JP2019108592A - Button-type electrolytic nickel mother board for production and production method thereof, and button-type electrolytic nickel production method using the same - Google Patents

Abstract

To provide a production method of a mother board for producing a button-type electrolytic nickel that extends a lifespan (mother board life) of insulation paint coated on a handy mother board.SOLUTION: A production method includes an insulation layer formation step (S10) for forming an insulation layer (8) on a metal plate (5). The insulation layer formation step (S10) includes: a masking sheet mounting step (S11) for mounting a masking sheet (6) having a plurality of masking patterns (3) corresponding to a button shape on a metal plate (5); and a coating step (S12) for applying insulation paint onto the surface of the metal plate by pressing a squeegee (2) from above the masking sheet (6). The thickness of epoxy resin is specified as 0.2-0.4 mm by setting the pressing pressure of the squeegee (2) to be 0.255 MPa. The insulation paint is a resin composition including bis-A type epoxy resin and phenol novolak type epoxy resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a base plate for producing button-type electric nickel, a method for producing the same, and a method for producing button-type electric nickel using the same, and more specifically, button-type electrodeposition in an electrolysis process in wet nickel smelting. A base plate for manufacturing button-type electric nickel capable of reducing the frequency of maintenance associated with repeated use of a base plate used to obtain a surface, a method for manufacturing the same, and a method for manufacturing button-type electric nickel using the same About.

<Square shaped electric nickel by electrowinning>
In the process of producing electric nickel, nickel is electrodeposited on a titanium cathode plate and the electrodeposited product is peeled off to form a sheet-like nickel plate having a thickness of about 0.5 to 1 mm, which is obtained as a seed. Use as a board. By electrodepositing nickel on the surface of the seed plate, an electric nickel plate having a thickness of about 10 to 15 mm is obtained. A wide electric nickel plate obtained by one electrowinning using this seed plate is cut at regular intervals into a strip-shaped semi-finished product, which is cut into small squares to form a general square-shaped electric nickel .

<Disadvantages of square electric nickel>
Although the applications and uses of electronickel in customers vary, electronickel may be used for electroplating using a titanium basket filled with small pieces of electronickel as an anode. At that time, depending on the handling method, in the case of rectangular electric nickel, a worker who throws it into a titanium basket may cut hands at sharp corners or the like, which may require special consideration. Furthermore, even in the electroplating process after being introduced, the corners may be caught on the mesh of the titanium basket to raise the shelf and not uniformly fall, and the filling state in the titanium basket may not be uniformly maintained. . As a result, a uniform current distribution is not formed on the anode surface, which contributes to uneven plating.

<Handy Nickel>
Then, in order to eliminate the fault of the said square-shaped electric nickel, the button-type electric nickel called "handy nickel" is manufactured according to a user's usage form (refer patent document 1). This handy nickel is a special shape of electric nickel having no sharp edges or corners, for example, a hemispherical or disk-like button shape. Such handy nickel is produced by electrowinning using a cathode having a circular electrodeposition surface (hereinafter, also referred to as "handy base plate" or simply as "base plate" or "cathode"). In addition, as a means for preventing hydrogen generation on the surface of the mother plate, a method of performing electrolysis by adjusting the Ni concentration or pH has also been developed (see Patent Document 2).

<Handy mother board>
The handy base plate is formed by applying an insulating paint on an electrode plate using a stainless material or the like, unlike a seed plate for producing square-shaped electric nickel. As the insulating paint, a resin composition or the like using an epoxy resin as a base material is used. Handy nickel can be obtained by electrowinning using a handy base plate. Handy nickel electrodeposited on the handy base plate is peeled off by mainly applying vibration or impact to the handy base plate after electrodeposition.

<Life of Handy Motherboard>
Although the handy mother board is used repeatedly, not only the handy nickel but also a part of the resin applied to the surface of the handy mother board is gradually peeled off when the peeling work is repeated. As a result, an electrodeposit having a prescribed shape can not be obtained. The lifetime of the handy mother board means the lifetime of the formed insulating layer. The life of the insulating layer needs to be considered in production control, and therefore, is controlled by setting the following criteria. That is, as the number of repeated use increases, the resin starts to adhere to the obtained handy nickel. When the defective handy nickel to which the resin adheres exceeds 2% of the whole, it is determined that the life of the insulating layer formed on the handy base plate has come. By such a life judgment, in the actual operation, optimum management is carried out in consideration of the defect rate of the product, the operation cost and the like.

<Regeneration of handy base plate by silica sand blast treatment>
As described above, the handy mother board is managed using the occurrence rate of the handy nickel to which the resin is attached as an index. With regard to handy base plates for which the life has come, conventionally, sandblasting using silica sand as an abrasive material peels off the resin, as well as biting of the insulating paint, difficulty in dropping handy nickel during energization and peeling off From the viewpoint of ease of peeling at the time of removal, etc., the surface roughness of the electrode plate was adjusted to an optimum value, and an insulating layer was formed again to reproduce.

JP 2002-302786 A Japanese Patent Laid-Open No. 2002-302787

  The present invention has been made in view of such problems, and it is possible to extend the life of the insulating layer applied to the handy base plate (hereinafter also referred to as "base plate life") in view of the purpose thereof It is an object of the present invention to provide a method of manufacturing a base plate for manufacturing button-type electric nickel.

  The present inventors have completed the present invention by optimizing the coating thickness of the insulating paint on the stainless steel base plate in order to solve the above-mentioned problems.

[1] One embodiment of the present invention is a base plate (10) for producing a button-type electric nickel, in which hemispherical or disk-shaped button-shaped metallic nickel (1) is electrodeposited on the surface (9) by an electrowinning method Manufacturing method of
Having an insulating layer forming step (S10) of forming an insulating layer (8) on the surface of the metal plate (5);
In the insulating layer forming step (S10),
A masking sheet (6) mounting step (S11) for placing a masking sheet (6) having a plurality of masking patterns (3) corresponding to the shape of the button type on the metal plate (5);
Applying an insulating paint on the surface of the metal plate (5) by pressing a squeegee (2) from above the masking sheet (6);
Have
A base plate for producing a button-type electric nickel in which the thickness of the insulating layer (8) is regulated to 0.2 to 0.4 mm by setting the pressing pressure of the squeegee (2) to 0.255 MPa. Is a manufacturing method of

[3] One embodiment of the present invention is a base plate (10) for producing button-type electric nickel, in which hemispherical or disk-shaped button-shaped metallic nickel (1) is electrodeposited on the surface (9) by an electrowinning method And
A cathode plate composed of a metal plate (5),
An insulating layer (8) formed on a portion of the surface of the cathode plate which does not require electrodeposition;
A plurality of electrodeposited surfaces (7) having a contour corresponding to the button type formed by the insulating layer (8);
Have
The insulating layer (8) is formed to have a thickness (T) of 0.2 mm or more and 0.4 mm or less.

[2, 4] Further, in one aspect of the present invention, it is preferable that the insulating paint uses a resin composition containing a bis-A-type epoxy resin and a phenol novolac-type epoxy resin.

[5] Further, one aspect of the present invention is a method for producing the above-mentioned hemispherical or disk-shaped electrowinning method using the production base plate (10) for button-type electric nickel according to the above [3] or [4]. It is a manufacturing method of button-type electric nickel which carries out electrodeposition of metal nickel (1) which makes a button type.

  According to the present invention, it is possible to provide a method of manufacturing a base plate for manufacturing button-type electric nickel, which can extend the life (base plate life) of the insulating layer applied to the handy base plate.

In a method for producing a production base plate for button-type electric nickel (hereinafter, also referred to as “main base plate” or “main cathode plate”) according to an embodiment of the present invention, an insulating layer is formed on the surface of a metal plate It is a figure explaining an insulating layer formation process, FIG. 1 (A) is the simple sectional view which visually recognized the base plate from thickness direction, FIG. 1 (B) has each shown the flowchart of the insulating layer formation process. FIG. 2 (A) is a plan view, FIG. 2 (B) is a sectional view taken along the line A-A, and FIG. 2 (C) is a partially enlarged cross section obtained by enlarging the same. Figures are shown respectively. The average value which measured the application | coating film thickness (masking thickness) of the insulating resin (insulating layer) coat | covered on the surface of the main base plate of FIG. 2 in several places, and a chart of a histogram, FIG. Example 1 of a result and Drawing 3 (B) show comparative example 1 which can not be adopted, respectively.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. Note that the present embodiment described below does not unduly limit the contents of the present invention described in the claims, and all of the configurations described in the present embodiment are essential as means for solving the present invention. Not necessarily. In addition, throughout the drawings, the same effect members and places are denoted by the same reference numerals even if there is a slight difference in the outer shape, and the description will not be repeated.

  FIG. 1 is a view for explaining a masking step of masking an insulating layer on the surface of a metal plate in a method of producing a production base plate (main base plate) of button-type electric nickel according to an embodiment of the present invention. 1 (A) is a simplified cross-sectional view of the mother plate as viewed in the thickness direction, and FIG. 1 (B) shows a flowchart of the masking process.

  As shown in FIG. 1A, the base plate 10 is configured by applying an insulating paint (hereinafter also referred to as “epoxy resin”) 8 on the surface of the metal plate 5. In order to form an insulating layer (the same reference numeral as “insulation paint”, “epoxy resin”) 8 on the surface 9 of the metal plate 5, the insulation paint 8 is applied on the masking sheet 6 using a squeegee 2. At this time, in order to regulate the thickness T of the applied epoxy resin 8 to 0.2 to 0.4 mm, the pressing pressure of the squeegee 2 is set to 0.255 MPa.

  A large number of round masking patterns 3 are arranged on the masking sheet 6, and the insulating paint 8 is applied to portions other than the masking patterns 3. The masking pattern 3 corresponds to a shape in which button-type electric nickel (hereinafter, also simply referred to as "nickel") 1 is viewed in plan.

  FIG. 1 (A) is an explanatory view, and the shape of the squeegee 2 is greatly simplified, and in fact it may be a roller structure as well as an elaborate spatula structure. The description of the support mechanism for setting the pressing pressure of the squeegee 2 to 0.255 MPa is omitted.

  As shown in FIG. 1B, the method of manufacturing the base plate 10 includes an insulating layer forming step (S10). In the insulating layer forming step (S10), the insulating paint (epoxy resin) 8 is applied to the surface of the metal plate 5 constituting the cathode plate. The insulating layer forming step (S10) includes a masking sheet placing step (S11) and a coating step (S12).

  In the masking sheet mounting step (S11), the masking sheet 6 is formed on the surface of the metal plate 5 so as to form a plurality of electrodeposition surfaces 7 on which the nickel 1 is electrodeposited into a circular or square outline corresponding to a button type. Put on. The masking sheet 6 has a plurality of masking patterns 3 corresponding to the button type. In the application step (S12), the insulating paint 8 is applied on the masking sheet 6 using the squeegee 2. At this time, in order to define the thickness T of the insulating paint 8 to be applied to 0.2 to 0.4 mm, the pressing pressure of the squeegee 2 is set to 0.255 MPa.

  FIG. 2 is a view for explaining the shape of the base plate, and FIG. 2 (A) is a plan view, FIG. 2 (B) is a sectional view taken along line AA thereof, and FIG. 2 (C) is an enlarged view thereof. Are shown respectively. Moreover, the top view said in FIG. 2 (A) means the figure visually recognized from the front in the attitude | position which stood up the main mother board 10 as shown in FIG. The main base plate 10 is, for example, a metal plate 5 having a length of 1100 × a width of 830 mm, and its material is preferably made of SUS316L or SUS304, and constitutes a cathode plate used in the electrolytic extraction method. The main base plate 10 and the main cathode plate are the same and are denoted by the same reference numerals.

  The main base plate 10 deposits a button-shaped hemispherical or disc-like nickel electrodeposit on its surface 9 (hereinafter, also referred to as "electrodeposition of nickel 1"). The shape of the button-shaped nickel 1 is also called a special shape, as opposed to general square electric nickel.

  As shown in FIG. 2A, the surface 9 of the base plate 10 has an insulating layer 8 and an electrodeposition surface 7. An insulating layer (hereinafter, also referred to as “masking resin”, “mask” or “nonconductive film”) 8 is formed for masking, and covers so as not to expose the metal. The electrodeposition surface 7 is not covered with the insulating layer 8 to form a plurality of circular or rounded outlines corresponding to the button shape. Here, in order to electrodeposit nickel 1 in a disk shape, a plurality of circular electrodeposition surfaces 7 corresponding to the button shape are illustrated in a staggered arrangement on the surface of the base plate 10.

  Although illustration is omitted, even if it is an electrodeposition surface in which the four sides of the square are formed into rounded corners with a suitable radius of curvature as the contour of the rounded corners described above, button-type electric nickel is produced and good results are obtained. can get. Several hundreds of electrodeposition surfaces 7 are formed on one surface of the base plate 10 per one surface, and button-type nickel 1 is electrodeposited by the number of the electrodeposition surfaces 7 in one electrodeposition process. It is configured to be able to. The front surface 9 of the base plate 10 refers to all the surfaces including the back surface of the base plate 10.

  As shown in FIG. 2B, in the insulating layer 8, the area of the conductive portion is appropriately adjusted by applying the insulating paint. As the insulating paint, an epoxy resin having a thickness T of 0.2 mm or more and 0.4 mm or less is applied. As an example, a resin composition containing a bis-A type epoxy resin and a phenol novolac type epoxy resin is suitable for the epoxy resin, and an embodiment is thereby disclosed.

  As shown in FIG. 2C, several hundreds are formed on the surface 9 of the base plate 10, and a plurality of circular electrodeposition surfaces 7 corresponding to the button-type nickel 1 to be electrodeposited are formed. Moreover, the electrodeposition surface 7 is arrange | positioned at zigzag form. By adopting the staggered arrangement, it is possible to obtain more pieces for one main base plate 10 than the lattice arrangement.

  The base plate 10 is used in an electrodeposition step in a button-type, i.e., special-shaped electronickel production process. On the surface 9 of the base plate 10, a plurality of circular electrodeposition surfaces 7 corresponding to the button type are arranged in a staggered manner. One electrodeposition surface 7 is formed in a circle having a diameter of 14 to 15 mm. Of the surface of the base plate 10, the portions other than the electrodeposition surface 7 are coated with an epoxy resin.

  As described above, the masking sheet 6 on which the plurality of masking patterns 3 corresponding to the electrodeposition surface 7 are formed is placed on the surface 9 of the base plate 10, and the epoxy resin is applied thereon using the squeegee 2. At this time, by always setting the pressing pressure of the squeegee 2 to 0.255 MPa, the thickness of the masking resin is defined to 0.2 to 0.4 mm. The electrodeposition surface 7 corresponding to the masking pattern 3 is formed by exposing the surface 9 of the metal plate 5.

  When the pressure is increased to 0.286 MPa, the thickness of the masking resin is reduced, so that the base plate life is shortened. As a result, the application of the insulating paint and the frequency of blasting increase, leading to the deterioration of the manufacturing cost. Hereinafter, a method (present method) for producing a button-type electric nickel using the base plate 10 will be briefly described by omitting illustration.

In this method, nickel 1 is electrodeposited in a semi-spherical or disk-like manner having a button shape by an electrowinning method in the electrolysis step in the wet smelting of nickel using the base plate 10. The base plate 10 after the application of the insulating paint is, for example, inserted into the battery case as a set of 52 sheets, and the conduction current and the immersion area (about 1120 [A / m ² ] or less) to obtain a predetermined current density. 1.56 ² / sheets) to adjust, 110 mm spacing between adjacent cathode, chamber temperature 55 to 60 ° C., adjusted to energization 4-7 days such that the feed fluid flow rate 30~45L / min.

  After that, vibration is applied to the upper part of the base plate 1 using a hammer to peel off the electrodeposited button-type nickel 1. Then, it is inserted into the battery case again and energized under the same conditions to electrodeposited and peel off. Repeat electrodeposition of When stripping is repeated about four times, the insulating layer 8 on the base plate 1 is degraded. Since the deteriorated insulating layer 8 is easily peeled off from the base plate 10, the peeled piece of the insulating layer 8 adheres to the button-type nickel 1.

  As described above, one of the quality control items is to monitor the degree to which the peeling pieces of the insulating layer 8 adhere to the nickel 1. The mother board 10 whose monitoring result exceeds the quality control standard is not reloaded into the battery case, but is recycled after passing through the respective steps of the regeneration treatment. Each step of the regeneration treatment mainly includes a sand blasting step and another insulating layer forming step. In the sand blasting process, the insulating layer applied to the surface of the base plate 10 is removed. More specific details of the sandblasting process will be described later.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to this embodiment. FIG. 3 is a chart of an average value and a histogram of the coated film thickness (masking thickness) of the insulating resin (insulating layer) coated on the surface of the main base plate of FIG. A) shows a successful example 1 and FIG. 3 (B) shows a non-adoptable comparative example 1, respectively.

Conditions for blasting Blasting material Neoblast G1 used Particle size 1.3 to 0.7 mm
Blasting device made by Nittsu Co., Ltd.
Abrasive material discharge distance 0.3m (distance from discharge nozzle to handy base plate 1)
Discharge angle The discharge pressure in the range of 20 to 30 ° downward with respect to the handy base plate 1 erected Discharge pressure 0.55MPa (pressure of compressed air)
Mother board moving speed 0.6 to 1.5 m / min

  In the electrowinning of button-type electric nickel 1 from a nickel chloride bath, the SUS base plate 10 with a height of about 1000 mm, a width of about 800 mm, and a thickness of about 5 mm is blasted to control the surface roughness, and then the insulating layer is formed Applied (see Figure 1). 52 insulating layer formation processed mother plates 10 were loaded per tank, and the current supply time of cathode was set to 22 kA for 7 days, and the amount of high purity nickel chloride aqueous solution was 35 L / min. The electrowinning operation of button-type electric nickel was carried out while supplying

  Here, in each of Example 1 in which the squeegee 2 pressing pressure is a low pressure, and Comparative Example 1 in which the squeegee 2 pressing pressure is a strong pressure, the resin attachment ratio at the end of 5 times of peeling was measured. The definition of resin attachment rate is the ratio of the weight of the handy nickel 1 to which the exfoliation piece of the masking resin 8 adheres to the weight of all the handy nickel 1 peeled off from the handy nickel base plate 1 is there.

Example 1
As shown in the measurement data of Example 1 where good results were obtained in FIG. 3 (A), when the squeegee 2 pressing pressure is 0.255 MPa, the insulating resin (coated on the surface 9 of the base plate 10 ( The average value of the coating film thickness (masking thickness) T of the insulating layer 8 measured at 15 to 16 points with respect to one main base plate 10 is 0.28 mm, and these are the histograms of FIG. The distribution is as shown in.

  By setting the squeegee 2 pressing pressure to 0.255 MPa, the thickness T to which the masking resin 8 is applied can be controlled in the range of 0.2 mm to 0.4 mm. As a result, the resin attachment rate at the end of 5 times of stripping was able to be significantly reduced to 0.21% compared to 7.68% of Comparative Example 1 described later. In other words, I succeeded in extending the mother board life.

Comparative Example 1
As shown in the measurement data of Comparative Example 1 which resulted in being not adopted in FIG. 3 (B), the insulating resin coated on the surface 9 of the base plate 10 when the squeegee 2 pressing pressure is 0.286 MPa. The average value of the coating film thickness (masking thickness) T of (insulation layer) 8 measured at 15 to 16 points for one main base plate 10 is 0.16 mm, and these are the histograms of FIG. 3 (B) The distribution is as shown in.

  As described above, according to the present invention, according to the present invention, a base plate for manufacturing button-type electric nickel capable of extending the life of the base plate, a method for manufacturing the same, and a method for manufacturing button-type electric nickel using the same Can provide Specifically, 52 sheets of the masking-treated base plate 10 were charged per bath, and the effect of significantly reducing the resin attachment rate at the end of 5 times of stripping was obtained.

  Although the embodiments of the present invention have been described in detail as described above, it is easily understood by those skilled in the art that many modifications can be made without substantially departing from the novel items and effects of the present invention. Will. Accordingly, all such modifications are intended to be included within the scope of the present invention.

  For example, in the specification or the drawings, the terms described together with the broader or synonymous different terms at least once can be replaced with the different terms anywhere in the specification or the drawings. Further, the configuration of the mother board and the specific method for the regeneration process thereof are not limited to those described in the embodiment of the present invention, and various modifications can be made.

  The present invention may be employed as a technique for extending the life of the insulating layer by the insulating paint applied on the cathode (handy base plate) used in producing the special shape of electric nickel. More specifically, circular electrodeposition in the production of nickel electrodeposits (handy nickel) deposited on a cathode whose surface is insulated with an insulator, so that an electrodeposit of a special shape can be obtained by electrowinning of an aqueous solution of nickel chloride. A base plate for the production of a button-type electric nickel in which the period until the circular electrodeposition surface can not be obtained can be extended by degradation and partial peeling of the applied and dried epoxy resin to obtain a surface. , A method of manufacturing the same, and a method of manufacturing button-type electric nickel using the same.

REFERENCE SIGNS LIST 1 nickel, 2 squeegee, 3 masking pattern, 5 metal plate, 6 masking sheet, 7 electrodeposited surface, 8 insulating layer, 9 (of this base plate 10) surface, 10 base plate for manufacturing of nickel electric nickel Board), T (insulation layer 8) thickness

Claims (5)

A method for producing a base plate for producing a button-type electric nickel, comprising electrodeposition of hemispherical or disk-shaped button-shaped metallic nickel on the surface by an electrowinning method,
Having an insulating layer forming step of forming an insulating layer on the surface of the metal plate,
In the insulating layer forming step,
A masking sheet placing step of placing a masking sheet having a plurality of masking patterns corresponding to the shape of the button type on the metal plate;
Applying an insulating paint on the surface of the metal plate by pressing a squeegee from above the masking sheet;
Have
The thickness of the insulating layer is regulated to 0.2 to 0.4 mm by setting the pressing pressure of the squeegee to 0.255 MPa.
A method of manufacturing a base plate for manufacturing button-type electric nickel.   The method according to claim 1, wherein the insulating paint is a resin composition containing a bis-A type epoxy resin and a phenol novolac type epoxy resin. A base plate for producing button-type electric nickel, in which a metallic nickel having a hemispherical or disk-like button shape is electrodeposited on the surface by an electrowinning method,
A cathode plate made of a metal plate,
An insulating layer formed on an unnecessary part of the surface of the cathode plate;
A plurality of electrodeposited surfaces having a contour corresponding to the button type formed by the insulating layer;
Have
The insulating layer is formed to have a thickness of 0.2 mm or more and 0.4 mm or less.
Base plate for manufacturing button-type electric nickel.   The mother plate for manufacturing button-type electric nickel according to claim 3, wherein the insulating layer is an insulator containing a bis-A type epoxy resin and a phenol novolac type epoxy resin.   A method for producing button-type electric nickel, wherein the hemispherical or disc-like button-shaped metallic nickel is electrodeposited by an electrolytic recovery method using the production-use base plate for button-type electric nickel according to claim 3 or 4.