WO2018168129A1 - Method for forming plating - Google Patents

Method for forming plating Download PDF

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Publication number
WO2018168129A1
WO2018168129A1 PCT/JP2017/044723 JP2017044723W WO2018168129A1 WO 2018168129 A1 WO2018168129 A1 WO 2018168129A1 JP 2017044723 W JP2017044723 W JP 2017044723W WO 2018168129 A1 WO2018168129 A1 WO 2018168129A1
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Prior art keywords
plating
cathode
paste
anode
particles
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PCT/JP2017/044723
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French (fr)
Japanese (ja)
Inventor
坂本　一三
雅史 鈴木
裕平 藤岡
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オムロン株式会社
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Priority to US16/490,139 priority Critical patent/US20200010971A1/en
Priority to CN201780085930.3A priority patent/CN110268103A/en
Priority to DE112017007235.2T priority patent/DE112017007235T5/en
Publication of WO2018168129A1 publication Critical patent/WO2018168129A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • 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
    • 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
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions

Definitions

  • This disclosure relates to a method for forming a plating.
  • Patent Document 1 when a plating film having a fluororesin film having a film thickness of 5 ⁇ m or less is formed on an electroless plating film or an electroless composite plating film, the fluororesin film and the fluororesin particles are converted to a cationic surfactant.
  • a method of forming a plating that uses a solution dispersed in water with an agent.
  • a cathode is disposed at a lower position in the vertical direction in the plating tank, and dispersed particles dispersed in the plating solution are gradually settled toward the cathode and deposited on the cathode.
  • a method of forming a plating is disclosed.
  • the base material and the electrode are immersed in the plating solution accommodated in the plating tank in order to form the plating. For this reason, there is a problem that the equipment is large and expensive. In addition, it is necessary to maintain a large amount of plating solution or to perform waste solution treatment, which also leads to an increase in cost.
  • the plating solution may be stirred to replenish the plating metal that is consumed near the cathode.
  • the plating solution may be stirred to replenish the plating metal that is consumed near the cathode.
  • it is difficult to form a high-concentration plating film because particles in the plating solution move. is there.
  • there are significant structural restrictions such as the need to install the cathode horizontally.
  • This disclosure is intended to provide a plating forming method capable of forming a high-concentration plating film with simple and inexpensive equipment using a small amount of plating solution.
  • the present disclosure provides: On one side of the cathode, apply a paste made by mixing particles in the plating solution, A liquid retaining member impregnated with the plating solution is disposed on one side of the anode, With the cathode and the anode facing each other, the liquid retaining member and the paste are brought into contact with each other, There is provided a plating forming method of forming a plating on one side of the cathode by applying a voltage between the cathode and the anode.
  • the liquid retaining member is arranged on one side of the anode and the paste is applied to one side of the cathode, so that a high concentration can be obtained at low cost without requiring large-scale equipment or a large amount of plating solution.
  • a plating film can be formed.
  • FIG. 1 shows a plating apparatus according to this embodiment.
  • a plate-like anode 1 and a plate-like cathode 2 are arranged so that their plate surfaces face each other, and a surface of the anode 1 facing the cathode 2 is impregnated with a plating solution 6.
  • the paste 4 is applied to the surface of the cathode 2 facing the anode, and the liquid retaining member 3 and the paste 4 are in contact with each other.
  • anode 1 a flat plate made of a platinum insoluble anode is used.
  • the insoluble anode 1 is used as the anode 1, but soluble materials such as Ag, Au, Pd, Rh, Ni, and Cr can also be used.
  • the cathode 2 is a flat plate made of a tough pitch copper (C1100) cathode.
  • the cathode 2 has a larger surface area on one side (that is, the facing surface) than the anode 1.
  • a DC power supply 5 is connected between the anode 1 and the cathode 2.
  • the urethane sponge is used for the liquid retaining member 3.
  • the urethane sponge has a flat plate shape, has substantially the same area as the cathode 2 and faces the cathode 2. In this case, the thickness of the liquid retaining member 3 is 10 mm or less. Thereby, the current from the anode can be transmitted efficiently.
  • the liquid retaining member 3 is impregnated with a palladium / nickel plating solution.
  • the plating solution 6 that can be impregnated is not limited thereto, and various other plating solutions 6 such as an Ag plating solution and an Au plating solution can be used depending on the application.
  • the paste 4 is a mixture of the plating solution 6 and the particles 7. That is, the paste 4 is mainly composed of the plating solution 6 and the particles 7 and can be applied to the surface of the cathode 2 as an object. is doing.
  • the plating solution 6 the same one as impregnated in the liquid retaining member 3 can be used. Here, a palladium / nickel plating solution is used.
  • zinc oxide coated with silica is used.
  • the particle diameter of the particles 7 is such that the primary particle diameter is 0.6 ⁇ m or less. The reason why the particle size of the particles 7 is set to 0.6 ⁇ m or less is to sufficiently increase the packing density of the particles in the plating film.
  • the particles 7 are not limited to zinc oxide, and metal materials, synthetic resin materials such as fluororesin, nylon, and polyethylene, and compounds such as graphite, fluorinated graphite, molybdenum dioxide, and boron nitride may be used. it can. In this case, for example, if a fluororesin is used, wettability can be imparted in addition to the performance of the conventional metal plating film.
  • the paste 4, the plating solution 6 and the particles 7 are modified with a surfactant as a dispersion aid.
  • a surfactant examples include a cationic surfactant, an amphoteric surfactant exhibiting a cationic property corresponding to the pH of the plating solution 6, and a nonionic surfactant.
  • the liquid retaining member 3 impregnated with the plating solution 6 is disposed on one surface (that is, the facing surface) of the anode 1, and the paste 4 is applied to one surface (that is, the facing surface) of the cathode 2.
  • the paste 4 is applied by a dispenser, a squeegee or the like, and the thickness is 0.1 mm to 0.5 mm. By setting the thickness of the paste 4 in this way, the current from the anode can be efficiently transmitted to the cathode 2.
  • the anode 1 and the cathode 2 are arranged to face each other, and the liquid retaining member 3 and the paste 4 are brought into surface contact.
  • the anode 1 and the cathode 2 may be opposed in the vertical direction, or may be opposed in other directions such as the horizontal direction.
  • the anode 1 and the cathode 2 are brought close to each other, and the liquid retaining member 3 and the paste 4 are pressurized. Further, the anode 1 is vibrated to vibrate the paste 4 through the liquid retaining member 3. Thereby, the particle
  • a voltage is applied between the anode 1 and the cathode 2
  • a plating film is formed on the surface of the cathode 2. That is, metal ions in the plating solution 6 contained in the paste 4 are reduced on the surface of the cathode 2, and a plating film is formed while entraining the particles 7 in the paste 4 due to current wraparound.
  • the formed plating film has the properties of the incorporated particles 7 in addition to the properties of the metal in the plating solution 6, and has a characteristic as a composite plating film.
  • the paste 4 is applied to the cathode 2 and the anode 1 is impregnated with the plating solution 6 in the liquid retaining member 3, the following advantages are obtained.
  • the plating solution 6 is only contained in the paste 4 and the liquid retaining member 3, the usage amount of the plating solution 6 can be significantly suppressed as compared with the case where the plating solution 6 is stored in a conventional plating tank. For this reason, a large-scale installation becomes unnecessary and the maintenance of the plating solution 6 and the waste liquid treatment can be simplified.
  • the paste 4 in which the particles 7 are mixed with the plating solution 6 is used, a high-concentration plating film can be formed.
  • the effect by the particles 7 can also be exhibited.
  • combining fluororesin particles with high hardness Ni plating can exhibit the effects of high wear resistance and low rolling resistance, and can be used for mechanical sliding parts and bearing parts.
  • metal material for example, zinc oxide
  • the electrical resistance is low, and the generated arc can be cooled and extinguished. It can be used.
  • Combining fluororesin particles with high hardness Ni plating can provide high wear resistance and low sliding resistance, and when used in a mold, can exhibit excellent releasability.
  • the anode 1 is a platinum insoluble anode
  • the cathode 2 is tough pitch copper (C1100)
  • the liquid retaining member 3 is urethane sponge
  • the plating solution 6 is mixed with a commercially available Pd—Ni (palladium / nickel) plating solution.
  • Pd—Ni palladium / nickel
  • the plating solution 6 used for the paste 4 was 10 ml.
  • two kinds of particles 7 mixed in the plating solution 6 having a primary particle diameter of 35 nm (0.035 ⁇ m) and 20 nm (0.02 ⁇ m) were prepared and their weights were prepared in the range of 1.5 g to 8.5 g.
  • the plating time was 5, 10, or 15 minutes, and the current density between the anode 1 and the cathode 2 was 5 to 25 A / dm 2 .
  • the composite plating particle concentration of the plating film formed can be increased by reducing the primary particle diameter of the particles and increasing the contained weight. Moreover, the film thickness of the plating film obtained was able to be enlarged by raising a current density.
  • the plating method includes: On one side of the cathode 2, a paste 4 obtained by mixing particles 7 in a plating solution 6 is applied, A liquid retaining member 3 impregnated with the plating solution 6 is disposed on one surface of the anode 1, With the cathode 2 and the anode 1 facing each other, the liquid retaining member 3 and the paste 4 are brought into contact with each other, By applying a voltage between the cathode 2 and the anode 1, plating is formed on one side of the cathode 2.
  • the plating film can be formed by simply placing the liquid retaining member 3 on one side of the anode 1 and applying the paste 4 on one side of the cathode 2. Therefore, a plating film can be formed at low cost without requiring large-scale equipment or a large amount of plating solution 6.
  • the plating method according to the second aspect of the present disclosure includes: The paste 4 is mixed with a surfactant.
  • the wettability of the plating surface can be improved, plating defects such as no plating and pits can be prevented, and generation of mist from the plating solution 6 can be suppressed.
  • the particles 7 are made of either metal or resin.
  • the particle 7 has a particle size of 0.02 ⁇ m or more and 0.6 ⁇ m or less.
  • the particle size of the particles 7 is set in the range of 0.02 ⁇ m or more and 0.6 ⁇ m or less, an effect that current flows around the particles and efficiently flows can be obtained.
  • the particle 7 is 10 wt% or more and 72 wt% or less with respect to the paste 4.
  • the particles 7 can be contained at a high concentration, so that a high concentration plating film can be formed.
  • a sponge is used for the liquid retaining member 3.
  • the plating forming method according to the present disclosure can be used to form plating films on the surfaces of various materials such as mechanical sliding parts, electrical contacts, and mold surfaces.

Abstract

According to the present invention, plating is formed on one side of a negative electrode by: coating the one side of the negative electrode with a paste formed by mixing particles in a plating liquid; disposing, on one side of a positive electrode, a liquid holding member impregnated with the plating liquid; making the negative electrode and the positive electrode face each other; bringing the liquid holding member and the paste into contact with each other; and applying a voltage between the negative electrode and the positive electrode.

Description

めっきの形成方法Plating formation method
　本開示は、めっきの形成方法に関する。 This disclosure relates to a method for forming a plating.
　特許文献１には、無電解めっき皮膜または無電解複合めっき皮膜上に、膜厚が5μm以下のフッ素樹脂膜を有するめっき皮膜を形成する際、フッ素樹脂膜を、フッ素樹脂粒子をカチオン系界面活性剤で水中に分散した溶液を用いて形成するようにしためっきの形成方法が開示されている。 In Patent Document 1, when a plating film having a fluororesin film having a film thickness of 5 μm or less is formed on an electroless plating film or an electroless composite plating film, the fluororesin film and the fluororesin particles are converted to a cationic surfactant. There is disclosed a method of forming a plating that uses a solution dispersed in water with an agent.
　また、特許文献２には、めっき槽内の鉛直方向の下位置に陰極を、配置し、めっき液中に分散させた分散粒子を陰極に向け徐々に沈降させ、陰極上に堆積させるようにしためっきの形成方法が開示されている。 Further, in Patent Document 2, a cathode is disposed at a lower position in the vertical direction in the plating tank, and dispersed particles dispersed in the plating solution are gradually settled toward the cathode and deposited on the cathode. A method of forming a plating is disclosed.
特開２００７－３９７１１号公報JP 2007-39711 A 特開２０１６-１４１８６２号公報JP 2016-141862 A
　しかしながら、前記めっきの形成方法では、めっき槽内に収容しためっき液中に、めっきを形成するために基材や電極を浸漬させるようにしている。このため、設備が大掛かりでコストがかかるという問題がある。また、大量のめっき液をメンテナンスしたり、廃液処理したりする必要があり、この点でもコストアップを招来してしまう。 However, in the plating forming method, the base material and the electrode are immersed in the plating solution accommodated in the plating tank in order to form the plating. For this reason, there is a problem that the equipment is large and expensive. In addition, it is necessary to maintain a large amount of plating solution or to perform waste solution treatment, which also leads to an increase in cost.
　また、後者の方法では、陰極付近で消耗するめっき金属を補給するためにめっき液を攪拌することがあるが、めっき液中の粒子が移動し、高濃度のめっき皮膜を形成することは困難である。また、陰極を水平に設置しなければならないなど、構成上の制約が大きい。 In the latter method, the plating solution may be stirred to replenish the plating metal that is consumed near the cathode. However, it is difficult to form a high-concentration plating film because particles in the plating solution move. is there. In addition, there are significant structural restrictions such as the need to install the cathode horizontally.
　本開示は、少量のめっき液を使用した簡単かつ安価な設備によって高濃度のめっき皮膜を形成できるめっきの形成方法を提供することを課題とする。 This disclosure is intended to provide a plating forming method capable of forming a high-concentration plating film with simple and inexpensive equipment using a small amount of plating solution.
　本開示は、前記課題を解決するための手段として、
　陰極の片面に、めっき液に粒子を混合してなるペーストを塗布し、
　陽極の片面に、前記めっき液を含浸した保液部材を配置し、
　前記陰極と前記陽極とを対向させて、前記保液部材と前記ペーストとを互いに接触させ、
　前記陰極と前記陽極との間に電圧を印加することにより、前記陰極の片面にめっきを形成する、めっきの形成方法を提供する。 As a means for solving the above problems, the present disclosure provides:
On one side of the cathode, apply a paste made by mixing particles in the plating solution,
A liquid retaining member impregnated with the plating solution is disposed on one side of the anode,
With the cathode and the anode facing each other, the liquid retaining member and the paste are brought into contact with each other,
There is provided a plating forming method of forming a plating on one side of the cathode by applying a voltage between the cathode and the anode.
　本開示によれば、陽極の片面に保液部材を配置し、陰極の片面にペーストを塗布するようにしているので、大掛かりな設備や大量のめっき液を必要とすることなく安価に高濃度のめっき皮膜を形成できる。 According to the present disclosure, the liquid retaining member is arranged on one side of the anode and the paste is applied to one side of the cathode, so that a high concentration can be obtained at low cost without requiring large-scale equipment or a large amount of plating solution. A plating film can be formed.
本実施形態に係るめっき形成装置の概略説明図である。It is a schematic explanatory drawing of the plating formation apparatus which concerns on this embodiment.
　以下、本開示に係る実施形態を添付図面に従って説明する。なお、以下の説明は、本質的に例示に過ぎず、本開示、その適用物、あるいは、その用途を制限することを意図するものではない。また、図面は模式的なものであり、各寸法の比率等は現実のものとは相違している。 Hereinafter, embodiments according to the present disclosure will be described with reference to the accompanying drawings. In addition, the following description is only an illustration essentially and does not intend restrict | limiting this indication, its application thing, or its use. Further, the drawings are schematic, and the ratio of each dimension is different from the actual one.
　図１は、本実施形態に係るめっき形成装置を示す。このめっき形成装置は、板状の陽極１と板状の陰極２とを板面同士が対向するように配置し、陽極１の陰極２に対する対向面にめっき液６を含浸させた保液部材３を配置して、陰極２の陽極に対する対向面にペースト４を塗布し、保液部材３とペースト４とが接触するように構成している。 FIG. 1 shows a plating apparatus according to this embodiment. In this plating forming apparatus, a plate-like anode 1 and a plate-like cathode 2 are arranged so that their plate surfaces face each other, and a surface of the anode 1 facing the cathode 2 is impregnated with a plating solution 6. The paste 4 is applied to the surface of the cathode 2 facing the anode, and the liquid retaining member 3 and the paste 4 are in contact with each other.
　陽極１には、白金不溶解アノードからなる平板が使用されている。ここでは、陽極１には不溶性陽極１を使用しているが、Ａｇ，Ａｕ，Ｐｄ，Ｒｈ，Ｎｉ，Ｃｒ等の溶解性の材料を使用することもできる。 As the anode 1, a flat plate made of a platinum insoluble anode is used. Here, the insoluble anode 1 is used as the anode 1, but soluble materials such as Ag, Au, Pd, Rh, Ni, and Cr can also be used.
　陰極２には、タフピッチ銅（Ｃ１１００）カソードからなる平板が使用されている。陰極２は陽極１に比べて片面（すなわち、対向面）の表面積が大きくなっている。 The cathode 2 is a flat plate made of a tough pitch copper (C1100) cathode. The cathode 2 has a larger surface area on one side (that is, the facing surface) than the anode 1.
　陽極１と陰極２との間には直流電源５が接続されている。 A DC power supply 5 is connected between the anode 1 and the cathode 2.
　保液部材３には、ウレタンスポンジが使用されている。ウレタンスポンジは平板状で、陰極２とほぼ同じ面積を有して陰極２と対向している。この場合、保液部材３の厚みは、10ｍｍ以下としている。これにより、陽極からの電流を効率良く伝えることができる。保液部材３には、パラジウム・ニッケルめっき液を含浸させている。但し、含浸できるめっき液６はこれに限らず、用途に応じて、例えば、Agめっき液やAuめっき液等、他の種々のめっき液６を使用できる。 ウ レ タ ン Urethane sponge is used for the liquid retaining member 3. The urethane sponge has a flat plate shape, has substantially the same area as the cathode 2 and faces the cathode 2. In this case, the thickness of the liquid retaining member 3 is 10 mm or less. Thereby, the current from the anode can be transmitted efficiently. The liquid retaining member 3 is impregnated with a palladium / nickel plating solution. However, the plating solution 6 that can be impregnated is not limited thereto, and various other plating solutions 6 such as an Ag plating solution and an Au plating solution can be used depending on the application.
　ペースト４には、めっき液６に粒子７を混合したものが使用されている。すなわち、ペースト４は、めっき液６と粒子７を主成分とし、対象物である陰極２の表面に塗布が可能で、塗布後にブラシによる圧力を受けても塗布形状を維持し、導電性を有している。めっき液６には、保液部材３に含浸させたものと同様なものを使用でき、ここではパラジウム・ニッケルめっき液が使用されている。粒子７には、シリカをコーティングした酸化亜鉛が使用されている。粒子７の粒径は、一次粒子径が0.6μｍ以下とされている。粒子７の粒径を0.6μｍ以下としたのは、めっき皮膜中の粒子の充填密度を十分に高くするためである。 The paste 4 is a mixture of the plating solution 6 and the particles 7. That is, the paste 4 is mainly composed of the plating solution 6 and the particles 7 and can be applied to the surface of the cathode 2 as an object. is doing. As the plating solution 6, the same one as impregnated in the liquid retaining member 3 can be used. Here, a palladium / nickel plating solution is used. For the particles 7, zinc oxide coated with silica is used. The particle diameter of the particles 7 is such that the primary particle diameter is 0.6 μm or less. The reason why the particle size of the particles 7 is set to 0.6 μm or less is to sufficiently increase the packing density of the particles in the plating film.
　但し、前記粒子７としては、酸化亜鉛に限らず、金属材料や、フッ素樹脂、ナイロン、ポリエチレン等の合成樹脂材料、黒鉛、フッ化黒鉛、二酸化モリブデン、窒化ホウ素等の化合物等を使用することができる。この場合、例えば、フッ素樹脂を使用すれば、従来の金属めっき被膜の性能に加えて、湿潤性を持たせることができる。 However, the particles 7 are not limited to zinc oxide, and metal materials, synthetic resin materials such as fluororesin, nylon, and polyethylene, and compounds such as graphite, fluorinated graphite, molybdenum dioxide, and boron nitride may be used. it can. In this case, for example, if a fluororesin is used, wettability can be imparted in addition to the performance of the conventional metal plating film.
　また、ペースト４、めっき液６及び粒子７には、分散助剤として界面活性剤を修飾している。使用できる界面活性剤としては、例えば、カチオン性界面活性剤、めっき液６のｐＨに対応してカチオン性を示す両性界面活性剤、非イオン性界面活性剤等が含まれる。界面活性剤を使用することで、めっき面の濡れ性を向上し、無めっき、ピットなどのめっきの欠陥を防止し、めっき液６からのミストの発生を抑制できる。 Further, the paste 4, the plating solution 6 and the particles 7 are modified with a surfactant as a dispersion aid. Examples of the surfactant that can be used include a cationic surfactant, an amphoteric surfactant exhibiting a cationic property corresponding to the pH of the plating solution 6, and a nonionic surfactant. By using the surfactant, the wettability of the plating surface can be improved, plating defects such as no plating and pits can be prevented, and generation of mist from the plating solution 6 can be suppressed.
　前記構成のめっき形成装置では、陽極１の片面（すなわち、対向面）にめっき液６を含浸させた保液部材３を配置し、陰極２の片面（すなわち、対向面）にペースト４を塗布する。ペースト４の塗布は、ディスペンサーやスキージ等により行い、厚さは0.1ｍｍから0.5ｍｍとしている。このようにペースト４の厚みを設定することで、陽極からの電流を効率良く陰極２に伝えることができる。 In the plating forming apparatus having the above-described configuration, the liquid retaining member 3 impregnated with the plating solution 6 is disposed on one surface (that is, the facing surface) of the anode 1, and the paste 4 is applied to one surface (that is, the facing surface) of the cathode 2. . The paste 4 is applied by a dispenser, a squeegee or the like, and the thickness is 0.1 mm to 0.5 mm. By setting the thickness of the paste 4 in this way, the current from the anode can be efficiently transmitted to the cathode 2.
　そして、陽極１と陰極２とを対向して配置し、保液部材３とペースト４とを面接触させる。この場合、陽極１と陰極２とは垂直方向に対向させてもよいし、水平方向等、他の向きに対向させてもよい。 Then, the anode 1 and the cathode 2 are arranged to face each other, and the liquid retaining member 3 and the paste 4 are brought into surface contact. In this case, the anode 1 and the cathode 2 may be opposed in the vertical direction, or may be opposed in other directions such as the horizontal direction.
　この状態で、陽極１と陰極２を接近させ、保液部材３とペースト４とを加圧する。また、陽極１を振動させて保液部材３を介してペースト４を加振する。これにより、ペースト４中の粒子７を凝集させることができる。そして、陽極１と陰極２の間に電圧を印加すると、陰極２の表面にめっき皮膜が形成される。すなわち、陰極２の表面で、ペースト４に含まれるめっき液６中の金属イオンが還元され、電流の回り込みにより、ペースト４中の粒子７を取り込みながらめっき皮膜が形成される。この場合、形成されるめっき皮膜は、めっき液６中の金属の性質に加えて、取り込まれた粒子７による性質を持ち、複合めっき皮膜としての特徴を有する。 In this state, the anode 1 and the cathode 2 are brought close to each other, and the liquid retaining member 3 and the paste 4 are pressurized. Further, the anode 1 is vibrated to vibrate the paste 4 through the liquid retaining member 3. Thereby, the particle | grains 7 in the paste 4 can be aggregated. When a voltage is applied between the anode 1 and the cathode 2, a plating film is formed on the surface of the cathode 2. That is, metal ions in the plating solution 6 contained in the paste 4 are reduced on the surface of the cathode 2, and a plating film is formed while entraining the particles 7 in the paste 4 due to current wraparound. In this case, the formed plating film has the properties of the incorporated particles 7 in addition to the properties of the metal in the plating solution 6, and has a characteristic as a composite plating film.
　このように、陰極２にペースト４を塗布し、陽極１に保液部材３にめっき液６を含浸させるようにしているので、次の利点がある。
（１）めっき液６がペースト４と保液部材３に含まれるだけであるので、従来のめっき槽にめっき液６を貯留する場合に比べてめっき液６の使用量を大幅に抑制できる。このため、大掛かりな設備が不要となり、めっき液６のメンテナンスや廃液処理も簡略化できる。
（２）ペースト４にめっき液６に粒子７を混合したものを使用しているので、高濃度のめっき皮膜を形成できる。
（３）形成されためっき被膜では、めっき液６の組成物による効果に加えて、粒子７による効果をも発揮させることができる。例えば、硬度の高いNiめっきに、フッ素樹脂粒子を組み合わせると、耐摩耗性が高く、ころがり抵抗の低いという効果を発揮させることができ、機械摺動部や軸受部に使用できる。また、電気抵抗値の低いAgめっきに、昇華温度の低い金属材料（例えば酸化亜鉛）粒子を組み合わせると、電気的抵抗が低く、発生するアークを冷却して消弧させることができ、電気接点に使用可能である。硬度の高いNiめっきに、フッ素樹脂粒子を組み合わせると、耐摩耗性が高く、すべり抵抗を低くすることができ、金型に使用すると、優れた離形性を発揮させることができる。 Thus, since the paste 4 is applied to the cathode 2 and the anode 1 is impregnated with the plating solution 6 in the liquid retaining member 3, the following advantages are obtained.
(1) Since the plating solution 6 is only contained in the paste 4 and the liquid retaining member 3, the usage amount of the plating solution 6 can be significantly suppressed as compared with the case where the plating solution 6 is stored in a conventional plating tank. For this reason, a large-scale installation becomes unnecessary and the maintenance of the plating solution 6 and the waste liquid treatment can be simplified.
(2) Since the paste 4 in which the particles 7 are mixed with the plating solution 6 is used, a high-concentration plating film can be formed.
(3) In the formed plating film, in addition to the effect by the composition of the plating solution 6, the effect by the particles 7 can also be exhibited. For example, combining fluororesin particles with high hardness Ni plating can exhibit the effects of high wear resistance and low rolling resistance, and can be used for mechanical sliding parts and bearing parts. In addition, by combining Ag plating with low electrical resistance value with metal material (for example, zinc oxide) particles with low sublimation temperature, the electrical resistance is low, and the generated arc can be cooled and extinguished. It can be used. Combining fluororesin particles with high hardness Ni plating can provide high wear resistance and low sliding resistance, and when used in a mold, can exhibit excellent releasability.
　以下の条件によりめっき皮膜を形成する実験を行った。
　すなわち、陽極１には白金不溶解アノード、陰極２にはタフピッチ銅（C1100）、保液部材３にはウレタンスポンジ、めっき液６には市販のPd-Ni（パラジウム・ニッケル）めっき液、混合する粒子７にはシリカコート酸化亜鉛をそれぞれ使用した。また、以下の表１に記載するように、ペースト４に使用するめっき液６は10mlとした。まためっき液６に混入する粒子７には、一次粒子径が35nm（0.035μm）と20nm（0.02μm）の２種類を用意し、その重量は1.5g～8.5gの範囲で４種類用意した。めっき時間は、5,10,15分のいずれかとし、陽極１と陰極２の間での電流密度は5～25A/dm2とした。 An experiment for forming a plating film under the following conditions was performed.
That is, the anode 1 is a platinum insoluble anode, the cathode 2 is tough pitch copper (C1100), the liquid retaining member 3 is urethane sponge, and the plating solution 6 is mixed with a commercially available Pd—Ni (palladium / nickel) plating solution. For the particles 7, silica-coated zinc oxide was used. Moreover, as described in Table 1 below, the plating solution 6 used for the paste 4 was 10 ml. In addition, two kinds of particles 7 mixed in the plating solution 6 having a primary particle diameter of 35 nm (0.035 μm) and 20 nm (0.02 μm) were prepared and their weights were prepared in the range of 1.5 g to 8.5 g. The plating time was 5, 10, or 15 minutes, and the current density between the anode 1 and the cathode 2 was 5 to 25 A / dm 2 .
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から明らかなように、粒子の一次粒子径を小さくし、含有する重量を大きくすることにより形成されるめっき皮膜の複合めっき粒子濃度を高くすることができた。また、電流密度を高めることで、得られるめっき被膜の膜厚を大きくすることができた。 As is clear from Table 1, the composite plating particle concentration of the plating film formed can be increased by reducing the primary particle diameter of the particles and increasing the contained weight. Moreover, the film thickness of the plating film obtained was able to be enlarged by raising a current density.
　以上、図面を参照して本開示における種々の実施形態を詳細に説明したが、最後に、本開示の種々の態様について説明する。なお、以下の説明では、一例として、参照符号も添えて記載する。 Although various embodiments in the present disclosure have been described in detail above with reference to the drawings, finally, various aspects of the present disclosure will be described. In the following description, reference numerals are also given as an example.
　本開示の第１態様のめっき形成方法は、
　陰極２の片面に、めっき液６に粒子７を混合してなるペースト４を塗布し、
　陽極１の片面に、前記めっき液６を含浸した保液部材３を配置し、
　前記陰極２と前記陽極１とを対向させて、前記保液部材３と前記ペースト４とを互いに接触させ、
　前記陰極２と前記陽極１との間に電圧を印加することにより、前記陰極２の片面にめっきを形成する。 The plating method according to the first aspect of the present disclosure includes:
On one side of the cathode 2, a paste 4 obtained by mixing particles 7 in a plating solution 6 is applied,
A liquid retaining member 3 impregnated with the plating solution 6 is disposed on one surface of the anode 1,
With the cathode 2 and the anode 1 facing each other, the liquid retaining member 3 and the paste 4 are brought into contact with each other,
By applying a voltage between the cathode 2 and the anode 1, plating is formed on one side of the cathode 2.
　第１態様のめっき形成方法によれば、陽極１の片面に保液部材３を配置し、陰極２の片面にペースト４を塗布するだけでめっき皮膜を形成することができる。したがって、大掛かりな設備や大量のめっき液６を必要とすることなく安価にめっき皮膜を形成できる。 According to the plating method of the first aspect, the plating film can be formed by simply placing the liquid retaining member 3 on one side of the anode 1 and applying the paste 4 on one side of the cathode 2. Therefore, a plating film can be formed at low cost without requiring large-scale equipment or a large amount of plating solution 6.
　本開示の第２態様のめっき形成方法は、
　前記ペースト４は界面活性剤を混合されている。 The plating method according to the second aspect of the present disclosure includes:
The paste 4 is mixed with a surfactant.
　第２態様のめっき形成方法によれば、めっき面の濡れ性を向上し、無めっき、ピットなどのめっきの欠陥を防止し、めっき液６からのミストの発生を抑制できる。 According to the plating formation method of the second aspect, the wettability of the plating surface can be improved, plating defects such as no plating and pits can be prevented, and generation of mist from the plating solution 6 can be suppressed.
　本開示の第３態様のめっき形成方法は、前記粒子７を、金属又は樹脂のいずれかで構成している。 In the plating forming method according to the third aspect of the present disclosure, the particles 7 are made of either metal or resin.
　本開示の第４態様のめっき形成方法は、前記粒子７が、0.02μｍ以上、0.6μｍ以下の粒径を有する。 In the plating formation method according to the fourth aspect of the present disclosure, the particle 7 has a particle size of 0.02 μm or more and 0.6 μm or less.
　第４態様のめっき形成方法によれば、粒子７の粒径を0.02μｍ以上、0.6μｍ以下の範囲としたので、電流が粒子の中に回り込み、効率よく流れるという効果が得られる。 According to the plating method of the fourth aspect, since the particle size of the particles 7 is set in the range of 0.02 μm or more and 0.6 μm or less, an effect that current flows around the particles and efficiently flows can be obtained.
　本開示の第５態様のめっき形成方法は、前記粒子７が、前記ペースト４に対して10重量％以上、72重量％以下である。 In the plating formation method according to the fifth aspect of the present disclosure, the particle 7 is 10 wt% or more and 72 wt% or less with respect to the paste 4.
　第５態様のめっき形成方法によれば、ペースト４であるので粒子７を高濃度に含有させることができるので、高濃度のめっき皮膜を形成可能となる。 According to the plating method of the fifth aspect, since the paste 4 is used, the particles 7 can be contained at a high concentration, so that a high concentration plating film can be formed.
　本開示の第６態様のめっき形成方法は、前記保液部材３にはスポンジを使用する。 In the plating forming method according to the sixth aspect of the present disclosure, a sponge is used for the liquid retaining member 3.
　なお、前記様々な実施形態または変形例のうちの任意の実施形態または変形例を適宜組み合わせることにより、それぞれの有する効果を奏するようにすることができる。また、実施形態同士の組み合わせまたは実施例同士の組み合わせまたは実施形態と実施例との組み合わせが可能であると共に、異なる実施形態または実施例の中の特徴同士の組み合わせも可能である。 It should be noted that, by appropriately combining any of the various embodiments or modifications, the effects possessed by them can be produced. In addition, combinations of the embodiments, combinations of the examples, or combinations of the embodiments and examples are possible, and combinations of features in different embodiments or examples are also possible.
　本開示は、添付図面を参照しながら好ましい実施形態に関連して充分に記載されているが、この技術の熟練した人々にとっては種々の変形や修正は明白である。そのような変形や修正は、添付した請求の範囲による本開示の範囲から外れない限りにおいて、その中に含まれると理解されるべきである。 Although the present disclosure has been fully described in connection with preferred embodiments with reference to the accompanying drawings, various variations and modifications will be apparent to those skilled in the art. Such changes and modifications are to be understood as included within the scope of the present disclosure as set forth in the appended claims.
　本開示に係るめっきの形成方法は、機械摺動部、電気接点、金型表面等、種々の材料の表面にめっき皮膜を形成するために使用できる。 The plating forming method according to the present disclosure can be used to form plating films on the surfaces of various materials such as mechanical sliding parts, electrical contacts, and mold surfaces.
　１…陽極
　２…陰極
　３…保液部材
　４…ペースト
　５…直流電源
　６…めっき液
　７…粒子 DESCRIPTION OF SYMBOLS 1 ... Anode 2 ... Cathode 3 ... Liquid holding member 4 ... Paste 5 ... DC power supply 6 ... Plating solution 7 ... Particle

Claims (6)

  1. 　陰極の片面に、めっき液に粒子を混合してなるペーストを塗布し、
    　陽極の片面に、前記めっき液を含浸した保液部材を配置し、
    　前記陰極と前記陽極とを対向させて、前記保液部材と前記ペーストとを互いに接触させ、
    　前記陰極と前記陽極との間に電圧を印加することにより、前記陰極の片面にめっきを形成する、めっきの形成方法。     On one side of the cathode, apply a paste made by mixing particles in the plating solution,
    A liquid retaining member impregnated with the plating solution is disposed on one side of the anode,
    With the cathode and the anode facing each other, the liquid retaining member and the paste are brought into contact with each other,
    A plating method, wherein a voltage is applied between the cathode and the anode to form a plating on one side of the cathode.
  2. 　前記ペーストは界面活性剤を混合されている、請求項１に記載のめっきの形成方法。 The method for forming a plating according to claim 1, wherein the paste is mixed with a surfactant.
  3. 　前記粒子は、金属又は樹脂のいずれかからなる、請求項１又は２に記載のめっきの形成方法。 The method for forming a plating according to claim 1 or 2, wherein the particles are made of either metal or resin.
  4. 　前記粒子は、0.02μｍ以上、0.6μｍ以下の粒径を有する、請求項１から３のいずれか１項に記載のめっきの形成方法。 The method for forming a plating according to any one of claims 1 to 3, wherein the particles have a particle size of 0.02 µm or more and 0.6 µm or less.
  5. 　前記粒子は、前記ペーストに対して10重量％以上、72重量％以下である、請求項１から４のいずれか１項に記載のめっきの形成方法。 The method for forming a plating according to any one of claims 1 to 4, wherein the particles are 10 wt% or more and 72 wt% or less with respect to the paste.
  6. 　前記保液部材はスポンジである、請求項１から５のいずれか１項に記載のめっきの形成方法。 The method for forming a plating according to any one of claims 1 to 5, wherein the liquid retaining member is a sponge.
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