WO2018016362A1 - Metal electrodeposition cathode plate and production method therefor - Google Patents
Metal electrodeposition cathode plate and production method therefor Download PDFInfo
- Publication number
- WO2018016362A1 WO2018016362A1 PCT/JP2017/025093 JP2017025093W WO2018016362A1 WO 2018016362 A1 WO2018016362 A1 WO 2018016362A1 JP 2017025093 W JP2017025093 W JP 2017025093W WO 2018016362 A1 WO2018016362 A1 WO 2018016362A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- conductive film
- cathode plate
- nickel
- conductive
- plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a metal electrodeposition cathode plate and a method for producing the same.
- small rounded (button-shaped) electric nickel with rounded corners.
- 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 in the production of a small block of nickel.
- 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.
- the conductive portion 12a becomes a concave portion and is non-conductive.
- the film 13 is a convex portion.
- thermosetting such as epoxy resin on the flat metal plate 12.
- 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.
- 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.
- FIG. 7A shows a photosensitive non-conductive resin 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.
- 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).
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the nonconductive film 23 is formed with a uniform film thickness. can do.
- 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.
- 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 inventors of the present invention have made extensive studies to solve the above-mentioned problem. As a result, it has been found that providing a protrusion on the metal plate to form a conductive portion and providing a non-conductive film on the metal surface other than the protrusion makes it difficult for the non-conductive film to be lost, thereby completing the present invention. .
- the first invention of the present invention is a metal plate in which a plurality of disk-like projections are arranged on at least one surface, and a non-conductive film formed on a surface other than the projections of the metal plate And the minimum film thickness of the non-conductive film at a position passing between the centers of adjacent protrusions is equal to or greater than the height of the protrusions.
- a second invention of the present invention is the metal electrodeposition cathode plate according to the first invention, wherein the height of the protrusion is 50 ⁇ m or more and 1000 ⁇ m or less.
- the minimum film thickness of the non-conductive film at a position passing between the centers of the adjacent protrusions and the height of the protrusions A difference is a metal electrodeposition cathode plate which is 200 micrometers or less.
- a fourth invention of the present invention is the metal electrodeposition cathode plate according to any one of the first to third inventions, wherein the metal plate is made of titanium or stainless steel.
- the fifth invention of the present invention is a metal electrodeposition cathode plate used in the production of electroplating nickel in any of the first to fourth inventions.
- 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 disc-shaped protrusions on at least one surface of the metal plate, and the metal A second step of forming a non-conductive film on the surface other than the protrusions of the plate, and in the second step, the minimum film thickness of the non-conductive film at a position passing between the centers of the adjacent protrusions is This is a method for manufacturing a metal electrodeposition cathode plate that is equal to or higher than the height of the protrusion.
- the present invention it is possible to provide a metal electrodeposition cathode plate that can be used repeatedly, and a method for producing the same, that is less likely to lack a non-conductive film.
- this embodiment a metal electrodeposition cathode plate used in the production of electric nickel
- 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.
- the cathode plate 1 includes a metal plate 2 in which a plurality of disc-shaped projections 2a are arranged, and a projection 2a of the metal plate 2. And a non-conductive film 3 formed on the surface other than the above.
- the cathode plate 1 is used by being hung by a hanging member 5 in an electrolytic cell containing, for example, an electrolytic solution containing nickel or an anode, and nickel having a desired shape is electrodeposited on the surface thereof.
- the metal plate 2 is a flat metal plate and has a plurality of disc-shaped protrusions 2a.
- the surface other than the protruding portion 2a is referred to as a “flat portion 2b” with respect to the protruding portion 2a.
- the height X of the protruding portion is a protruding height from the surface of the flat portion 2 b in the metal plate 2.
- the size of the metal plate 2 is not particularly limited, and may be set as appropriate according to the desired size and number of electric nickel to be manufactured. 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 protrusion 2a is provided on one surface, and when the protrusion 2a is provided on both surfaces. Is preferably, for example, about 3 mm or more and 10 mm or less. If the thickness of the metal plate 2 is too small, the protrusions 2a and the flat portions 2b tend to be warped. 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 forms only loose adhesion with an electrodeposit such as nickel, but titanium and stainless steel are preferred.
- the plurality of disk-shaped protrusions 2 a are exposed from a non-conductive film 3 to be described later and function as conductive parts, and the non-conductive film 3 is formed with a predetermined thickness. Accordingly, a concave step is formed by the adjacent protrusion 2a.
- the surface exposed from the non-conductive film 3 in the protrusion 2a may be referred to as “conductive part 2c”.
- nickel 4 is electrodeposited by electrolytic treatment.
- the size of the disc-shaped protrusion 2a may be set as appropriate according to the desired size of the electric nickel, and the diameter may be, for example, 5 mm or more and 30 mm or less. Further, the height X of the protrusion 2a is preferably 50 ⁇ m or more and 1000 ⁇ m or less, and more preferably 100 ⁇ m or more and 500 ⁇ m or less. If the height X of the protrusion 2a is too small, the film thickness of the non-conductive film 3 formed on the flat portion 2b of the metal plate 2 becomes insufficient, and stress during electrodeposition of the nickel 4 and the electric nickel It tends to be lost due to the impact at the time of peeling.
- the height X of the protrusion 2a is excessive, for example, when the non-conductive film is formed by screen printing, the number of times of application increases and the productivity decreases.
- the height X is excessively large, distortion of the metal plate 2 is likely to occur during the processing of the projecting portion 2a, and the metal plate 2 is likely to warp, making it difficult to form the nonconductive film 3.
- 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.
- the non-conductive film 3 is formed on a flat portion 2 b that is a surface other than the protruding portion 2 a in the metal plate 2, whereby a plurality of protruding portions 2 a arranged on the metal plate 2 are formed.
- the surface, that is, the conductive portion 2c is exposed.
- the nickel 4 is electrodeposited on the conductive portion 2c of the metal plate 2, the nickel 4 is formed by being divided into small blocks.
- the non-conductive film 3 is formed on the flat portion 2 b having a concave step formed by the adjacent protrusion 2 a, so that it is formed with a predetermined thickness.
- the non-conductive film 3 has a minimum film thickness Y that is equal to or greater than the height X of the protrusion 2a, and is preferably the same.
- the “minimum film thickness Y of the non-conductive film” is defined as the minimum film thickness of the non-conductive film 3 at a position passing between the centers of the adjacent protrusions 2a. As shown in FIG. 2A, the non-conductive film 3 is formed between the adjacent projecting portions 2a so that the central portion rises due to the surface tension. In this case, the minimum film thickness Y of the non-conductive film 3 is the film thickness of the end that comes into contact with the side surface of the protrusion 2a. Moreover, when the film thickness is thick, the non-conductive film 3 may be formed on the surface of the protrusion 2a.
- the minimum film thickness Y of the non-conductive film 3 at this time is not the film thickness of the non-conductive film 3 formed on the surface of the protrusion 2a, but the film of the non-conductive film 3 formed at a position on the flat portion 2b.
- the minimum value of the thickness In the cathode plate 1, although the film thickness varies depending on the position of the projection 2 a to be selected, the minimum value is the minimum film thickness Y.
- the non-conductive film 3 is formed on the flat portion 2b having a concave step formed by the adjacent protrusion 2a. For this reason, the non-conductive film 3 is unlikely to have a thin film thickness at the end, unlike the conventional non-conductive film 13 shown in FIG. It becomes difficult to be lost. Further, unlike the conventional non-conductive film 23 shown in FIG. 7, the non-conductive film 3 does not protrude in a convex shape, and its end is protected by a concave step. 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 minimum film thickness Y of the non-conductive film 3 is equal to or greater than the height X of the protrusion 2a, the nickel 4 is peeled off from the cathode plate 1 without being caught on the peripheral edge of the protrusion 2a. Can be taken.
- FIG. 3 when the minimum film thickness Y of the non-conductive film 3 is less than the height X of the protrusion 2a, when the electrodeposited nickel 4 is peeled off from the cathode plate 1, for example, FIG. The portion indicated by “A” inside is caught on the peripheral edge of the protruding portion 2a and is difficult to peel off.
- the upper limit of the minimum film thickness Y of the non-conductive film 3 is not particularly limited, but the difference (Y ⁇ X) between the minimum film thickness Y and the height X of the protrusion 2a is preferably 200 ⁇ m or less, and preferably 100 ⁇ m or less. Is more preferably 50 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
- the minimum film thickness Y of the non-conductive film 3 is not particularly limited as long as it is equal to or greater than the height X of the protrusion 2a, but it is not necessary to make it thicker than necessary. For example, it is difficult to apply the non-conductive film 3 beyond 200 ⁇ m from the height X of the protrusion 2a by screen printing.
- the material of the non-conductive film 3 is also applied to the surface of the protrusion 2a, and the surface area of the conductive portion 2c is reduced.
- the initial current density may increase, there is no problem if there is no problem in the characteristics of the electrodeposited nickel 4.
- the non-conductive film 3 attached on the surface of the protrusion 2a is very thin and is likely to be lost.
- the non-conductive film 3 formed on the flat portion 2b is thick and suppresses the loss. So no problem.
- the non-conductive film 3 is not particularly limited as long as the non-conductive film 3 is non-conductive and is made of a material that is less corroded by the electrolyte used.
- a thermosetting resin or a photo-curing (ultraviolet-curing resin) resin from the viewpoint of easy film formation.
- Specific examples include insulating resins such as epoxy resins, phenol resins, polyamide resins, and polyimide resins.
- the nickel 4 is peeled off from the cathode plate 1, whereby a plurality of small-bulk electric nickel can be obtained from one cathode plate 1.
- the non-conductive film 3 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.
- cathode plate 1 which concerns on this Embodiment electrodeposited nickel 4
- it is not limited to nickel
- the manufacturing method of the cathode plate 1 according to the present embodiment is a first step of forming a plurality of disc-shaped protrusions 2a on at least one surface of the metal plate 2 (FIG. 4A). ) And a second step (FIG. 4B) for forming the non-conductive film 3 on the surface of the metal plate 2 other than the protrusions 2a.
- a plurality of disc-shaped protrusions 2 a are formed on the surface of the metal plate 2. For example, a portion other than the protrusion 2a is cut away from the flat metal plate 2 to leave the protrusion 2a having the height X, thereby forming the flat portion 2b.
- the processing method is not particularly limited, and can be performed by, for example, wet etching processing, end mill processing, laser processing, or the like.
- 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.
- 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
- etching solution for example, ferric chloride solution
- the protrusion 2a may be formed only on one surface of the metal plate 2 or may be formed on both surfaces of the metal plate 2.
- the non-conductive film 3 is formed on the flat portion 2b that is the surface of the metal plate 2 other than the protruding 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.
- the non-conductive film 3 is formed so that the minimum film thickness Y of the non-conductive film 3 at a position passing between the centers of the adjacent protrusions 2a is equal to or greater than the height X of the protrusion 2a.
- the above-described screen printing and thermal curing or photocuring may be repeated until the desired film thickness is obtained.
- the cathode plate 1 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 film on the metal plate hardly lost by the simple method described above.
- 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 having a size of 200 mm ⁇ 100 mm ⁇ 4 mm to form disk-shaped protrusions 2a (18 pieces). At this time, the size of the protrusion 2a was 14 mm in diameter and the height was 300 ⁇ m, and the minimum distance between the centers of adjacent protrusions 2a was 21 mm.
- a non-conductive film 3 was formed by applying a thermosetting epoxy resin on the flat portion 2b of the metal plate 2 by screen printing and curing it by heating at 150 ° C. for 60 minutes.
- the difference between the minimum film thickness Y of the non-conductive film 3 and the height X of the protrusion at an arbitrary position passing through the center of the adjacent protrusion 2a is arbitrarily determined by a laser displacement meter. When measured at 10 locations, it was in the range of 40 to 70 ⁇ m. Therefore, the minimum film thickness Y of the non-conductive film 3 was 340 ⁇ m.
- Example 2 A cathode plate 1 was produced in the same manner as in Example 1 except that the height X of the protrusion 2a of the metal plate 2 was 500 ⁇ m and the nonconductive film 3 was formed with a predetermined thickness on the flat portion 2b.
- the difference between the minimum film thickness Y of the non-conductive film 3 and the height X of the protruding portion 2a was measured with a laser displacement meter at any 10 points. Therefore, the minimum film thickness Y of the non-conductive film 3 was 510 ⁇ m.
- Example 3 A cathode plate 1 was produced in the same manner as in Example 1 except that the height X of the protruding portion 2a of the metal plate 2 was 60 ⁇ m and the nonconductive film 3 was formed with a predetermined thickness on the flat portion 2b. In the cathode plate 1 produced in this manner, the difference between the minimum film thickness Y of the non-conductive film 3 and the height X of the protrusions was measured with an laser displacement meter at any 10 points. Therefore, the minimum film thickness Y of the non-conductive film 3 was 120 ⁇ m.
- Example 4 A cathode plate 1 was produced in the same manner as in Example 1 except that the height X of the protruding portion 2a of the metal plate 2 was 100 ⁇ m and the nonconductive film 3 was formed with a predetermined thickness on the flat portion 2b.
- the difference between the minimum film thickness Y of the non-conductive film 3 and the height X of the protrusions was measured with a laser displacement meter at any 10 points. Therefore, the minimum film thickness Y of the non-conductive film 3 was 200 ⁇ m.
- Example 5 A cathode plate 1 was produced in the same manner as in Example 1 except that the height X of the protruding portion 2a of the metal plate 2 was 40 ⁇ m and the nonconductive film 3 was formed with a predetermined thickness on the flat portion 2b.
- the difference between the minimum film thickness Y of the non-conductive film 3 and the height X of the protruding portion 2a was measured with a laser displacement meter at an arbitrary 10 points. Therefore, the minimum film thickness Y of the non-conductive film 3 was 50 ⁇ m.
- Comparative Example 1 a conventional cathode plate 11 as shown in FIGS. 5 and 6 was produced. 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. In the cathode plate 11 thus produced, the maximum film thickness of the non-conductive film 13 was measured at an arbitrary 10 locations with a laser displacement meter and found to be in the range of 90 to 110 ⁇ m.
- Example 2 A cathode plate was produced in the same manner as in Example 1 except that the height of the protruding portion of the metal plate was 500 ⁇ m and the nonconductive film was formed with a predetermined thickness on the flat portion. In the cathode plate produced in this way, the difference between the minimum film thickness of the non-conductive film and the height of the protrusion was measured with a laser displacement meter at 10 locations, which was in the range of ⁇ 200 to ⁇ 150 ⁇ m.
- the minimum film thickness Y of the non-conductive film 3 was 300 ⁇ m. The minimum film thickness Y of the non-conductive film 3 is smaller than the height of the protrusions of 500 ⁇ m.
- 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.
- Table 1 below shows the evaluation results together with the configuration of the cathode plate.
- the non-conductive film 3 is formed on the flat portion 2b of the metal plate 2, and the cathode plate 1 in which the minimum film thickness Y of the non-conductive film 3 is equal to or greater than the height X of the protrusion 2a is used.
- the loss of the non-conductive film 3 was suppressed, and it could be used sufficiently repeatedly.
- the number of repeated uses exceeded 10 times.
- Comparative Example 1 in which the non-conductive film 13 was formed in a convex shape on the flat metal plate 12, the non-conductive film was lost and could not be used repeatedly enough. Further, in Comparative Example 2 in which the minimum film thickness Y of the non-conductive film is less than the height X of the protrusion, nickel was caught on the peripheral edge of the protrusion when the nickel was peeled off, and it was difficult to remove.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
Description
本発明は、金属電着用陰極板及びその製造方法に関する。 The present invention relates to a metal electrodeposition cathode plate and a method for producing the same.
従来より、ニッケルメッキのアノード原料として供せられる電気ニッケルは、アノード保持具となるチタンバスケット内に入れられ、ニッケルメッキ槽内に吊るされて使用されている。このとき、アノード原料である電気ニッケルとしては、陰極板に電着された板状の電気ニッケルを切断して小片状としたものを使用していた。 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.
しかしながら、小片状の電気ニッケルは、角部が鋭いためチタンバスケットへ投入する際の取り扱いが困難であった。また、その小片状の電気ニッケルは、チタンバスケットに投入後に角部がチタンバスケットの網目に引っ掛っていわゆる棚吊りを起こし、チタンバスケット内での充填状態が変化して、メッキむらの発生要因となることがあった。 However, the small pieces of electro nickel were difficult to handle when throwing them into the titanium basket due to the sharp corners. 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 uneven plating. There was sometimes.
そこで、角部の取れた丸みのある小塊状(ボタン状)の電気ニッケルの使用が提案されている。小塊状の電気ニッケルは、例えば、複数の円形状の導電部を等間隔に配列している陰極板を用いて、電解によりその導電部にニッケルを析出させた後、導電部から電着したニッケルを剥ぎ取ることにより製造することができる。このような方法によれば、1枚の陰極板から複数の小塊状の電気ニッケルを効率的に製造することができる。 Therefore, it has been proposed to use small rounded (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.
図5は、小塊状の電気ニッケルの製造に用いられる従来の陰極板の一例を示す図である。陰極板11は、平板状の金属板12上に、導電部12aとなる箇所を残して非導電膜13でマスキングが施されており、この陰極板11では、導電部12aが凹部となり、非導電膜13が凸部となっている。このような陰極板11を用いることで、その導電部12aに適度な大きさのニッケルを電着させ、小塊状の電気ニッケルを製造する。
FIG. 5 is a diagram showing an example of a conventional cathode plate used in the production of a small block of nickel. The
陰極板11のように、金属板12上に非導電膜13を形成する方法としては、例えば、図6(a)に示すように、平板状の金属板12上に、エポキシ樹脂等の熱硬化性の非導電性樹脂をスクリーン印刷法により塗布して加熱することで所望のパターンを有する非導電膜13を形成する方法がある(特許文献1、2参照)。なお、図6(b)は、非導電膜13を形成した陰極板11を用いてニッケル(電気ニッケル)14を導電部12aに電着析出させた状態を示すものである。陰極板11では、ニッケル14が、導電部12aから電着析出しはじめ、厚さ(縦)方向だけではなく平面(横)方向にも成長し、非導電膜13の上部にも盛り上がった状態となる。
As a method of forming the
また、例えば図7(a)に示すように、金属板22上に、感光性の非導電性樹脂を塗布し、露光及び現像により導電部22aに相当する箇所の非導電性樹脂を除去して、所望のパターンを有する非導電膜23を形成する方法も提案されている。なお、図7(b)は、非導電膜23を形成した陰極板21を用いてニッケル(電気ニッケル)24を導電部22aに電着析出させた状態を示すものである。陰極板21においても、ニッケル24は、導電部22aから電着析出しはじめ、厚さ方向だけではなく平面方向にも成長していく。
Further, for example, as shown in FIG. 7A, a photosensitive non-conductive resin is applied on the
さらに、導電部となる複数のスタッドが等間隔に複数配列されるように組み込まれた金属の構造体の周囲を射出成形法により絶縁性樹脂で固めることによって、非導電部を構成する陰極板を製造する方法も提案されている(特許文献3参照)。 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).
さて、上述したような陰極板を用いて小塊状の電気ニッケルの製造する場合、陰極板に形成される非導電膜(非導電部)の寿命が長いこと、その非導電膜が欠落(劣化)した場合でも容易に整備可能であることが要求される。 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.
図6(a)に示したように、金属板12に非導電性樹脂をスクリーン印刷により塗布して非導電膜13を形成した場合、非導電膜13の膜厚は、導電部12aに近づくにしたがって徐々に薄くなるため、導電部12aとの境界で非常に薄くなる。このような非導電膜13の膜厚の変化は、非導電性樹脂の塗布量、非導電性樹脂の粘性及び粘性の温度特性、非導電性樹脂の硬化温度、金属表面の表面粗さや表面自由エネルギー等に依存する。そのため、非導電膜13の膜厚は、導電部12aとの境界で非常に薄くなる。
As shown in FIG. 6A, when the
上述したように、図5、図6に示すような陰極板11を用いて小塊状の電気ニッケルを製造すると、ニッケル14は、導電部12aから電着析出しはじめ、縦方向だけでなく横方向にも成長するため、徐々に非導電膜13の上にも盛り上がった状態となる。そのため、導電部12aとの境界近傍に形成される薄い非導電膜13の部分においては、電解液の浸透により金属板12との密着性が低下しやすくなるとともに、ニッケル14の電着時の応力やその電気ニッケルの剥ぎ取り時の衝撃によって欠落しやすくなる。また、一度、非導電膜13の欠落が発生すると、その周辺の非導電膜13が金属板12の表面から浮き上がるため、その間隙にさらに電解液が侵入しやすくなり、その結果、引き続きニッケルを電着させようとすると、金属板12の表面から浮き上がった非導電膜13の間隙に電解液が潜り込んでニッケル14が電着していく。そして、その間隙に潜り込んで電着したニッケル14を剥ぎ取ろうとすると、ニッケル14が噛み込んでいる非導電膜13をさらに欠落させてしまう。
As described above, when small-sized electronickel is manufactured using the
このように、従来の陰極板11においては、連鎖的に非導電膜13の欠落が発生し、欠落部分が広がっていくと隣接する導電部12aから成長したニッケル14同士が連結しやすくなり、所望の形状の電気ニッケルを得ることができず、不良品となる。したがって、非導電膜13の欠落が発生する前に、すべての非導電膜13を剥ぎ取り、再度非導電膜3を形成して陰極板11を整備する必要が生じる。しかしながら、実際には、数回から多くても10回未満程度のニッケルの電着処理を行った段階で陰極板11の整備を行う必要が生じてしまい、生産性が低下するばかりか整備コストも増大する。
Thus, in the
一方、図7(a)に示したように、感光性の非導電性樹脂を用いて露光及び現像により非導電膜23を形成した陰極板21では、均一な膜厚に非導電膜23を形成することができる。しかしながら、電着後にニッケル24を剥ぎ取る際に、そのニッケル24が凸部を構成する非導電膜23の段差に引っ掛かり、その非導電膜23に大きな衝撃が加わりやすくなるため、やはり非導電膜23の欠落が発生してしまう。
On the other hand, as shown in FIG. 7A, in the
なお、特許文献3のように射出成形により非導電部を構成する方法では、形成される非導電部の寿命は長くなるものの、陰極板それ自体の製造コストが高くなり、非導電部が劣化した場合の陰極板の整備が困難である。
In addition, in the method of forming the non-conductive portion by injection molding as in
本発明は、このような従来の事情に鑑み、金属板上の非導電膜が欠落しにくく、繰り返し使用可能な金属電着用陰極板及びその製造方法を提供することを目的とする。 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.
本発明者らは、上述した解題を解決するために鋭意検討を重ねた。その結果、金属板に突起部を設けて導電部とし、突起部以外の金属表面に非導電膜を設けることで、非導電膜が欠落しにくくなることを見出し、本発明を完成するに至った。 The inventors of the present invention have made extensive studies to solve the above-mentioned problem. As a result, it has been found that providing a protrusion on the metal plate to form a conductive portion and providing a non-conductive film on the metal surface other than the protrusion makes it difficult for the non-conductive film to be lost, thereby completing the present invention. .
(1)本発明の第1の発明は、少なくとも一方の表面に複数の円盤状の突起部が配列している金属板と、前記金属板の突起部以外の表面に形成される非導電膜とを有し、隣接する前記突起部の中心間を通る位置における前記非導電膜の最小膜厚は、前記突起部の高さと同一以上である、金属電着用陰極板である。 (1) The first invention of the present invention is a metal plate in which a plurality of disk-like projections are arranged on at least one surface, and a non-conductive film formed on a surface other than the projections of the metal plate And the minimum film thickness of the non-conductive film at a position passing between the centers of adjacent protrusions is equal to or greater than the height of the protrusions.
(2)本発明の第2の発明は、第1の発明において、前記突起部の高さは、50μm以上1000μm以下である、金属電着用陰極板である。 (2) A second invention of the present invention is the metal electrodeposition cathode plate according to the first invention, wherein the height of the protrusion is 50 μm or more and 1000 μm or less.
(3)本発明の第3の発明は、第1又は第2の発明において、隣接する前記突起部の中心間を通る位置における前記非導電膜の最小膜厚と、前記突起部の高さとの差は、200μm以下である、金属電着用陰極板である。 (3) According to a third aspect of the present invention, in the first or second aspect, the minimum film thickness of the non-conductive film at a position passing between the centers of the adjacent protrusions and the height of the protrusions A difference is a metal electrodeposition cathode plate which is 200 micrometers or less.
(4)本発明の第4の発明は、第1乃至大3のいずれかの発明において、前記金属板は、チタン又はステンレス鋼からなる、金属電着用陰極板である。 (4) A fourth invention of the present invention is the metal electrodeposition cathode plate according to any one of the first to third inventions, wherein the metal plate is made of titanium or stainless steel.
(5)本発明の第5の発明は、第1乃至第4のいずれかの発明において、メッキ用電気ニッケルの製造に使用される、金属電着用陰極板である。 (5) The fifth invention of the present invention is a metal electrodeposition cathode plate used in the production of electroplating nickel in any of the first to fourth inventions.
(6)本発明の第6の発明は、金属電着用陰極板の製造方法であって、金属板の少なくとも一方の表面に、複数の円盤状の突起部を形成する第1工程と、前記金属板の突起部以外の表面に、非導電膜を形成する第2工程とを有し、前記第2工程では、隣接する前記突起部の中心間を通る位置における前記非導電膜の最小膜厚が、前記突起部の高さと同一以上となるようにする、金属電着用陰極板の製造方法である。 (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 disc-shaped protrusions on at least one surface of the metal plate, and the metal A second step of forming a non-conductive film on the surface other than the protrusions of the plate, and in the second step, the minimum film thickness of the non-conductive film at a position passing between the centers of the adjacent protrusions is This is a method for manufacturing a metal electrodeposition cathode plate that is equal to or higher than the height of the protrusion.
本発明によれば、非導電膜が欠落しにくく、繰り返し使用可能な金属電着用陰極板及びその製造方法を提供することができる。 According to the present invention, it is possible to provide a metal electrodeposition cathode plate that can be used repeatedly, and a method for producing the same, that is less likely to lack a non-conductive film.
以下、本発明の金属電着用陰極板を、電気ニッケルの製造に使用される金属電着用陰極板に適用した実施形態(以下、「本実施の形態」という)について詳細に説明する。なお、本発明は、以下の実施形態に限定されるものではなく、本発明の要旨を変更しない範囲で適宜変更することができる。 Hereinafter, an embodiment in which the metal electrodeposition cathode plate of the present invention is applied to a metal electrodeposition cathode plate used in 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.金属電着用陰極板>
(1)陰極板の構成
本実施の形態に係る陰極板1は、図1に示すように、複数の円盤状の突起部2aが配列している金属板2と、金属板2の突起部2a以外の表面に形成される非導電膜3とを有する。陰極板1は、後述するように、例えばニッケルを含む電解液や陽極を収容する電解槽内に吊下げ部材5により吊下げられて使用され、その表面に所望とする形状のニッケルを電着析出させる。
<1. Metal electrodeposition cathode plate>
(1) Configuration of Cathode Plate As shown in FIG. 1, the
[金属板]
金属板2は、図1及び図2(a)に示すように、平板状の金属の板であり、複数の円盤状の突起部2aを有する。ここで、金属板2において、突起部2a以外の表面を、突起部2aに対して「平坦部2b」という。また、「突起部の高さX」は、金属板2における平坦部2bの表面からの突出高さとする。
[Metal plate]
As shown in FIGS. 1 and 2A, the
なお、図2では、金属板2の一方の面に突起部2aを有する例を示しているが、その両方の面に突起部2aを有していてもよい。
In addition, in FIG. 2, although the example which has the
金属板2の大きさは、特に限定されず、製造する電気ニッケルの所望の大きさや数に応じて適宜設定すればよい。例えば、一辺が100mm以上、2000mm以下の矩形状の大きさとすることができる。また、金属板2の厚みとしては、突起部2aを一方の表面に設ける場合には、例えば、1.5mm以上、5mm以下程度であることが好ましく、突起部2aを両方の表面に設ける場合には、例えば、3mm以上、10mm以下程度であることが好ましい。金属板2の厚みが過小であると、突起部2aと平坦部2bとによって反りが生じやすくなる傾向がある。一方で、金属板2の厚みが過大であると、金属板2の重量が増大して取り扱いが困難になる。
The size of the
金属板2の材質としては、使用する電解液による腐食が小さく、ニッケル等の電着物とゆるい接着しか形成しない金属であれば特に限定されないが、チタン、ステンレス鋼が好ましく挙げられる。
The material of the
金属板2において、複数の円盤状の突起部2aは、その表面が後述する非導電膜3から露出して導電部としての機能を果たすとともに、非導電膜3が所定の厚みをもって成膜されるべく、隣接する突起部2aによって凹状の段差を形成する。以下、突起部2aのうち、非導電膜3から露出する面を「導電部2c」ということがある。導電部2cでは、電解処理によりニッケル4を電着析出する。
In the
円盤状の突起部2aの大きさは、所望の電気ニッケルの大きさに応じて適宜設定されればよいが、その直径としては、例えば、5mm以上、30mm以下とすることができる。また、突起部2aの高さXは、50μm以上、1000μm以下であることが好ましく、100μm以上、500μm以下であることがより好ましい。突起部2aの高さXが過小であると、金属板2の平坦部2b上に形成される非導電膜3の膜厚が不十分となり、ニッケル4の電着時の応力やその電気ニッケルの剥ぎ取り時の衝撃によって欠落しやすくなる。一方、突起部2aの高さXが過大であると、例えばスクリーン印刷で非導電膜を形成するとき、塗布回数が多くなり生産性が低下する。また、その高さXが過大であると、突起部2a加工時に金属板2の歪が生じやすくなり、金属板2が反りやすくなるため、非導電膜3の形成が困難になる。なお、金属板2の歪による影響を小さくするため、金属板2の厚みを厚くすることも可能であるが、金属板2の重量が増大し取扱いが困難になる。
The size of the disc-shaped
また、金属板2の表面、すなわち、金属板2における円盤状の突起部2aの表面には、サンドブラストやエッチングにより細かい凹凸を設けてもよい。これにより、突起部2aに電着したニッケル4が電解処理中に脱落することなく、適度な衝撃で剥ぎ取ることができる。この場合、後述する非導電膜3の膜厚は、金属板2の最大表面粗さRzの2倍以上であることが好ましい。非導電膜3の膜厚が金属板2の最大表面粗さRzの2倍より小さいと、非導電膜3のピンホールや絶縁不良部分の発生が懸念される。
Further, fine irregularities may be provided on the surface of the
[非導電膜]
非導電膜3は、図2に示すように、金属板2における突起部2a以外の表面である平坦部2b上に形成され、これにより、金属板2上に複数配列している突起部2aの表面、すなわち導電部2cが露出された状態となる。そして、このような金属板2の導電部2cにニッケル4が電着析出することにより、そのニッケル4は小塊状の形状に個々に分割されて形成される。
[Non-conductive film]
As shown in FIG. 2, the
ここで、陰極板1において、非導電膜3は、隣接する突起部2aによって形成された凹状の段差を有する平坦部2b上に形成されることになるため、所定の厚みをもって形成されることになる。本実施の形態に係る陰極板1においては、その非導電膜3は、その最小膜厚Yが突起部2aの高さXと同一以上であり、同一であることが好ましい。
Here, in the
なお、「非導電膜の最小膜厚Y」は、隣接する突起部2aの中心間を通る位置における非導電膜3の最小膜厚として定義される。非導電膜3は、図2(a)に示すように、隣接する突起部2aの間では、その表面張力により中央部が盛り上がって形成される。この場合、非導電膜3の最小膜厚Yは、突起部2aの側面と当接する端部の膜厚である。また、非導電膜3は、その膜厚が厚い場合、突起部2aの表面上に形成されることもある。このときの非導電膜3の最小膜厚Yは、突起部2aの表面上に形成された非導電膜3の膜厚ではなく、平坦部2b上の位置に形成された非導電膜3の膜厚のうちの最小値とする。なお、陰極板1において、選択する突起部2aの位置によって膜厚に変動はあるものの、そのうちの最小値を最小膜厚Yとする。
The “minimum film thickness Y of the non-conductive film” is defined as the minimum film thickness of the
非導電膜3は、隣接する突起部2aによって形成された凹状の段差を有する平坦部2b上に形成される。そのため、非導電膜3は、図6に示す従来の非導電膜13のように、端部の膜厚が薄くなりにくく、ニッケル4の電着時の応力や電着後の剥ぎ取り時の衝撃によっても欠落しにくくなる。また、非導電膜3は、図7に示す従来の非導電膜23のように、凸状に突出しておらず、その端部が凹状の段差によって保護されている。よって、ニッケル4を陰極板1から剥ぎ取る際にも、ニッケル4が非導電膜3の端部に与える衝撃は小さく、非導電膜3が欠落しにくい。このように、陰極板1においては、非導電膜3が欠落しにくいことから、非導電膜3を交換することなく、繰り返し電着に使用することが可能であり、整備コストの低減、生産性の向上を図ることが可能である。
The
さらに、非導電膜3の最小膜厚Yは、突起部2aの高さXと同一以上であるため、ニッケル4を陰極板1から剥ぎ取る際に、突起部2aの周縁部に引っ掛けることなく剥ぎ取ることができる。一方、図3に示すように、非導電膜3の最小膜厚Yが突起部2aの高さX未満となる場合には、電着したニッケル4を陰極板1から剥ぎ取る際、例えば、図中の「A」で示す箇所において突起部2aの周縁部に引っ掛かり、剥ぎ取りづらくなる。
Furthermore, since the minimum film thickness Y of the
非導電膜3の最小膜厚Yの上限は、特に制限されないが、最小膜厚Yと突起部2aの高さXとの差(Y-X)は、200μm以下であることが好ましく、100μm以下であることがより好ましく、50μm以下であることがさらにより好ましく、5μm以下であることが特に好ましい。ここで、上述したように、非導電膜3の最小膜厚Yは、突起部2aの高さXと同一以上であれば特に制限されないが、必要以上に厚くする必要はない。例えば、非導電膜3をスクリーン印刷により突起部2aの高さXより200μmを超えて塗布することは難しい。スクリーン印刷で突起部2aの高さXより膜厚200μm超の非導電膜3を形成しようとすると、複数回に亘ってスクリーン版のパターンのサイズを微調整しながら実施する必要が生じるため、その調整が困難であり生産性が低下してしまう。
The upper limit of the minimum film thickness Y of the
なお、スクリーン印刷法によって、金属板2上の平坦部2bに非導電膜3を形成する場合、非導電膜3の材料が突起部2aの表面にも塗布されて導電部2cの表面積が減少し、初期の電流密度が増加することがあるが、電着したニッケル4の特性に不具合が発生しなければ問題ない。また、突起部2aの表面上に付着した非導電膜3は、膜厚が非常に薄いため欠落しやすいが、平坦部2b上に形成される非導電膜3は、膜厚が厚く欠落が抑制されるため問題ない。
When the
非導電膜3は、非導電性のものであり、使用する電解液による腐食が小さい材料からなるものであれば特に限定されない。例えば、成膜が容易であるという観点から、熱硬化樹脂又は光硬化(紫外線硬化等)樹脂により構成することが好ましい。具体的には、エポキシ系樹脂、フェノール系樹脂、ポリアミド系樹脂、ポリイミド系樹脂等の絶縁樹脂が挙げられる。
The
(2)陰極板を用いた電気ニッケルの製造
上述した構成からなる陰極板1では、図2(b)に示すように、非導電膜3から露出する突起部2aの表面が導電部2cとなって、ニッケル4を電着析出させる。陰極板1において、ニッケル4は、厚さ方向だけではなく平面方向にも成長するため、非導電膜3の上部に盛り上がった状態になる。このことから、隣接する突起部2aの表面の導電部2cから成長したニッケル4同士が接触する前に電着を終了することが好ましい。
(2) Manufacture of electric nickel using cathode plate In the
そして、ニッケルの電着が終了した後、陰極板1からそのニッケル4を剥ぎ取ることで、1枚の陰極板1より複数の小塊状の電気ニッケルを得ることができる。上述したように、本実施の形態に係る陰極板1では、非導電膜3が欠落しにくいことから、非導電膜3を交換することなく、繰り返し使用することができ、整備コストの低減、生産性の向上を図ることができる。
Then, after the nickel electrodeposition is completed, the
なお、本実施の形態に係る陰極板1は、ニッケル4を電着したが、ニッケルに限定されず、銀、金、亜鉛、錫、クロム、コバルト、又はこれらの合金を電着してもよい。
In addition, although the
<2.金属電着用陰極板の製造方法>
本実施の形態に係る陰極板1の製造方法は、図4に示すように、金属板2の少なくとも一方の表面に複数の円盤状の突起部2aを形成する第1工程(図4(a))と、金属板2の突起部2a以外の表面に非導電膜3を形成する第2工程(図4(b))とを有する。
<2. Method for producing metal electrodeposition cathode plate>
As shown in FIG. 4, the manufacturing method of the
[第1工程]
第1工程では、金属板2の表面に、複数の円盤状の突起部2aを形成する。例えば、平板状の金属板2に対して、突起部2a以外の部分を削って、高さXとなる突起部2aを残し、平坦部2bを形成する。加工方法としては、特に制限されず、例えば、ウェットエッチング加工、エンドミル加工、レーザー加工等により行うことができる。
[First step]
In the first step, a plurality of disc-shaped
例えば、平板状のステンレス鋼板をウェットエッチングで加工する場合には、ステンレス鋼板の表面に感光性のエッチングレジストを塗布し、続いて、所望のパターンを描画したフィルムやガラスを通して露光し、エッチングする部分のエッチングレジストを現像処理により除去する。そして、現像処理されたステンレス鋼板をエッチング液(例えば、塩化第二鉄溶液)に付け、エッチングレジストが除去されたステンレス鋼板の一部を除去し、最後にエッチングレジストを剥離することで、所望のパターンに対応した、複数の円盤状の突起部2aを形成することができる。
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 disc-shaped
なお、突起部2aは、金属板2の一方の表面のみに形成してもよいし、金属板2の両方の表面に形成してもよい。
Note that the
[第2工程]
第2工程では、金属板2の突起部2a以外の表面となる平坦部2bに、非導電膜3を形成する。非導電膜3の形成方法としては、特に制限されず、スクリーン印刷により行うことができる。非導電膜3の材料が熱硬化樹脂又は光硬化樹脂である場合には、必要に応じて熱硬化又は光硬化を行えばよい。
[Second step]
In the second step, the
このとき、隣接する突起部2aの中心間を通る位置における非導電膜3の最小膜厚Yが、突起部2aの高さXと同一以上となるように、非導電膜3を形成する。一度のスクリーン印刷で、所望の膜厚が得られない場合には、所望の膜厚が得られるまで、上述したスクリーン印刷、及び熱硬化又は光硬化を繰り返してもよい。
At this time, the
本実施の形態に係る陰極板の製造方法によれば、上述した簡易な方法で、金属板上の非導電膜が欠落しにくく、繰り返し使用可能な陰極板1を得ることができる。
According to the method for manufacturing a cathode plate according to the present embodiment, it is possible to obtain the
以下に、本発明の実施例を示してより具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。なお、便宜上、図1乃至図6で示した部材と同一の機能をもつ部材には同一符号を付して説明する。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. For convenience, members having the same functions as those shown in FIGS. 1 to 6 will be described with the same reference numerals.
<陰極板の作製>
[実施例1]
図1、図2に示すような陰極板1を作製した。具体的には、まず、200mm×100mm×4mmのステンレス鋼製の金属板2に、ウェットエッチングを施し、円盤状の突起部2a(18個)を形成した。このとき、突起部2aの大きさは、直径14mm、高さX300μmとし、隣接する突起部2aの最小中心間距離は21mmとした。
<Preparation of cathode plate>
[Example 1]
A
次に、スクリーン印刷法により、熱硬化性エポキシ樹脂を金属板2における平坦部2b上に塗布し、150℃60分の加熱により硬化させて非導電膜3を形成した。このようにして作製した陰極板1において、レーザー変位計により、隣接する突起部2aの中心間を通る位置における非導電膜3の最小膜厚Yと突起部の高さXとの差を任意の10か所で測定したところ、40~70μmの範囲であり、したがって、非導電膜3の最小膜厚Yは340μmであった。
Next, a
[実施例2]
金属板2の突起部2aの高さXを500μmとし、平坦部2bに非導電膜3を所定の厚みで形成した以外は、実施例1と同様に、陰極板1を作製した。このようにして作製した陰極板1において、レーザー変位計により、非導電膜3の最小膜厚Yと突起部2aの高さXとの差を任意の10か所で測定したところ、10~50μmの範囲であり、したがって、非導電膜3の最小膜厚Yは510μmであった。
[Example 2]
A
[実施例3]
金属板2の突起部2aの高さXを60μmとし、平坦部2bに非導電膜3を所定の厚みで形成した以外は、実施例1と同様に、陰極板1を作製した。このようにして作製した陰極板1において、レーザー変位計により、非導電膜3の最小膜厚Yと突起部の高さXとの差を任意の10か所で測定したところ、60~90μmの範囲であり、したがって、非導電膜3の最小膜厚Yは120μmであった。
[Example 3]
A
[実施例4]
金属板2の突起部2aの高さXを100μmとし、平坦部2bに非導電膜3を所定の厚みで形成した以外は、実施例1と同様に、陰極板1を作製した。このようにして作製した陰極板1において、レーザー変位計により、非導電膜3の最小膜厚Yと突起部の高さXとの差を任意の10か所で測定したところ、100~150μmの範囲であり、したがって、非導電膜3の最小膜厚Yは200μmであった。
[Example 4]
A
[実施例5]
金属板2の突起部2aの高さXを40μmとし、平坦部2bに非導電膜3を所定の厚みで形成した以外は、実施例1と同様に、陰極板1を作製した。このようにして作製した陰極板1において、レーザー変位計により、非導電膜3の最小膜厚Yと突起部2aの高さXとの差を任意の10か所で測定したところ、10~40μmの範囲であり、したがって、非導電膜3の最小膜厚Yは50μmであった。
[Example 5]
A
[比較例1]
比較例1では、図5、図6に示すような従来の陰極板11を作製した。具体的には、200mm×100mm×4mmのステンレス鋼製の平板状の金属板12に、直径14mmとなる導電部12a(18個)を残して、スクリーン印刷法により、熱硬化性エポキシ樹脂を塗布し、150℃60分の加熱により硬化させて非導電膜13を形成し、陰極板11を作製した。このようにして作製した陰極板11において、レーザー変位計により、非導電膜13の最大膜厚を任意の10か所で測定したところ90~110μmの範囲であった。
[Comparative Example 1]
In Comparative Example 1, a
[比較例2]
金属板の突起部の高さを500μmとし、平坦部に非導電膜を所定の厚みで形成した以外は、実施例1と同様に、陰極板を作製した。このようにして作製した陰極板において、レーザー変位計により、非導電膜の最小膜厚と突起部の高さとの差を10か所で測定したところ、-200~-150μmの範囲であり、したがって、非導電膜3の最小膜厚Yは300μmであった。なお、この非導電膜3の最小膜厚Yは、突起部の高さ500μmよりも小さいものである。
[Comparative Example 2]
A cathode plate was produced in the same manner as in Example 1 except that the height of the protruding portion of the metal plate was 500 μm and the nonconductive film was formed with a predetermined thickness on the flat portion. In the cathode plate produced in this way, the difference between the minimum film thickness of the non-conductive film and the height of the protrusion was measured with a laser displacement meter at 10 locations, which was in the range of −200 to −150 μm. The minimum film thickness Y of the
[比較例3]
200mm×100mm×4mmのステンレス鋼製の金属板に、ウェットエッチングを施し、高さが2000μmとなる突起部(18個)を形成した。しかしながら、金属板の反りが大きく、スクリーン印刷による非導電膜の形成が困難であった。
[Comparative Example 3]
A metal plate made of stainless steel having 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, the warpage of the metal plate is large and it is difficult to form a non-conductive film by screen printing.
<電気ニッケルの製造>
各実施例及び比較例にて作製した陰極板を用いて、電解処理により電気ニッケルを製造した。具体的には、塩化ニッケル電解液を収容した電解槽中に、陰極板と、200mm×100mm×10mmの電気ニッケルからなる陽極板とを、対向させて浸漬した。そして、初期電流密度710A/m2、電解時間3日間の条件で、陰極板の表面にニッケルを電着させた。電解後、陰極板上に析出した電気ニッケルを剥ぎ取り、小塊状のメッキ用電気ニッケルを得た。
<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.
<評価>
電解処理に使用した陰極板を、そのまま繰り返し利用できる回数を評価した。非導電膜の欠落が広がると、隣接する突起部、導電部で電着したニッケル同士が連結し、所望の形状の電気ニッケルを得られないことがある。したがって、非導電膜が突起部との境界から平坦部方向に1mm以上に亘って欠落した場合には、使用を中止し、その時点までの繰り返し回数を評価した。また、非導電膜が欠落し、導電部の径が1mm以上拡大した場合にも、使用を中止し、この時点までの繰り返し回数を評価した。
<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, the nickel which is electrodeposited at the adjacent protrusions and conductive parts may be connected to each other, so that the desired form of electric nickel may not be obtained. Therefore, when the non-conductive film was missing over 1 mm from the boundary with the protrusion in the flat part direction, the use was stopped and the number of repetitions up to that point was evaluated. Also, when the non-conductive film was missing and the diameter of the conductive part expanded by 1 mm or more, the use was stopped and the number of repetitions up to this point was evaluated.
下記表1に、陰極板の構成とともに評価結果を示す。 Table 1 below shows the evaluation results together with the configuration of the cathode plate.
表1に示すように、金属板2の平坦部2bに非導電膜3が形成され、非導電膜3の最小膜厚Yが突起部2aの高さXと同一以上である陰極板1を用いた実施例1~5では、非導電膜3の欠落が抑制され、十分に繰り返し使用することができた。特に、突起部2aの高さXが50μm以上となる実施例1~4では、繰り返し使用回数が10回を超えていた。
As shown in Table 1, the
一方、平板状の金属板12に凸状に非導電膜13が形成された比較例1では、非導電膜が欠落してしまい、十分に繰り返し使用することができなかった。また、非導電膜の最小膜厚Yが突起部の高さX未満である比較例2では、ニッケルの剥ぎ取り時に、ニッケルが突起部の周縁部に引っ掛かり、剥ぎ取りが困難であった。
On the other hand, in Comparative Example 1 in which the
1 陰極板
2 金属板
2a 突起部
2b 平坦部
2c 導電部
3 非導電膜
4 ニッケル
DESCRIPTION OF
Claims (6)
前記金属板の突起部以外の表面に形成される非導電膜と、を有し、
隣接する前記突起部の中心間を通る位置における前記非導電膜の最小膜厚は、前記突起部の高さと同一以上である、
金属電着用陰極板。 A metal plate in which a plurality of disc-shaped protrusions are arranged on at least one surface;
A non-conductive film formed on the surface other than the protrusions of the metal plate,
The minimum film thickness of the non-conductive film at a position passing between the centers of the adjacent protrusions is equal to or greater than the height of the protrusions.
Cathode plate for metal electrodeposition.
請求項1に記載の金属電着用陰極板。 The height of the protrusion is not less than 50 μm and not more than 1000 μm.
The cathode plate for metal electrodeposition according to claim 1.
請求項1又は2に記載の金属電着用陰極板。 The difference between the minimum film thickness of the non-conductive film at the position passing between the centers of the adjacent protrusions and the height of the protrusions is 200 μm or less.
The cathode plate for metal electrodeposition according to claim 1 or 2.
請求項1乃至3のいずれか1項に記載の金属電着用陰極板。 The metal plate is made of titanium or stainless steel.
The metal electrodeposition cathode plate according to any one of claims 1 to 3.
請求項1乃至4のいずれか1項に記載の金属電着用陰極板。 Used in the production of electro nickel for plating,
The metal electrodeposition cathode plate according to any one of claims 1 to 4.
金属板の少なくとも一方の表面に、複数の円盤状の突起部を形成する第1工程と、
前記金属板の突起部以外の表面に、非導電膜を形成する第2工程と、を有し、
前記第2工程では、隣接する前記突起部の中心間を通る位置における前記非導電膜の最小膜厚が、前記突起部の高さと同一以上となるようにする、製造方法。 A method for producing a metal electrodeposition cathode plate,
A first step of forming a plurality of disc-shaped protrusions on at least one surface of the metal plate;
A second step of forming a non-conductive film on the surface of the metal plate other than the protrusions,
In the second step, the minimum film thickness of the non-conductive film at a position passing between the centers of the adjacent protrusions is equal to or greater than the height of the protrusions.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP17830882.1A EP3489395A4 (en) | 2016-07-21 | 2017-07-10 | Metal electrodeposition cathode plate and production method therefor |
| CN201780040988.6A CN109415832A (en) | 2016-07-21 | 2017-07-10 | Cathode plate for metal electrodeposition and its manufacturing method |
| CA3030941A CA3030941C (en) | 2016-07-21 | 2017-07-10 | Metal electrodeposition cathode plate and production method therefor |
| US16/317,141 US20190233960A1 (en) | 2016-07-21 | 2017-07-10 | Metal electrodeposition cathode plate and production method therefor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-143531 | 2016-07-21 | ||
| JP2016143531A JP6724624B2 (en) | 2016-07-21 | 2016-07-21 | Metal electrodeposited cathode plate and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2018016362A1 true WO2018016362A1 (en) | 2018-01-25 |
Family
ID=60992989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2017/025093 Ceased WO2018016362A1 (en) | 2016-07-21 | 2017-07-10 | Metal electrodeposition cathode plate and production method therefor |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20190233960A1 (en) |
| EP (1) | EP3489395A4 (en) |
| JP (1) | JP6724624B2 (en) |
| CN (1) | CN109415832A (en) |
| CA (1) | CA3030941C (en) |
| WO (1) | WO2018016362A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2019146474A1 (en) | 2018-01-29 | 2019-08-01 | コニカミノルタ株式会社 | 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS46919Y1 (en) * | 1966-04-04 | 1971-01-13 | ||
| JPS52152832A (en) * | 1976-06-15 | 1977-12-19 | Int Nickel Co | Method of producing ordinary electrolytic nickel or annular nickel product from electroplating bath providing precipitates of large stress |
| JPS57185762U (en) * | 1981-05-15 | 1982-11-25 | ||
| JPS6288754U (en) * | 1985-11-25 | 1987-06-06 | ||
| JP2008106292A (en) * | 2006-10-24 | 2008-05-08 | Sumitomo Metal Mining Co Ltd | Method for manufacturing cathode for electrowinning specially shaped electro nickel |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10317197A (en) * | 1997-05-14 | 1998-12-02 | Sumitomo Metal Mining Co Ltd | Electric nickel for plating, cathode plate for manufacturing the same, and manufacturing method |
| AU2009291494B2 (en) * | 2008-09-09 | 2015-05-07 | Glencore Technology Pty Limited | A cathode and a method of forming a cathode |
-
2016
- 2016-07-21 JP JP2016143531A patent/JP6724624B2/en active Active
-
2017
- 2017-07-10 CA CA3030941A patent/CA3030941C/en active Active
- 2017-07-10 EP EP17830882.1A patent/EP3489395A4/en not_active Withdrawn
- 2017-07-10 US US16/317,141 patent/US20190233960A1/en not_active Abandoned
- 2017-07-10 WO PCT/JP2017/025093 patent/WO2018016362A1/en not_active Ceased
- 2017-07-10 CN CN201780040988.6A patent/CN109415832A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS46919Y1 (en) * | 1966-04-04 | 1971-01-13 | ||
| JPS52152832A (en) * | 1976-06-15 | 1977-12-19 | Int Nickel Co | Method of producing ordinary electrolytic nickel or annular nickel product from electroplating bath providing precipitates of large stress |
| JPS57185762U (en) * | 1981-05-15 | 1982-11-25 | ||
| JPS6288754U (en) * | 1985-11-25 | 1987-06-06 | ||
| JP2008106292A (en) * | 2006-10-24 | 2008-05-08 | Sumitomo Metal Mining Co Ltd | Method for manufacturing cathode for electrowinning specially shaped electro nickel |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP3489395A4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6724624B2 (en) | 2020-07-15 |
| CA3030941A1 (en) | 2018-01-25 |
| JP2018012865A (en) | 2018-01-25 |
| EP3489395A1 (en) | 2019-05-29 |
| CA3030941C (en) | 2020-12-15 |
| EP3489395A4 (en) | 2020-04-08 |
| CN109415832A (en) | 2019-03-01 |
| US20190233960A1 (en) | 2019-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6500937B2 (en) | Negative electrode plate for metal electrodeposition and method of manufacturing the same | |
| KR102474454B1 (en) | Deposition mask manufacturing method and deposition mask | |
| JP4744790B2 (en) | Deposition mask, deposition mask frame assembly, and manufacturing method thereof | |
| WO2018016362A1 (en) | Metal electrodeposition cathode plate and production method therefor | |
| KR20110039489A (en) | Electric casting method | |
| JP6638589B2 (en) | Cathode plate for metal electrodeposition and method for producing the same | |
| NO149896B (en) | RECTANGULAR REPEATED USE UNITS OF CATODE | |
| US3695927A (en) | Electrodeposition process for producing perforated foils with raised portions at the edges of the holes | |
| WO2011158731A1 (en) | Substrate for mounting semiconductor element and method for manufacturing the substrate | |
| JP6737035B2 (en) | Metal electrodeposited cathode plate and method for producing the same | |
| JP6737036B2 (en) | Metal electrodeposited cathode plate and method for producing the same | |
| JP7188219B2 (en) | Cathode plate for metal electrodeposition | |
| JP7188218B2 (en) | Cathode plate for metal electrodeposition | |
| JP7238524B2 (en) | Cathode plate for metal electrodeposition | |
| US2225734A (en) | Electrolytic method of making screens | |
| JP7188216B2 (en) | Manufacturing method of cathode plate for metal electrodeposition | |
| JP7188217B2 (en) | Manufacturing method of cathode plate for metal electrodeposition | |
| KR101843035B1 (en) | Producing methods of the mother plate and mask | |
| US2225733A (en) | Process for the electrolytic production of metal screens | |
| JP6825470B2 (en) | Test power wearing cathode plate and its manufacturing method | |
| JP2024008385A (en) | Manufacturing method of cathode plate for metal electrodeposition | |
| EP1871925A2 (en) | Method for electroforming a studded plate and a copy die, electroforming die for this method, and copy die | |
| JP3771229B2 (en) | Method for manufacturing nozzle substrate for inkjet nozzle | |
| KR20060054858A (en) | Manufacturing method of surface irregularities forming thin film by electroforming and irregularities thin film | |
| KR20180123786A (en) | Method of inducing vertical groth in electroforming |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17830882 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 3030941 Country of ref document: CA |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 2017830882 Country of ref document: EP Effective date: 20190221 |