness. In the cathode plate fabricated in this manner, the difference between the minimum film thickness of the non-conductive film and the height of the protrusion was measured at arbitrary 10 places by using a laser displacement meter, and the results were in a range of from −200 to −150 μm and the minimum film thickness Y of the
non-conductive film 3 was thus 300 μm. Incidentally, the minimum film thickness Y of thenon-conductive film 3 is thinner than 500 μm of the height of the protrusion. - A metal plate which was made of stainless steel and had a size of 200 mm×100 mm×4 mm was subjected to wet etching to form protrusions (18 pieces) having a height of 2000 μm. However, warpage of the metal plate was severe and it was difficult to form a non-conductive film by screen printing.
- Electric nickel was produced by an electrolytic treatment using the cathode plates fabricated in the respective Examples and Comparative Examples. Specifically, the cathode plate and an anode plate which was composed of electric nickel and had a size of 200 mm×100 mm×10 mm were dipped in an electrolytic tank containing a nickel chloride electrolytic solution so as to face each other. Thereafter, nickel was electrodeposited on the surface of the cathode plate under the conditions of an initial current density of 710 A/m2 and an electrolysis time of 3 days. After the electrolysis, the electric nickel precipitated on the cathode plate was peeled off to obtain blobby electric nickel for plating.
- The number of times, by which the cathode plate used in the electrolysis treatment was able to be repeatedly utilized as it was, was evaluated. Nickel electrodeposited at the adjacent protrusions and conductive portions are connected to each other and electric nickel having a desired shape cannot be obtained in some cases when the loss of the non-conductive film expands. Hence, the use was stopped and the number of repetitions up to this time point was evaluated in a case in which the non-conductive film was lost from the boundary with the protrusion in the direction of the flat area by 1 mm or more. In addition, the use was stopped and the number of repetitions up to this time point was evaluated in a case in which the non-conductive film was lost and the diameter of the conductive portion increased by 1 mm or more as well.
- The evaluation results are presented in the following Table 1 together with the configuration of the cathode plate.
-
TABLE 1 Height Minimum Maximum X of film film protrusion thickness thickness Y − X Number of (μm) Y (μm) (μm) (μm) repeated use Example 1 300 340 — 40 20 or more Example 2 500 510 — 10 20 or more Example 3 60 120 — 60 16 Example 4 100 200 — 100 20 or more Example 5 40 50 — 10 9 Comparative — — 90~110 — 7 Example 1 Comparative 500 300 — −200 (Difficult Example 2 to peel off) - As presented in Table 1, in Examples 1 to 5 using the
cathode plates 1 in which thenon-conductive film 3 was formed on theflat area 2 b of themetal plate 2 and the minimum film thickness Y of thenon-conductive film 3 was the same as or greater than the height X of theprotrusion 2 a, loss of thenon-conductive film 3 was suppressed and it was possible to sufficiently repeatedly use thecathode plates 1. Particularly, in Examples 1 to 4 in which the height X of theprotrusion 2 a was 50 μm or more, the number of repeated use was more than 10 times. - On the other hand, in Comparative Example 1 in which the
non-conductive film 13 was formed in a convex shape on the flat plate-shapedmetal plate 12, the non-conductive film was lost and it was not possible to sufficiently repeatedly use the cathode plate. In addition, in Comparative Example 2 in which the minimum film thickness Y of the non-conductive film was less than the height X of the protrusion, nickel was caught by the peripheral portion of the protrusion at the time of peeling off of nickel and it was difficult to peel off nickel. -
- 1 CATHODE PLATE
- 2 METAL PLATE
- 2 a PROTRUSION
- 2 b FLAT AREA
- 2 c CONDUCTIVE PORTION
- 3 NON-CONDUCTIVE FILM
- 4 NICKEL
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JP2016143531A JP6724624B2 (en) | 2016-07-21 | 2016-07-21 | Metal electrodeposited cathode plate and method for producing the same |
JP2016-143531 | 2016-07-21 | ||
PCT/JP2017/025093 WO2018016362A1 (en) | 2016-07-21 | 2017-07-10 | Metal electrodeposition cathode plate and production method therefor |
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EP (1) | EP3489395A4 (en) |
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JP6638589B2 (en) * | 2016-07-21 | 2020-01-29 | 住友金属鉱山株式会社 | Cathode plate for metal electrodeposition and method for producing the same |
US11795312B2 (en) | 2018-01-29 | 2023-10-24 | Konica Minolta, Inc. | Resin composition for three-dimensional modeling, three-dimensional modeled article, and method for manufacturing three-dimensional modeled article |
KR102017567B1 (en) * | 2018-11-27 | 2019-09-03 | 주식회사 웨스코일렉트로드 | An anode for electrolysis |
JP7188219B2 (en) * | 2019-03-25 | 2022-12-13 | 住友金属鉱山株式会社 | Cathode plate for metal electrodeposition |
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JPS46919Y1 (en) * | 1966-04-04 | 1971-01-13 | ||
US4040915A (en) * | 1976-06-15 | 1977-08-09 | The International Nickel Company, Inc. | Method for producing regular electronickel or S nickel rounds from electroplating baths giving highly stressed deposits |
JPS6038678Y2 (en) * | 1981-05-15 | 1985-11-19 | 住友金属鉱山株式会社 | Mother plate for metal electrodeposition |
JPS6288754U (en) * | 1985-11-25 | 1987-06-06 | ||
JPH10317197A (en) * | 1997-05-14 | 1998-12-02 | Sumitomo Metal Mining Co Ltd | Electric nickel for plating, cathode plate for for its production and production |
JP2008106292A (en) * | 2006-10-24 | 2008-05-08 | Sumitomo Metal Mining Co Ltd | Method for producing cathode for electrowinning of special shape electric nickel |
US20110233055A1 (en) * | 2008-09-09 | 2011-09-29 | Steelmore Holdingd Pty Ltd | cathode and a method of forming a cathode |
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CN109415832A (en) | 2019-03-01 |
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EP3489395A4 (en) | 2020-04-08 |
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