Counter electrode, method of fabricating counter electrode, plating device, and plating method

Abstract

To provide a counter electrode capable of forming a sound plating layer.SOLUTION: The counter electrode, i.e., a counter electrode as an electrode in a plating device forming a partial plating film on a structure by feeding an electric current between the structure and the electrode with a gel substance including a plaiting component in a state of being coated on the structure to be partially plated, or a porous film impregnated with a plating component in a state of being applied to the structure to be partially plated, is characterized in that the flexibility of the counter electrode is equal to or lower than that of the gel substance being used or of the porous film. The counter electrode is fabricated as a conductive paste by applying a solvent containing a conductive substance onto a gel substance including a plating component or onto a porous film.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a counter electrode for performing partial plating, a method for manufacturing the counter electrode, a plating apparatus, and a plating method.

Background Art

[0002] One of the plating techniques is gel plating technology. Gel plating technology can perform patterning by applying a gelled plating solution in an arbitrary shape, and can perform partial plating without using complicated masking or equipment. Regarding gel plating technology, for example, Patent Documents 1 to 3 have been proposed.

[0003] Patent Document 1 describes a gel plating method in which a gel-like plating composition is applied onto an object to be plated, and a plating film is formed on the object to be plated by electrolytic reduction of plating metal ions in the gel-like plating composition. Here, a dispenser is used to apply the gel-like plating composition to the object to be plated. It is described that the nozzle of the dispenser is used as an anode and the object to be plated is used as a cathode.

[0004] Patent Document 2 describes adding polyethylene glycol to a general electrolytic copper plating solution composed of copper sulfate and sulfuric acid to gel the plating solution. Then, the gelled plating solution is placed on a metal copper plate in a plating tank, and the metal copper plate is connected to a power source as an anode.

[0005] Patent Document 3 describes a technique in which a gelled plating solution is placed only on the part to be plated, and an anode is connected thereto for electrolytic plating.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, when gel plating is carried out by the method of Patent Document 1, since the anode shape does not correspond to the shape of the repaired portion by plating, there is a problem that the location dependence of the degree of repair becomes large. Further, Patent Document 2 uses a metal copper plate as the anode. In the methods of Patent Documents 2 and 3, when the gel is attached to the object to be plated, the counter electrode does not deform according to the deformation of the gel. Therefore, when the gel is deformed, the adhesion between the gel and the counter electrode cannot be maintained, and there is a problem that the possibility of plating defects increases.

[0008] The present invention is an invention for solving the above problems, and an object thereof is to provide a counter electrode capable of forming a sound plating layer, a method for manufacturing the counter electrode, a plating apparatus, and a plating method.

Means for Solving the Problems

[0009] To achieve the above object, the counter electrode of the present invention is an electrode as the counter electrode in a plating apparatus that generates a partial plating film on the structure by passing an electric current between the structure and the electrode in a state where a gel-like substance containing a plating component is applied on the structure to be partially plated or in a state where a porous film impregnated with the plating component is applied on the structure to be partially plated, and the flexibility of the counter electrode is equal to or less than that of the gel-like substance or the porous film used. Other aspects of the present invention will be described in the embodiments described later.

Effects of the Invention

[0010] According to the present invention, a sound plating layer can be formed.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Embodiments for Carrying Out the Invention

[0012] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate. FIG. 1 is a diagram showing the structure (counter electrode structure) of a counter electrode for performing partial plating using a gel. FIG. 2 is a diagram showing a plating object (structure) with a defective part repaired. As shown in FIG. 1, after applying or adhering a gel plating composition 2 to a plating object 1 (structure), a current is passed (applied) from a plating power source 5 between the plating object 1 and an anode 3 (counter electrode) having a lead wire 4.

[0013] The anode 3 (counter electrode) is brought into contact with the gel plating composition 2. The gel plating composition 2 is brought into contact with the surface of the object to be plated 1. That is, the anode 3 is electrically connected to the object to be plated 1 via the gel plating composition 2. The gel plating composition 2 contains a metal or metal ions for forming a plating repair layer 6 (see Fig. 2) on the surface of the object to be plated 1. Therefore, in this state, when a constant current is applied to the object to be plated 1, the gel plating composition 2, and the anode 3 (counter electrode), the metal ions contained in the gel plating composition 2 (including those in which the metal has become metal ions due to energization) receive electrons on the surface of the object to be plated 1 and are deposited on the surface as a metal.

[0014] Thereby, a plating repair layer 6 composed of plating particles (particles of the plated metal deposited on the surface of the object to be plated 1) is formed on the surface of the object to be plated 1. Note that the contact between the anode 3 and the gel plating composition 2 only requires that they be electrically connected, and the connection method is not limited.

[0015] Here, the gel plating composition 2 refers to a plating solution (aqueous solution) containing a metal or metal ions to be plated, to which a gelling agent is added to make it gel-like. As the plating solution, a known plating solution used for electroplating, for example, an electrolytic plating solution can be used. Examples of the electrolytic plating solution include an electrolytic copper plating solution, an electrolytic nickel plating solution, an electrolytic gold plating solution, an electrolytic tin plating solution, an electrolytic silver plating solution, a chromium plating solution, and the like.

[0016] More specifically, as the electrolytic copper plating solution, for example, a copper sulfate / sulfuric acid / additive-based solution (e.g., Cu matte copper sulfate bath) can be used (see the second embodiment described later). As the electrolytic nickel plating solution, for example, a nickel sulfate / boric acid / additive-based solution (e.g., Ni bright Watts bath) can be used (see the first embodiment described later). As the electrolytic gold plating solution, for example, a potassium cyanide / glycinate / additive-based solution can be used. As the electrolytic tin plating solution, for example, a stannous sulfate / sulfuric acid / additive-based solution can be used. As the electrolytic silver plating solution, for example, a silver cyanide / potassium cyanide / additive-based solution (e.g., Ag thickened silver cyanide bath) can be used. As the chromium plating solution, for example, anhydrous chromic acid / sulfuric acid (e.g., Cr surge bath) can be used (see the third embodiment described later).

[0017] The type of plating metal is not particularly limited, and examples include copper (Cu), nickel (Ni), gold (Au), tin (Sn), silver (Ag), palladium (Pd), chromium (Cr), etc. The concentration of the plating metal ions in the plating solution varies depending on the type of plating metal, but usually 20 g / L or more is required, preferably 80 g / L or more, and particularly preferably 100 g / L or more.

[0018] The gel plating composition 2 may contain various additives such as a complexing agent, a reducing agent, a leveling agent, a brightening agent, and a pH adjuster.

[0019] Examples of the gelling agent include, but are not limited to, agar, xanthan gum, carrageenan, roasted bean gum, guar gum, diutan gum, welan gum, gellan gum, methyl cellulose, hydroxypropyl methyl cellulose, pectic acid, high-methoxyl pectin (HM pectin), alginic acid, gelatin, polyvinyl chloride, etc. The gelling agent can gel an aqueous solution and can be any agent that does not interfere with electroplating. The gelling agent can be selected from one of the above-mentioned agents or a mixture of two or more.

[0020] A method that does not use a gel may be employed, for example, by incorporating the plating solution into a porous membrane. Examples of the porous membrane include silicone-based, fluorine-based, cellulose acetate propionate and / or cellulose acetate butyrate, spongy urethane, polyolefin-based, cellulose-based, polyvinyl chloride-based, ethylene vinyl acetate copolymer, etc., and an appropriate one can be used as needed.

[0021] Here, examples of the object to be plated 1 include conductive materials such as copper alloys such as copper and brass, and aluminum, iron, stainless steel (SUS), etc.

[0022] The gel plating composition 2 can be applied or adhered according to the shape of the damaged part to perform partial electroplating only on the damaged part and repair it.

[0023] The anode 3 can be any one as long as its shape is variable. The anode 3 may be a soluble electrode or an insoluble electrode. The necessary condition for the anode 3 is to have a softness that can follow the shape change of the gel when the gel is attached. That is, when attaching to the gel, the softness of the anode 3 is softer than the hardness of the gel.

[0024] That is, in a state where a gel-like substance containing a plating component is applied on the structure to be partially plated, or in a state (placed state) where a porous membrane impregnated with a plating component is applied on the structure to be partially plated, a current is passed (applied) between the structure and the electrode, and as a counter electrode (anode 3) as an electrode in a plating apparatus for generating a partial plating film on the structure, the flexibility of the counter electrode is equal to or less than that of the gel-like substance or porous membrane used.

[0025] Incidentally, the hardness and flexibility of the gel-like substance, porous membrane, and counter electrode can be evaluated by various methods such as a bending test, for example. By the way, "equal to or less than" means that the numerical values of hardness and flexibility are approximately the same or less, but the lower limit value in "less than" is appropriately set within the range that exhibits the effect of forming a sound plating layer (within the range that does not damage the effect).

[0026] As a measurement method, for example, there is measurement by dynamic viscoelasticity using nanoindentation. In dynamic nanoindentation, a dynamic vibration load is applied while the indenter and the sample are in contact, and the dynamic viscoelasticity is calculated from the vibration and phase difference given by measuring the displacement of the vibrating indenter and the rigidity of the sample.

[0027] There are the following two types of electrodes with variable shapes. (1) Method of using a conductive paste The conductive paste is composed of metal particles (fillers), organic substances (various resins), surfactants, and polymers (binders). In order to prevent the gel from drying, it is preferable to use a room temperature curing type.

[0028] As the metal particles that are conductive substances, use a conductive paste containing at least one of Ag, C, Cu, Ni, and Au, a thinner or toluene as a solvent, and one of epoxy-based, phenol-based, and acrylic-based as a binder resin.

[0029] Examples of soluble electrodes include electrodes made of copper or silver. When using a soluble electrode, if possible, the same metal as the metal ions contained in the gel plating composition 2, for example, when performing Ni plating, it is preferable that Ni is contained as a conductive substance.

[0030] Examples of insoluble electrodes include electrodes coated with a substance mainly composed of a gold electrode, a platinum group element, etc. Even if a prepared one as needed is used, commercially available ones such as ECA202 manufactured by Nihon Handa for nickel and Dotite room temperature curing type manufactured by Fujikura Kasei for silver can also be used.

[0031] As a method of use, after preparing the gel plating composition 2, a conductive paste is applied onto the gel plating composition 2 using a dispenser or screen printing. A flexible lead wire, such as a copper tape or the like, is connected thereto. After attaching this to the object to be plated, it is dried and solidified at room temperature.

[0032] (2) Method of using a metal mesh Examples of the soluble electrode include electrodes made of copper, silver, etc. When using a soluble electrode, if possible, the same metal as the metal ions contained in the gel plating composition 2, for example, when performing Ni plating, it is preferable that Ni is contained as a conductive substance. Examples of the insoluble electrode include electrodes coated with a gold electrode, a substance mainly composed of a platinum group element, etc. The necessary condition is that the hardness (flexibility) is equal to or less than that of the gel to be used. Since the hardness of the gel varies depending on the type and concentration of the gelling agent used, it is preferable to select the mesh to be used accordingly.

[0033] <First Embodiment> This embodiment is based on the method of (1) above, and the details are shown in FIG. 3. FIG. 3 is a diagram showing a plating method using a counter electrode for performing partial plating using a gel. (S1) Preparation of gel composition (porous membrane) A Ni Watts bath is prepared, xanthan gum and 10 g / L of roasted bean gum are added thereto, heated and dissolved up to 70 °C, and then poured into a predetermined mold to prepare a gel composition. When not using the gel composition, spongy urethane is selected as the porous membrane and the Watts bath is contained therein.

[0034] (S2) Application of conductive paste As the conductive paste, a commercially available Ni-containing product was used. The application method used a dispenser. (S3) Connection of lead wire A conductive copper flexible tape was used as the lead wire.

[0035] (S4) Partial plating Attachment to the plating site (repair site) In order to improve the adhesion, it is effective to bring the gel composition or the porous film into close contact with the object to be plated (nickel) at a temperature of 80°C. (S5) Curing of the conductive paste by leaving it at room temperature (S8) Plating is carried out by passing an electric current between the object to be plated 1 and the lead wire 4 As the current density, direct current 10 A / dm 2 was used. Note that A / dm 2 is the number of amperes per square decimeter (= 0.1 m 2 ). By the above steps (S1 to S4, S8), as shown in Fig. 2, partial plating for repairing the defective part becomes possible.

[0036] That is, in a state where a gel-like substance containing a plating component is applied onto the structure to be partially plated, or in a state where a porous film impregnated with the plating component is applied onto the structure to be partially plated, an electric current is passed between the structure and the electrode to produce a partial plating film on the structure. This is a method for producing a counter electrode as the electrode in the plating method, and the counter electrode is produced as a conductive paste by applying a solvent containing a conductive substance onto a gel-like substance containing a plating component (on the gel-like substance) or a porous film (on the porous film). The flexibility of the counter electrode is equal to or less than that of the gel-like substance or porous film used.

[0037] <Second Embodiment, Third Embodiment> In other combinations (Second Embodiment and Third Embodiment) as well, similar good results could be obtained. Table 1 shows the conditions including the First Embodiment.

[0038]

Table 1

[0039] <Fourth Embodiment> FIG. 4 is a diagram showing a plating method using a counter electrode for performing partial plating using a gel in the case where the amount of plating repair is large. This example relates to a repair method for thick films. In the gel plating method, it is effective to use a paste containing the same components as those to be plated on the counter electrode. By eluting the same amount as the amount to be plated from the counter electrode, the amount of metal ions in the gel that decreases due to plating is maintained. However, when using a dispenser, since the thickness of the counter electrode is limited, it is not possible to ensure a sufficient thickness to replenish the decreasing metal ions. When the anode disappears, plating cannot be maintained. Therefore, when performing a large amount of plating (when the amount of repair is large), it is preferable to use an insoluble electrode as the counter electrode and increase the amount of metal ions in the gel (inside the porous film) by thickening the gel (porous film). This example relates to the relevant content.

[0040] This example is based on the method of (1) above, and specifically shows the details of an example when the amount of plating repair is large in FIG. 4. Note that in FIG. 4, S6 and S7 are added compared to FIG. 3. (S1) Preparation of gel composition (porous film) Prepare a Ni Watts bath, add xanthan gum and 10 g / L of roasted bean gum to it, heat and dissolve it up to 70°C, and then pour it into a predetermined mold to prepare a gel composition. When not using the gel composition, spongy urethane is selected as the porous film and the Watts bath is contained therein. (S2) Application of conductive paste As the conductive paste, a commercially available Ni-containing product was used. The application method used a dispenser. (S3) Connection of lead wire As the lead wire, a conductive copper flexible tape was used. (S4) Attachment to the site to be partially plated (repair site) In order to improve the adhesion, it is effective to bring the gel composition or the porous film into close contact with the object to be plated (nickel) while raising the temperature of the object to be plated to 80°C. (S5) Curing of conductive paste by standing at room temperature (S6) Overlay of gel composition (S7) Improvement in adhesion between the gel composition in (S1) and the gel composition in (S6) by heating (S8) Electroplating is performed by passing an electric current between the object to be plated 1 and the lead wire 4 As the current density, direct current 10 A / dm 2 was used.

[0041] <Fifth Embodiment> FIG. 5 is a diagram showing a counter electrode structure for performing partial plating using a gel and a schematic configuration of a plating apparatus using the same, in which the shape of the counter electrode is adjusted to match the shape of the repair site and the position is set so as to be applied on the target structure.

[0042] In order to efficiently plate the repair portion, it is preferable to adjust the shape of the counter electrode to match the shape of the repair site and to install the counter electrode so that its position is applied on the target structure. An example for achieving this is this embodiment. Details will be described with reference to FIG. 5. In FIG. 5, an initial state 51 and an application state 52 are shown. In the initial state 51, a camera 7 for photographing the repair site, a control device 8, a dispenser 9, and a dispenser nozzle 10 are arranged.

[0043] That is, when producing a counter electrode used to generate a partial plating film on a structure by applying a gel-like substance or a porous film containing a plating component onto the structure to be partially plated and applying an electric current between the structure and the counter electrode, the plating apparatus includes a shape memory device (for example, the memory device of the control device 8) that records the shape of the repair portion on the structure, an application device (for example, the dispenser 9 and the dispenser nozzle 10) that reproduces the shape recording and applies a conductive paste, and a plating power supply 5 for applying an electric current.

[0044] First, an image of the repair area is taken using the camera 7. Then, the gel plating composition 2 is attached to the object to be plated in the same manner as the method shown in the first embodiment. Next, the conductive paste is applied onto the gel plating composition 2 at the target position of the repair area in the same shape as the image taken using the camera 7, using the control device 8. Thereafter, the plating repair portion is plated by the same operation as in Example 1. The plating conditions used are the same as those in Example 1.

[0045] That is, in the method for manufacturing the counter electrode, it is preferable to record the shape of the repair portion on the structure, place the gel-like substance on the repair portion, and then apply the conductive paste in a shape substantially the same as the recorded shape using the coating device.

[0046] <Sixth Embodiment> FIG. 6 is a diagram showing the structure of the counter electrode for performing partial plating using the metal mesh 11 and the plating method using the counter electrode. This embodiment is an example in the case of using a metal mesh as a counter electrode with a variable shape. Details will be described with reference to FIG. 6.

[0047] Since the gel plating composition to be used is the same as that in the first embodiment, the details are omitted. (S1a) Prepare a thick gel composition (porous film) (S2a) Install the metal mesh 11 on the gel Unlike the case of the conductive paste, since the drying and solidifying process of the paste is not required, the gel plating composition can be prepared thick from the beginning, and the metal mesh 11 (with lead wires) serving as the counter electrode can be embedded in the state before the gel is completely solidified, and then gelled. (S4) Install the gel with the counter electrode embedded in the plating target portion (repair portion) (S8) Perform plating by passing an electric current between the object to be plated 1 and the lead wire 4 Plating can be performed by the above method. Here, a nickel mesh 200 was used as the metal mesh 11. The nickel mesh 200 is a mesh that is resistant to strong alkaline caustic soda up to 315°C of heat resistance and has excellent corrosion resistance.

[0048] That is, in a state where a gel-like substance containing a plating component is applied onto a structure to be partially plated, or in a state where a porous film impregnated with a plating component is applied onto a structure to be partially plated, a counter electrode as an electrode in a plating method for generating a partial plating film on the structure by passing an electric current between the structure and the electrode, wherein the flexibility of the counter electrode is equal to or less than that of the gel-like substance or porous film to be used, and the counter electrode is a metal mesh.

[0049] FIG. 7 is a block diagram of a computer 980. The control device 8 (shape memory device) shown in FIG. 5 includes one or more computers 980 shown in FIG. 7. In FIG. 7, the computer 980 includes a CPU 981, a storage unit 982, a communication I / F (interface) 983, an input / output I / F 984, and a media I / F 985. Here, the storage unit 982 includes a RAM 982a, a ROM 982b, and an HDD 982c. The communication I / F 983 is connected to a communication circuit 986. The input / output I / F 984 is connected to an input / output device 987. The input / output device 987 includes a keyboard, a mouse, and the like. The media I / F 985 reads and writes data from and to a recording medium 988.

[0050] The ROM 982b stores an IPL (Initial Program Loader) and the like to be executed by the CPU. The HDD 982c stores a control program, various data, and the like. The CPU 981 realizes various functions by executing a control program and the like read from the HDD 982c into the RAM 982a.

[0051] As described above, in the plating using a gel, when the gel is attached to the object to be plated, since the counter electrode does not deform according to the deformation of the gel, if the gel deforms, the adhesion between the gel and the counter electrode cannot be maintained, and there is a high possibility of plating defects. This problem was solved by using an electrode with a variable shape as the anode. Further, by reducing plating defects according to the present embodiment, the time for repairing the object is reduced, and the time loss for the user of the object is reduced. Furthermore, by reducing plating defects, waste material loss is prevented and environmental load reduction is enabled.

Explanation of Signs

[0052] 1 Object to be plated (structure) 2 Gel plating composition (gel-like substance) 3 Anode (counter electrode, counter electrode) 4 Lead wire 5 Plating power supply (plating device) 6 Plating repair layer (repair part) 7 Camera 8 Control device (shape memory device) 9 Dispenser (coating device) 10 Dispenser nozzle (coating device) 11 Metal mesh

Claims

1. A counter electrode as the electrode in a plating apparatus that generates a partial plating film on the structure by passing an electric current between the structure and the electrode in a state where a gel substance containing a plating component is applied on the structure to be partially plated or in a state where a porous film impregnated with the plating component is applied on the structure to be partially plated, wherein the flexibility of the counter electrode is equal to or less than that of the gel substance or porous film to be used The counter electrode is characterized by the above.

2. The counter electrode according to claim 1, wherein the counter electrode is a metal mesh The counter electrode is characterized by the above.

3. A method for manufacturing a counter electrode as the electrode in a plating method that generates a partial plating film on the structure by passing an electric current between the structure and the electrode in a state where a gel substance containing a plating component is applied on the structure to be partially plated or in a state where a porous film impregnated with the plating component is applied on the structure to be partially plated, wherein the counter electrode is manufactured as a conductive paste by applying a solvent containing a conductive substance to a gel substance containing a plating component or a porous film The method for manufacturing a counter electrode is characterized by the above.

4. The method for manufacturing a counter electrode according to claim 3, wherein the flexibility of the counter electrode is equal to or less than that of the gel substance or porous film to be used The method for manufacturing a counter electrode is characterized by the above.

5. The method for manufacturing a counter electrode according to claim 3, wherein the applied conductive paste contains at least one of Ag, C, Cu, Ni, and Au as the conductive substance, thinner or toluene as the solvent, and any one of epoxy-based, phenol-based, and acrylic-based as the binder resin The method for manufacturing a counter electrode is characterized by the above.

6. The method for manufacturing a counter electrode according to claim 3, recording the shape of the repair part on the structure, placing a gel substance on the repair part, and then applying the conductive paste in a shape substantially the same as the recorded shape using a coating device The method for manufacturing a counter electrode is characterized by the above.

7. A plating apparatus that generates a partial plating film on the structure by passing an electric current between the structure and the counter electrode in a state where a gel substance containing a plating component is applied on the structure to be partially plated or in a state where a porous film impregnated with the plating component is applied on the structure to be partially plated, A shape memory device that records the shape of the repair part on the structure, An application device that reproduces the shape record and applies a conductive paste, A plating power source for applying the current, and A plating device characterized by the above.

8. Manufacture a counter electrode by the method for manufacturing a counter electrode according to any one of Claims 3 to 6, Pass a current between the manufactured counter electrode and the structure to generate a partial plating film on the structure A plating method characterized by the above.

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