JP2008127641A - Method for producing composite plated material - Google Patents
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- JP2008127641A JP2008127641A JP2006315036A JP2006315036A JP2008127641A JP 2008127641 A JP2008127641 A JP 2008127641A JP 2006315036 A JP2006315036 A JP 2006315036A JP 2006315036 A JP2006315036 A JP 2006315036A JP 2008127641 A JP2008127641 A JP 2008127641A
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本発明は、複合めっき材の製造方法に関し、特にスイッチやコネクタなどの接点や端子部品などの材料として使用される銀めっき材の製造方法に関する。 The present invention relates to a method for manufacturing a composite plating material, and more particularly, to a method for manufacturing a silver plating material used as a material for contacts and terminal parts such as switches and connectors.
一般に、スイッチやコネクタ等の接点や端子部品等の材料として、導体素材に銀めっきを施した銀めっき材が使用されている。これは、これらの接点や端子部品等が摺動過程で加熱して銅や銅合金等の導体素材を酸化してしまうことを防止するためである。 In general, a silver plating material obtained by applying silver plating to a conductor material is used as a material for contacts and terminal parts such as switches and connectors. This is to prevent these contact points, terminal components, and the like from being heated in the sliding process and oxidizing a conductive material such as copper or a copper alloy.
しかし、銀めっきは軟質で摩耗し易く、摩擦係数が高いという問題がある。特許文献１では、この問題を解決するため、電気めっきにより被めっき材としての導体素材上に施す皮膜を、銀マトリクス中に黒鉛粒子を分散させた複合材の皮膜にすることで耐摩耗性を向上させることが提案されている。また、特許文献２では、このような黒鉛粒子を含む銀めっき皮膜の適用に適しためっき浴として、炭素粒子の分散に適した湿潤剤を使用しためっき浴が提案されている。さらに、特許文献３では、ゾル−ゲル法によって炭素粒子に金属酸化物をコーティングし、銀めっき液中への黒鉛粒子の分散性を高めることで、めっき皮膜中への黒鉛粒子の複合化量を多くする技術が提案されている。特許文献４、５では、炭素粒子を酸化処理してから銀めっき液に添加することにより、分散剤などの添加物を使用することなく、且つ炭素粒子の表面をコーティングすることなく、炭素粒子を良好に分散させた銀めっき液を使用した技術が提案されている。 However, silver plating is soft and easy to wear, and has a problem of high friction coefficient. In Patent Document 1, in order to solve this problem, the coating applied on the conductor material as the material to be plated by electroplating is made of a composite material in which graphite particles are dispersed in a silver matrix, thereby improving wear resistance. It has been proposed to improve. Patent Document 2 proposes a plating bath using a wetting agent suitable for dispersing carbon particles as a plating bath suitable for application of such a silver plating film containing graphite particles. Furthermore, in Patent Document 3, the composite amount of the graphite particles in the plating film is increased by coating the carbon particles with a metal oxide by a sol-gel method and enhancing the dispersibility of the graphite particles in the silver plating solution. Many techniques have been proposed. In Patent Documents 4 and 5, the carbon particles are oxidized without being added to the silver plating solution after being oxidized, and without using an additive such as a dispersant and without coating the surface of the carbon particles. A technique using a well-dispersed silver plating solution has been proposed.
上記特許文献１〜５の複合めっき技術で用いられる黒鉛粒子は、一般に「平たい鱗片状」と呼ばれる形状をしており、被めっき材上の複合めっき皮膜中では、めっき皮膜と平行に折り重なった状態で分散している。
しかし、上記の特許文献１〜５の複合めっき技術により得られる銀−黒鉛粒子複合めっき皮膜では、この複合めっき皮膜の耐熱摩耗を向上させるＣ（炭素粒子）の含有量（以下、Ｃ含有量と呼ぶ）を確保しながら生産性を向上させることが非常に難しい。即ち、生産性を上げるために複合めっき処理において電気めっきを行う際の電流密度を上昇させると複合めっき皮膜中のＣ含有量が減少し、複合めっき皮膜の耐摩耗性が低下してしまう。そのため、スイッチやコネクタの高耐久化に対応することが可能である高い耐摩耗性の複合めっき皮膜を備えた複合めっき材を、従来よりも高い生産効率で製造可能な複合めっき材の製造方法の開発が望まれていた。 However, in the silver-graphite particle composite plating film obtained by the composite plating techniques of Patent Documents 1 to 5 described above, the content of C (carbon particles) that improves the heat-resistant wear of the composite plating film (hereinafter referred to as C content) It is very difficult to improve productivity while securing. That is, when the current density at the time of performing electroplating in the composite plating process is increased in order to increase productivity, the C content in the composite plating film is reduced, and the wear resistance of the composite plating film is reduced. Therefore, a composite plating material manufacturing method capable of manufacturing a composite plating material having a high wear-resistant composite plating film capable of supporting high durability of switches and connectors with higher production efficiency than before. Development was desired.
本発明は、このような従来の問題点を鑑み、従来公知の銀−炭素粒子複合めっき製造技術を用いて製造する場合よりも高い生産効率で、耐摩耗性の高い複合めっき皮膜を備えた複合めっき材を製造可能とすることを目的とする。 In view of such conventional problems, the present invention is a composite comprising a composite plating film having a high wear resistance and a higher production efficiency than that produced using a conventionally known silver-carbon particle composite plating production technique. An object is to make it possible to produce a plating material.
本発明者らは、上記課題を解決する為に鋭意研究した結果、従来公知のめっき材製造技術において摺動材料として使われる鱗片状の黒鉛とは形状が異なる塊状の黒鉛を使用することによって、高い耐摩耗性の銀−炭素粒子複合めっき皮膜を備えた複合めっき材を製造する際の生産性を著しく向上させることができることを見出し、本発明を完成するに至った。 As a result of earnest research to solve the above problems, the present inventors have used massive graphite having a shape different from that of scaly graphite used as a sliding material in a conventionally known plating material manufacturing technique. It has been found that the productivity in producing a composite plating material having a high wear-resistant silver-carbon particle composite plating film can be remarkably improved, and the present invention has been completed.
本発明は、かかる知見に基づいてなされたものである。即ち、本発明によれば、酸化処理を行った塊状の炭素粒子と、銀マトリクス配向調整剤を添加した銀めっき液を使用して、銀層中に炭素粒子を含有する複合材からなる皮膜を被めっき材上に形成することを特徴とする、複合めっき材の製造方法が提供される。 The present invention has been made based on such knowledge. That is, according to the present invention, a film composed of a composite material containing carbon particles in a silver layer is formed using a massive carbon particle subjected to oxidation treatment and a silver plating solution to which a silver matrix alignment modifier is added. A method for producing a composite plating material is provided, which is formed on a material to be plated.
上記複合めっき材の製造方法において、前記銀マトリクス配向調整剤がセレンイオンを含んでいてもよい。 In the method for producing a composite plating material, the silver matrix alignment regulator may contain selenium ions.
上記複合めっき材の製造方法において、前記銀マトリクス配向調整剤がセレノシアン酸カリウムであってもよい。 In the method for producing a composite plating material, the silver matrix alignment regulator may be potassium selenocyanate.
上記複合めっき材の製造方法において、前記銀マトリクス配向調整剤の濃度がセレンに換算して５〜２０ｍｇ／Ｌであってもよい。 In the method for producing a composite plating material, the concentration of the silver matrix alignment regulator may be 5 to 20 mg / L in terms of selenium.
上記複合めっき材の製造方法において、前記銀めっき液を用いて電流密度４Ａ／ｄｍ２以上の電気めっきを行うことによって、前記皮膜が形成されていてもよい。 In the method for producing a composite plating material, the coating may be formed by performing electroplating with a current density of 4 A / dm 2 or more using the silver plating solution.
上記複合めっき材の製造方法において、前記被めっき材上に形成された皮膜中の炭素粒子の含有量が０．６〜２．０質量％であってもよい。 In the method for producing a composite plating material, the content of carbon particles in the film formed on the material to be plated may be 0.6 to 2.0% by mass.
上記複合めっき材の製造方法において、前記被めっき材上に形成された皮膜表面における炭素粒子の面積占有率が５〜１９面積％であってもよい。 In the method for producing a composite plating material, the area occupation ratio of carbon particles on the surface of the film formed on the material to be plated may be 5 to 19 area%.
上記複合めっき材の製造方法において、前記被めっき材上に形成された皮膜の厚さが２〜１０μmであってもよい。 In the method for producing a composite plating material, a thickness of a film formed on the material to be plated may be 2 to 10 μm.
また、本発明によれば、銀層中に塊状の炭素粒子を含有する複合材からなる皮膜が被めっき材に形成された構成を有し、前記銀層の銀マトリクスが２２０配向に構成されていることを特徴とする、複合めっき材が提供される。 Further, according to the present invention, the silver layer has a configuration in which a film made of a composite material containing massive carbon particles is formed on the material to be plated, and the silver matrix of the silver layer is configured in 220 orientation. A composite plating material is provided.
本発明によれば、複合めっき材を製造する際に、被めっき材上に形成される複合めっき皮膜の耐摩耗性を高く維持したまま、電気めっき処理を行う際の電流密度を高くして生産性を向上させることができる。このようにして製造された複合めっき材は、例えばスイッチやコネクタなどの端子の高寿命化に十分に対応可能な材料として、使用することが可能である。 According to the present invention, when producing a composite plating material, while maintaining high wear resistance of the composite plating film formed on the material to be plated, the current density during the electroplating process is increased and produced. Can be improved. The composite plating material manufactured in this way can be used as a material that can sufficiently cope with the extension of the service life of terminals such as switches and connectors.
以下、図面を参照しながら、本発明の好適な実施形態について説明をする。なお、本明細書及び図面において、実質的に同一の機能構成を有する要素については、同一の符号を付することにより重複説明を省略する。 Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In the present specification and drawings, elements having substantially the same functional configuration are denoted by the same reference numerals, and redundant description is omitted.
図２は、本発明の実施の形態に係る製造方法の手順の一例を示すフロー図である。以下では、図２を用いて本発明の製造方法により、複合めっき材を製造する手順を説明する。 FIG. 2 is a flowchart showing an example of the procedure of the manufacturing method according to the embodiment of the present invention. Below, the procedure which manufactures a composite plating material with the manufacturing method of this invention using FIG. 2 is demonstrated.
（ステップ０）
複合めっき材の製造を開始する。
(Step 0)
Started production of composite plating materials.
（ステップ１）
塊状炭素粒子としての塊状黒鉛粒子を酸化処理する。なお、一般的な黒鉛の分類は図１のようになっている。この酸化処理により塊状黒鉛粒子の表面から脂肪酸炭化水素（アルカン、アルケン）及び芳香族炭化水素（アルキルベンゼン）等の親油性有機物を除去する。
(Step 1)
The massive graphite particles as the massive carbon particles are oxidized. The general classification of graphite is as shown in FIG. By this oxidation treatment, lipophilic organic substances such as fatty acid hydrocarbon (alkane, alkene) and aromatic hydrocarbon (alkylbenzene) are removed from the surface of the massive graphite particles.
塊状黒鉛粒子の酸化処理としては、例えばＯ２ガス等による乾式酸化処理方法又は湿式酸化処理方法を用いることができる。なお、乾式及び湿式の酸化処理方法以外の酸化処理方法を用いてもよい。好ましくは、表面積の大きい炭素粒子を均一に処理できると考えられる湿式酸化処理を用いて酸化処理を行う。 As the oxidation treatment of the massive graphite particles, for example, a dry oxidation method or a wet oxidation method using O 2 gas or the like can be used. An oxidation method other than the dry and wet oxidation methods may be used. Preferably, the oxidation treatment is performed using a wet oxidation treatment that is considered to be capable of uniformly treating carbon particles having a large surface area.
本実施の形態で用いる湿式酸化方法について説明する。まず、原料である塊状の炭素粒子を水中に懸濁させた後に、酸化剤を適量添加する。添加する酸化剤としては、例えば硝酸、過酸化水素、過マンガン酸カリウム、過硫酸カリウム又は過塩素酸ナトリウム等を用いることができる。添加された酸化剤により、炭素粒子に付着している親油性有機物が酸化されて水に溶けやすい形態になるために、これらの親油性有機物が炭素粒子表面から適宜除去されると考えられる。なお、酸化剤を用いて懸濁液内での除去を行った後に、この懸濁液を濾過して取出した炭素粒子を水洗することで、炭素粒子の表面からの親油性有機物の除去効果をさらに高めることができる。 The wet oxidation method used in this embodiment will be described. First, after suspending massive carbon particles as a raw material in water, an appropriate amount of an oxidizing agent is added. As the oxidizing agent to be added, for example, nitric acid, hydrogen peroxide, potassium permanganate, potassium persulfate, sodium perchlorate, or the like can be used. It is considered that these lipophilic organic substances are appropriately removed from the surface of the carbon particles because the added oxidant oxidizes the lipophilic organic substances adhering to the carbon particles and easily dissolves in water. After removing the suspension within the suspension using an oxidizing agent, the carbon particles taken out by filtering the suspension are washed with water, thereby removing the lipophilic organic matter from the surface of the carbon particles. It can be further increased.
上述したように酸化処理を行った後の炭素粒子は、３００℃に加熱した際に発生するガスに、アルカン、アルケンなどの親油性脂肪族炭化水素、及びアルキルベンゼン等の親油性芳香族炭化水素が含まれないことを特徴とする。炭素粒子を３００℃に加熱した際に発生するガスを分析する際には、例えば、パージアンドトラップ・ガスクロマトグラフ質量分析装置（日本分析工業ＪＨＳ−１００、島津 ＧＣＭＡＳ ＱＰ‐５０５０Ａ）を使用することができる。 As described above, the carbon particles after the oxidation treatment include lipophilic aliphatic hydrocarbons such as alkane and alkene, and lipophilic aromatic hydrocarbons such as alkylbenzene in the gas generated when heated to 300 ° C. It is not included. When analyzing the gas generated when the carbon particles are heated to 300 ° C., for example, a purge and trap gas chromatograph mass spectrometer (Nippon Analytical Industries JHS-100, Shimadzu GCMAS QP-5050A) may be used. it can.
なお、酸化処理後の炭素粒子に脂肪族炭化水素及び芳香族炭化水素が若干含まれている場合であっても、後述するステップ２の手順にて炭素粒子を複合めっき液に分散させる際に問題なく分散させることができるが、より適切に分散させるために、分子量１６０以上の上記炭化水素（脂肪族炭化水素及び芳香族炭化水素）が含まれていないようにするのが好ましい。さらに、酸化処理後の炭素粒子を３００℃以上に加熱した際に発生するガスのガス強度（パージアンドトラップ・ガスクロマトグラフ質量分析強度）が、分子量１６０未満の上記炭化水素（脂肪族炭化水素及び芳香族炭化水素）について５、０００、０００以下になっているのが好ましい。 Even if the carbon particles after the oxidation treatment contain some aliphatic hydrocarbons and aromatic hydrocarbons, there is a problem in dispersing the carbon particles in the composite plating solution in the procedure of Step 2 described later. However, in order to disperse more appropriately, it is preferable not to include the above hydrocarbons (aliphatic hydrocarbons and aromatic hydrocarbons) having a molecular weight of 160 or more. Further, the above-mentioned hydrocarbons (aliphatic hydrocarbons and aromatics) whose gas intensity (purge and trap gas chromatograph mass spectrometry intensity) generated when the oxidized carbon particles are heated to 300 ° C. or higher are less than 160 molecular weight. Group hydrocarbons) are preferably 5,000,000 or less.
上記酸化処理によって、炭素粒子が含有する脂肪酸炭化水素及び芳香族炭化水素の含有量を所定以下にすることによって、後述するステップ２の手順にて、界面活性剤を添加することなく、炭素粒子を複合めっき液中に均一に分散させることができる。これに対して、酸化処理後の炭素粒子に分子量の大きな炭化水素が含まれている場合には、炭素粒子の表面が親油性の強い炭化水素で被覆されて複合めっき溶液中の炭素粒子が互いに凝集し、炭素粒子がめっき皮膜中に複合化されなくなってしまう恐れがある。 By making the content of fatty acid hydrocarbons and aromatic hydrocarbons contained in the carbon particles below a predetermined level by the oxidation treatment, the carbon particles are added without adding a surfactant in the procedure of Step 2 described later. It can be uniformly dispersed in the composite plating solution. On the other hand, when the carbon particles after the oxidation treatment contain hydrocarbons having a large molecular weight, the carbon particles are coated with strongly lipophilic hydrocarbons so that the carbon particles in the composite plating solution are mutually bonded. Aggregation may cause the carbon particles to not be combined into the plating film.
（ステップ２）
酸化処理した塊状黒鉛粒子を複合めっき液としての銀めっき液に分散懸濁させる。複合めっき液としてはシアン銀めっき液を使用することが好ましく、特に、シアン銀カリウム及びシアン化カリウムからなるシアン系銀めっき液であることが好ましい。また、複合めっき液中での炭素粒子の濃度は４０〜１２０ｇ／Ｌであることが望ましい。これは、炭素粒子の濃度が４０ｇ／Ｌ未満である場合には、炭素粒子の複合化量が著しく低下してしまい、また、炭素粒子の濃度が１２０ｇ／Ｌを超える場合には、複合めっき液の粘度が増加し、撹拌が困難になってしまうからである。
(Step 2)
Oxidized massive graphite particles are dispersed and suspended in a silver plating solution as a composite plating solution. As the composite plating solution, a cyan silver plating solution is preferably used, and in particular, a cyan-based silver plating solution composed of potassium cyan silver and potassium cyanide is preferable. The concentration of carbon particles in the composite plating solution is preferably 40 to 120 g / L. This is because when the concentration of carbon particles is less than 40 g / L, the amount of carbon particles combined is significantly reduced, and when the concentration of carbon particles exceeds 120 g / L, a composite plating solution is used. This is because the viscosity of the resin increases and stirring becomes difficult.
（ステップ３）
塊状黒鉛粒子を分散させた銀めっき液中に、銀マトリクス配向調整剤を添加する。本実施の形態では、銀マトリクス配向調整剤としてＳｅ（セレン）イオンを含む調整剤を添加する。銀マトリクス配向方向はＳｅ（セレン）イオン濃度によって著しく変化するため、セレンイオンの添加濃度は５〜２０ｍｇ／Ｌであるのが望ましい。銀マトリックス配向調整剤を銀めっき液に添加すると、従来では１１１面に配向しているＡｇマトリクスの配向方向を変化させ、２２０面にすることができる。めっき皮膜は微細な結晶粒子からなり、その結晶粒子の成長方向によってその特性が大きく変化すると考えられ、複合化される炭素粒子の結晶方位と銀めっきマトリクスの結晶粒子の配向が最適な場合に、摩擦や摺動にともなう銀マトリクスの変形が容易になり、炭素粒子の潤滑性とあいまって、耐摩耗性が向上すると考えられる。
(Step 3)
A silver matrix alignment regulator is added to the silver plating solution in which massive graphite particles are dispersed. In the present embodiment, a regulator containing Se (selenium) ions is added as a silver matrix orientation regulator. Since the silver matrix alignment direction varies significantly depending on the Se (selenium) ion concentration, the addition concentration of selenium ions is preferably 5 to 20 mg / L. When a silver matrix alignment regulator is added to the silver plating solution, the orientation direction of the Ag matrix conventionally aligned in the 111 plane can be changed to 220 plane. The plating film is composed of fine crystal particles, and its characteristics are considered to vary greatly depending on the growth direction of the crystal particles. When the crystal orientation of the composited carbon particles and the orientation of the crystal particles of the silver plating matrix are optimal, It is considered that the silver matrix is easily deformed due to friction and sliding, and the wear resistance is improved in combination with the lubricity of the carbon particles.
（ステップ４）
銀めっき液を用いた電気めっきにより、被めっき材としての導体素材上に複合めっき皮膜を形成する。なお、電気めっきを行う際の電流密度の大きさを４Ａ／ｄｍ２以上にすると、生産効率を非常に向上させることができて好ましい。本実施の形態では、被めっき材として、例えば厚さ０．８ｍｍの銅板を用いている。また、この被めっき材には、めっき皮膜の密着性を向上させることを目的として、電気めっきを行う前に予め下地めっきを施しておいてもよい。下地めっきは、例えばＡｇストライクめっきであってよい。
(Step 4)
A composite plating film is formed on a conductor material as a material to be plated by electroplating using a silver plating solution. Note that it is preferable that the current density at the time of electroplating is 4 A / dm 2 or more because production efficiency can be greatly improved. In the present embodiment, a copper plate having a thickness of, for example, 0.8 mm is used as the material to be plated. In addition, for the purpose of improving the adhesion of the plating film, the material to be plated may be preliminarily plated before electroplating. The base plating may be, for example, Ag strike plating.
（ステップ５）
上記ステップ０〜ステップ１の手順により、被めっき材上に複合めっき皮膜が形成され、複合めっき材の製造が終了する。
(Step 5)
The composite plating film is formed on the material to be plated by the procedure from Step 0 to Step 1, and the production of the composite plating material is completed.
なお、本実施の形態で製造された複合めっき材では、銀層中に０．７〜２．０質量％の炭素粒子を含有する複合材が、複合めっき皮膜として被めっき材である導体素材の表面上に形成されている。また、複合めっき皮膜の表面における炭素粒子の面積占有率が５〜１８面積％になっている。なお、複合めっき皮膜の厚さは、２〜１０μｍにするのが好ましい。これは、複合めっき皮膜の厚さが２μｍ未満である場合には、耐摩耗性が不十分であり、複合めっき皮膜の厚さが１０μｍを越える場合には、生産効率が悪くなってしまうからである。 In the composite plating material manufactured in the present embodiment, the composite material containing 0.7 to 2.0% by mass of carbon particles in the silver layer is a conductor material that is a material to be plated as a composite plating film. It is formed on the surface. Moreover, the area occupation rate of the carbon particle in the surface of a composite plating film is 5-18 area%. The thickness of the composite plating film is preferably 2 to 10 μm. This is because the wear resistance is insufficient when the thickness of the composite plating film is less than 2 μm, and the production efficiency deteriorates when the thickness of the composite plating film exceeds 10 μm. is there.
以上の実施形態によれば、銀マトリクス配向調整剤を添加した、複合めっき液としての銀めっき液中に摺動材として分散させる炭素粒子を塊状とすることによって、電気めっきにより被めっき材上に複合めっき皮膜を形成する際に電流密度の大きさを上昇させて生産効率を向上させても、高い耐摩耗性の複合めっき皮膜を備えた複合めっき材を製造することが可能になる。特に、電気めっきの際の電流密度の大きさを従来よりも大きい値である４Ａ／ｄｍ２以上にした場合に、従来よりも高い耐摩耗性の複合めっき皮膜を備えた複合めっき材を製造することができる。また、銀マトリクス配向調整剤がセレンイオンを含むことにより、Ａｇマトリクスを耐摩耗性材料により適した２２０配向にする効果がある。 According to the above embodiment, the carbon particles dispersed as the sliding material in the silver plating solution as the composite plating solution to which the silver matrix alignment modifier is added are made into a lump shape, thereby being electroplated on the material to be plated. Even if the current density is increased when forming the composite plating film to improve the production efficiency, it is possible to produce a composite plating material having a high wear-resistant composite plating film. In particular, when the current density at the time of electroplating is set to 4 A / dm 2 or more, which is a larger value than before, a composite plating material having a composite plating film with higher wear resistance than the conventional one is manufactured. be able to. Further, when the silver matrix alignment regulator contains selenium ions, there is an effect that the Ag matrix is made into 220 alignment more suitable for the wear resistant material.
さらに、銀層中に０．６〜２．０質量％の炭素粒子を含有する複合材を、被めっき材である導体素材の表面上に複合めっき皮膜として形成したことによって、耐摩耗性向上の効果がある。めっき膜中の炭素粒子は質量％で０．７％、表面被覆率で５％未満となる場合耐摩耗性が低下すると考えられる。 Furthermore, the composite material containing 0.6 to 2.0% by mass of carbon particles in the silver layer is formed as a composite plating film on the surface of the conductor material that is the material to be plated, thereby improving the wear resistance. effective. When the carbon particles in the plating film are 0.7% by mass and the surface coverage is less than 5%, the wear resistance is considered to be lowered.
さらに、製造する複合めっき材の複合めっき皮膜の厚さを２〜１０μｍにしたことによって、複合めっき皮膜の耐摩耗性は充分に高く、且つ適度な厚さであるためにその生産効率を低下させる恐れがない。 Furthermore, since the thickness of the composite plating film of the composite plating material to be manufactured is 2 to 10 μm, the wear resistance of the composite plating film is sufficiently high and the thickness is moderate, so that the production efficiency is lowered. There is no fear.
以上、添付図面を参照しながら本発明の好適な実施形態について説明したが、本発明は係る例に限定されない。当業者であれば、特許請求の範囲に記載された技術的思想の範疇内において、各種の変更例又は修正例に想到し得ることは明らかであり、それらについても当然に本発明の技術的範囲に属するものと了解される。 As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, this invention is not limited to the example which concerns. It is obvious for those skilled in the art that various changes or modifications can be conceived within the scope of the technical idea described in the claims, and of course, the technical scope of the present invention is also possible. It is understood that it belongs to.
上述した実施形態では、銀マトリクス配向調整剤としてＫＳｅＣＮ（セレノシアン酸カリウム）を用いる場合について説明したが、銀マトリクス配向調整剤としてはＫＳｅＣＮ（セレノシアン酸カリウム）以外の材料を用いてもよい。 In the above-described embodiment, the case where KSeCN (potassium selenocyanate) is used as the silver matrix alignment regulator has been described. However, a material other than KSeCN (potassium selenocyanate) may be used as the silver matrix alignment regulator.
上述した実施形態では、被めっき材としての導体素材が厚さ０．８ｍｍの銅板である場合について説明したが、被めっき材は、その他の材料であってもよい。また、電気めっきを行う前に被めっき材に予め施す下地めっきがＡｇストライクめっきである場合について説明したが、Ａｇストライクめっき以外の下地めっきを用いてもよい。さらに、被めっき材に下地めっきを施さないで電気めっきを行ってもよい。 In the above-described embodiment, the case where the conductor material as the material to be plated is a copper plate having a thickness of 0.8 mm has been described, but the material to be plated may be other materials. Moreover, although the case where the base plating previously applied to the material to be plated before the electroplating is Ag strike plating has been described, base plating other than Ag strike plating may be used. Furthermore, electroplating may be performed without applying base plating to the material to be plated.
本発明を、実施例と比較例を用いて説明する。 The present invention will be described using examples and comparative examples.
以下の表1において、実施例１〜７の各データは本発明の製造方法を用いて製造した複合めっき材の各特性を示し、比較例１〜８の各データは従来公知の製造方法を用いて製造した複合めっき材の各特性を示している。 In the following Table 1, each data of Examples 1-7 shows each characteristic of the composite plating material manufactured using the manufacturing method of this invention, and each data of Comparative Examples 1-8 uses a conventionally well-known manufacturing method. Each characteristic of the composite plating material manufactured in this way is shown.
上記表１に示す各データの特性は、以下のようにして測定した。 The characteristics of each data shown in Table 1 were measured as follows.
＜複合めっき皮膜中の炭素粒子の含有量＞
被めっき材上に形成された複合めっき皮膜中の炭素粒子の含有量（質量％）は、以下のようにして測定した。製造した複合めっき材（被めっき材を含む）から試験片を切り出し、銀及び炭素の分析用にそれぞれ用意する。この試験片中の銀の含有量（Ｘ：質量）を、ＩＣＰ装置（ジャーレルアッシュ社製のＩＲＩＳ／ＡＲ）を用いてプラズマ分光分析法によって求めた。さらに、試験片中の炭素の含有量（Ｙ：質量）を、微量炭素・硫黄分析装置（堀場製作所製のＥＭＩＡ−Ｕ５１０）を用いて燃焼赤外線吸収法によって求めた。得られたＸ及びＹの値から複合めっき皮膜中の炭素粒子の含有量（質量％）をＹ／（Ｘ＋Ｙ）として算出した。
<Content of carbon particles in composite plating film>
The content (mass%) of carbon particles in the composite plating film formed on the material to be plated was measured as follows. A test piece is cut out from the manufactured composite plating material (including the material to be plated) and prepared for analysis of silver and carbon, respectively. The silver content (X: mass) in the test piece was determined by plasma spectroscopy using an ICP device (IRIS / AR manufactured by Jarrel Ash). Further, the carbon content (Y: mass) in the test piece was determined by a combustion infrared absorption method using a trace carbon / sulfur analyzer (EMIA-U510 manufactured by Horiba, Ltd.). The content (mass%) of carbon particles in the composite plating film was calculated as Y / (X + Y) from the obtained X and Y values.
＜複合めっき皮膜表面における炭素粒子の面積占有率＞
被めっき材上に形成された複合めっき皮膜の表面における炭素粒子の面積占有率（面積％）は、以下のようにして、製造した複合めっき材から切り出した試験片の表面観察することにより求めた。試験片の表面を超深度形状顕微鏡（キーエンス社製のＶＫ−８５００）により対物レンズ倍率１００倍で超深度画像として撮影し、この画像をＰＣ上で画像解析アプリケーション（ＳＣＩＯＮ ＣＯＲＰＯＲＡＴＩＯＮ社製のＳＣＩＯＮ ＩＭＡＧＥ）により解析する。具体的には、撮影した画像を白黒で取り込み、階調を二値化することにより銀部分と炭素粒子部分に分離した。画像全体のピクセル数（即ち、銀部分のピクセル数と炭素粒子部分のピクセル数とを合計したピクセル数）をＡ、炭素粒子部分のピクセル数をＢとして各々算出する。得られたＡ及びＢの値から複合めっき皮膜の表面における炭素粒子の面積占有率（面積％）をＢ／Ａとして算出した。
<Area occupancy of carbon particles on the composite plating film surface>
The area occupation ratio (area%) of carbon particles on the surface of the composite plating film formed on the material to be plated was determined by observing the surface of the test piece cut out from the manufactured composite plating material as follows. . The surface of the test piece was taken as an ultra-deep image with an ultra-deep shape microscope (VK-8500, manufactured by Keyence Corporation) at an objective lens magnification of 100 times, and this image was image-analyzed on a PC (SCION IMAGE, SCION IMAGE). Analyze by Specifically, the captured image was captured in black and white, and the gradation was binarized to separate the silver portion and the carbon particle portion. The number of pixels of the entire image (that is, the total number of pixels of the silver part and the number of pixels of the carbon particle part) is calculated as A, and the number of pixels of the carbon particle part is calculated as B. From the obtained values of A and B, the area occupancy (area%) of carbon particles on the surface of the composite plating film was calculated as B / A.
＜耐摩耗性＞
被めっき材上に形成された複合めっき皮膜の耐摩耗性は、図３に示すように、本発明又は従来公知の製造方法により製造した２つの複合めっき材１０、１１を用いて測定した。これら２つの複合めっき材１０、１１のうちの一方（１０）を評価資料として固定し、他方（１１）をこの評価資料１０に一定の荷重で押当てた状態で図３の両矢印１２で示す摺動方向に所定の摺動距離を往復移動させ、両者（１０、１１）を継続的に摺動させた。この摺動によって評価資料である複合めっき材１０の被めっき材が露出した摺動回数（万回）を測定し、その測定値を耐摩耗性とした。図３に示すように、圧子１０には、曲率半径がＲ３ｍｍである湾曲部がインデント加工により形成されており、この湾曲部を評価資料１０と摺動させるようになっている。なお、圧子１１を評価資料１０に押当てる際の荷重を０．５Ｎとした。また、圧子１０を往復移動させる際の摺動距離を１０ｍｍ、摺動速度２．５Ｈｚとした。
<Abrasion resistance>
As shown in FIG. 3, the wear resistance of the composite plating film formed on the material to be plated was measured using two
次に、上記表１に示す各データ（実施例１〜７及び比較例１〜８）について、複合めっき材を製造した際の各条件について説明する。 Next, for each data (Examples 1 to 7 and Comparative Examples 1 to 8) shown in Table 1 above, each condition when the composite plating material is manufactured will be described.
[実施例１]
複合めっき皮膜に用いる炭素粒子としては、平均粒径３μmの塊状黒鉛粒子（エスイーシー社製のカーボンＳＧＬ−３）を用いた。また、酸化剤としては過硫酸カリウムを用いた。この炭素粒子を３Ｌの純水に混合し、炭素粒子が純水の６質量％になるようにした。なお、炭素粒子が純水の１〜２０質量％の範囲になるようにするのが望ましい。この混合溶液を攪拌しながら昇温した。この場合には、酸化剤として過硫酸カリウムを用いているため、混合溶液の温度を５０℃に設定した。その後、０．１ｍｏｌ／Ｌの過硫酸カリウム水溶液１．２Ｌを徐々に滴下し、滴下後２時間の間、攪拌を維持した。２時間経過後、ろ紙によりろ別を行い、分離した炭素粒子の水洗を行った。
[Example 1]
As the carbon particles used for the composite plating film, massive graphite particles having an average particle diameter of 3 μm (carbon SGL-3 manufactured by ESC Corporation) were used. Further, potassium persulfate was used as the oxidizing agent. The carbon particles were mixed with 3 L of pure water so that the carbon particles became 6% by mass of pure water. It is desirable that the carbon particles be in the range of 1 to 20% by mass of pure water. The mixed solution was heated while stirring. In this case, since potassium persulfate was used as the oxidizing agent, the temperature of the mixed solution was set to 50 ° C. Thereafter, 1.2 L of a 0.1 mol / L potassium persulfate aqueous solution was gradually added dropwise, and stirring was maintained for 2 hours after the addition. After the elapse of 2 hours, it was filtered off with filter paper, and the separated carbon particles were washed with water.
上記の酸化処理の操作によって、炭素粒子に付着していたノナン、デカン、３−メチル−２−ヘプテン等の親油性脂肪族炭化水素及び、キシレン等の親油性芳香族炭化水素が除去され、水分散性の良い炭素粒子が得られた。この炭素粒子に付着していた親油性脂肪族炭化水素及び、親油性芳香族炭化水素の分析については、３００℃に加熱し発生したガスの分析を行った。分析には、パージアンドトラップ・ガスクロマトグラフ質量分析装置：日本分析工業ＪＨＳ−１００、島津 ＧＣＭＡＳ
ＱＰ−５０５０Ａを使用した。
By the above oxidation treatment, lipophilic aliphatic hydrocarbons such as nonane, decane and 3-methyl-2-heptene and lipophilic aromatic hydrocarbons such as xylene adhering to the carbon particles are removed, and water is removed. Carbon particles with good dispersibility were obtained. For the analysis of the lipophilic aliphatic hydrocarbon and the lipophilic aromatic hydrocarbon adhering to the carbon particles, the gas generated by heating to 300 ° C. was analyzed. For analysis, purge and trap gas chromatograph mass spectrometer: Nippon Analytical Industry JHS-100, Shimadzu GCMAS
QP-5050A was used.
上述したように酸化処理した炭素粒子を、シアン銀カリウムが２８０ｇ／Ｌ、シアン化カリウムが９０ｇ／Ｌからなり、銀／遊離シアンモル比が１．０１であるシアン銀めっき液中に８０ｇ／Ｌとなるように分散懸濁させた。次に銀マトリクス配向調整剤としてのＫＳｅＣＮを、Ｓｅイオンに換算して１２ｍｇ／Ｌ添加し、銀−炭素粒子複合めっき液を作成した。 The carbon particles oxidized as described above are 80 g / L in a cyan silver plating solution containing 280 g / L of cyanogen potassium and 90 g / L of potassium cyanide and a silver / free cyan molar ratio of 1.01. To be dispersed and suspended. Next, 12 mg / L of KSeCN as a silver matrix alignment regulator was added in terms of Se ions, and a silver-carbon particle composite plating solution was prepared.
被めっき材としては、厚さ０．８ｍｍの銅板を用いた。尚、めっき膜の密着性を向上させるため、下地めっきとして、Ａｇストライクめっきを予め行った。この際のＡｇストライクめっき浴の組成は、シアン銀カリウムを３ｇ／Ｌ、シアン化カリウムを１００ｇ／Ｌとした。ストライクめっきは、温度を２５℃、電流密度を３Ａ／ｄｍ２に設定して実施した。前述の銀−炭素粒子複合めっき液を用い、前述の前処理を行った銅板に対して、温度を２５℃、電流密度を６Ａ／ｄｍ２に設定して電気めっきを行い、銀−炭素粒子複合めっき材を作成した。作成した複合めっき材の複合めっき皮膜の膜厚は５μｍとした。 A copper plate having a thickness of 0.8 mm was used as the material to be plated. In addition, in order to improve the adhesiveness of a plating film, Ag strike plating was performed beforehand as base plating. The composition of the Ag strike plating bath at this time was 3 g / L for cyanogen silver potassium and 100 g / L for potassium cyanide. The strike plating was performed with the temperature set at 25 ° C. and the current density set at 3 A / dm 2 . Using the silver-carbon particle composite plating solution described above, electroplating is performed on the copper plate that has been subjected to the above-described pretreatment at a temperature of 25 ° C. and a current density of 6 A / dm 2 , thereby producing a silver-carbon particle composite. A plating material was created. The film thickness of the composite plating film of the prepared composite plating material was 5 μm.
複合めっき皮膜中の炭素粒子の含有量は、１．８質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、１５面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数については、５０万回以上の摺動回数を超えても評価試料の複合めっき材は露出しなかった。 The carbon particle content in the composite plating film was 1.8% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 15 area%. Furthermore, the composite plating material of the evaluation sample was not exposed even when the number of sliding times (until exposure) showing wear resistance exceeded the number of sliding times of 500,000 times or more.
[実施例２]
電気めっきを行う際に電流密度を９Ａ／ｄｍ２に設定して電気めっきを行ったこと以外は、実施例１と同じ条件及び手順で複合めっき材を製造した。なお、膜厚は実施例１と同様に５μｍとした。複合めっき皮膜中の炭素粒子の含有量は、１．７質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、１３面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数については、５０万回以上の摺動回数を超えても評価資料の複合めっき材は露出しなかった。
[Example 2]
A composite plating material was produced under the same conditions and procedures as in Example 1 except that the electroplating was performed with the current density set to 9 A / dm 2 when electroplating. The film thickness was 5 μm as in Example 1. The carbon particle content in the composite plating film was 1.7% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 13 area%. Further, regarding the number of sliding times (until exposure) showing wear resistance, the composite plating material of the evaluation material was not exposed even when the number of sliding times exceeded 500,000 times.
[実施例３]
複合めっき皮膜に用いる炭素粒子として平均粒径５μmの塊状黒鉛粒子（エスイーシー社製のカーボンＳＧＬ−５）を用いたこと以外は、実施例１と同じ条件及び手順で、複合めっき材を製造した。なお、膜厚は実施例１と同様に５μｍとした。複合めっき皮膜中の炭素粒子の含有量は、１．３質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、９面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数については、５０万回以上の摺動回数を超えても評価資料の複合めっき材は露出しなかった。
[Example 3]
A composite plating material was produced under the same conditions and procedures as in Example 1 except that massive graphite particles having an average particle diameter of 5 μm (carbon SGL-5 manufactured by ESC Corporation) were used as carbon particles used in the composite plating film. The film thickness was 5 μm as in Example 1. The carbon particle content in the composite plating film was 1.3% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 9 area%. Further, regarding the number of sliding times (until exposure) showing wear resistance, the composite plating material of the evaluation material was not exposed even when the number of sliding times exceeded 500,000 times.
[実施例４]
複合めっき皮膜に用いる炭素粒子として平均粒径５μmの塊状黒鉛粒子（エスイーシー社製のカーボンＳＧＬ−５）を用いたことと、電気めっきを行う際に電流密度を９Ａ／ｄｍ２に設定して電気めっきを行ったこと以外は、実施例１と同じ条件及び手順で複合めっき材を製造した。なお、膜厚は実施例１と同様に５μｍとした。複合めっき皮膜中の炭素粒子の含有量は、１．２質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、９面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数は、５０万回以上であった。
[Example 4]
As the carbon particles used for the composite plating film, massive graphite particles having an average particle size of 5 μm (carbon SGL-5 manufactured by ESC Corporation) were used, and the current density was set to 9 A / dm 2 when electroplating. A composite plating material was produced under the same conditions and procedures as in Example 1 except that plating was performed. The film thickness was 5 μm as in Example 1. The carbon particle content in the composite plating film was 1.2% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 9 area%. Furthermore, the number of sliding operations (until exposure) showing wear resistance was 500,000 times or more.
[実施例５]
複合めっき皮膜に用いる炭素粒子として平均粒径１２μmの塊状黒鉛粒子（エスイーシー社製のカーボンＳＧＬ−１２）を用いたこと以外は、実施例１と同じ条件及び手順で複合めっき材を製造した。なお、膜厚は実施例１と同様に５μｍとした。複合めっき皮膜中の炭素粒子の含有量は、０．８質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、６面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数は、５０万回以上であった。
[Example 5]
A composite plating material was produced under the same conditions and procedures as in Example 1 except that massive graphite particles having an average particle size of 12 μm (carbon SGL-12 manufactured by ESC Corporation) were used as the carbon particles used in the composite plating film. The film thickness was 5 μm as in Example 1. The carbon particle content in the composite plating film was 0.8% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 6 area%. Furthermore, the number of sliding operations (until exposure) showing wear resistance was 500,000 times or more.
[実施例６]
複合めっき皮膜に用いる炭素粒子として平均粒径１２μmの塊状黒鉛粒子（エスイーシー社製のカーボンＳＧＬ−１２）を用いたことと、電気めっきを行う際に電流密度を９Ａ／ｄｍ２に設定して電気めっきを行ったこと以外は、実施例１と同じ条件及び手順で複合めっき材を製造した。なお、膜厚は実施例１と同様に５μｍとした。複合めっき皮膜中の炭素粒子の含有量は、０．７質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、５面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数は、５０万回以上であった。
[Example 6]
As the carbon particles used for the composite plating film, massive graphite particles having an average particle diameter of 12 μm (carbon SGL-12 manufactured by ESC Corporation) were used, and the current density was set to 9 A / dm 2 when electroplating. A composite plating material was produced under the same conditions and procedures as in Example 1 except that plating was performed. The film thickness was 5 μm as in Example 1. The carbon particle content in the composite plating film was 0.7% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 5 area%. Furthermore, the number of sliding operations (until exposure) showing wear resistance was 500,000 times or more.
[実施例７]
複合めっき皮膜に用いる炭素粒子として平均粒径５μmの塊状黒鉛粒子（エスイーシー社製のカーボンＳＧＬ−５）を用いたことと、膜厚を３μｍとしたこと以外は、実施例１と同じ条件及び手順で複合めっき材を製造した。複合めっき皮膜中の炭素粒子の含有量は、０．６質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、６面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数は、５０万回以上であった。
[Example 7]
The same conditions and procedure as in Example 1 except that massive graphite particles having an average particle size of 5 μm (carbon SGL-5 manufactured by ESC Corporation) were used as the carbon particles used in the composite plating film, and the film thickness was 3 μm. The composite plating material was manufactured. The carbon particle content in the composite plating film was 0.6% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 6 area%. Furthermore, the number of sliding operations (until exposure) showing wear resistance was 500,000 times or more.
[比較例１]
複合めっき皮膜に用いる炭素粒子として平均粒径５μmの鱗片状黒鉛粒子（エスイーシー社製のカーボンＳＮＯ−５）を用いて実施例１と概ね同様の条件及び手順で複合めっき材を製造した。但し、酸化処理した炭素粒子を銀めっき液に分散懸濁させる際には、シアン銀カリウムが１００ｇ／Ｌ、シアン化カリウムが１２０ｇ／Ｌからなり、銀／遊離シアンモル比が０．２７であるシアン銀めっき液中に８０ｇ／Ｌとなるように分散懸濁させた。その後、銀マトリクス配向調整剤としてのＫＳｅＣＮを、Ｓｅイオンに換算して４ｍｇ／Ｌ添加し、銀−炭素粒子複合めっき液を作成した。また、電気めっきを行う際に電流密度を３Ａ／ｄｍ２に設定して電気めっきを行った。
[Comparative Example 1]
A composite plating material was produced under substantially the same conditions and procedures as in Example 1 using scaly graphite particles (carbon SNO-5 manufactured by ESC Corporation) having an average particle size of 5 μm as carbon particles used in the composite plating film. However, when dispersing and suspending the oxidized carbon particles in the silver plating solution, cyan silver plating comprising 100 g / L of cyan cyan potassium and 120 g / L of potassium cyanide and a silver / free cyan molar ratio of 0.27. It was dispersed and suspended in the liquid at 80 g / L. Thereafter, 4 mg / L of KSeCN as a silver matrix alignment regulator was added in terms of Se ions to prepare a silver-carbon particle composite plating solution. Moreover, when performing electroplating, the current density was set to 3 A / dm 2 and electroplating was performed.
複合めっき皮膜中の炭素粒子の含有量は、１．７質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、２２面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数については、４８万回程度であった。 The carbon particle content in the composite plating film was 1.7% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 22 area%. Furthermore, the number of sliding operations (until exposure) showing wear resistance was about 480,000 times.
[比較例２]
電気めっきを行う際に電流密度を６Ａ／ｄｍ２に設定して電気めっきを行ったこと以外は、比較例１と同じ条件及び手順で、複合めっき材を製造した。複合めっき皮膜中の炭素粒子の含有量は、１．１質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、１９面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数は、１３万回程度であった。
[Comparative Example 2]
A composite plating material was produced under the same conditions and procedures as in Comparative Example 1 except that the electroplating was performed by setting the current density to 6 A / dm 2 when electroplating. The carbon particle content in the composite plating film was 1.1% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 19 area%. Furthermore, the number of sliding operations (until exposure) showing wear resistance was about 130,000 times.
[比較例３]
複合めっき皮膜に用いる炭素粒子として平均粒径５μmの鱗片状黒鉛粒子（エスイーシー社製のカーボンＳＮＯ−５）を用いたことと、電気めっきを行う際に電流密度を３Ａ／ｄｍ２に設定して電気めっきを行ったこと以外は、実施例１と同じ条件及び手順で、複合めっき材を製造した。複合めっき皮膜中の炭素粒子の含有量は、２．５質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、３４面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数は、５０万回以上であった。
[Comparative Example 3]
The scale-like graphite particles having an average particle size of 5 μm (carbon SNO-5 manufactured by ESC Corporation) were used as the carbon particles used in the composite plating film, and the current density was set to 3 A / dm 2 when performing electroplating. A composite plating material was produced under the same conditions and procedures as in Example 1 except that electroplating was performed. The carbon particle content in the composite plating film was 2.5% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 34 area%. Furthermore, the number of sliding operations (until exposure) showing wear resistance was 500,000 times or more.
[比較例４]
複合めっき皮膜に用いる炭素粒子として平均粒径５μmの鱗片状黒鉛粒子（エスイーシー社製のカーボンＳＮＯ−５）を用いたこと以外は、実施例１と概ね同様の条件及び手順で複合めっき材を製造した。複合めっき皮膜中の炭素粒子の含有量は、１．５質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、２５面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数については、９万回程度であった。
[Comparative Example 4]
A composite plating material is produced under substantially the same conditions and procedures as in Example 1 except that scaly graphite particles having an average particle diameter of 5 μm (carbon SNO-5 manufactured by ESC Corporation) are used as carbon particles used in the composite plating film. did. The carbon particle content in the composite plating film was 1.5% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 25 area%. Furthermore, the number of sliding operations (until exposure) showing wear resistance was about 90,000 times.
[比較例５]
電気めっきを行う際に電流密度を３Ａ／ｄｍ２に設定して電気めっきを行ったこと以外は、実施例１と同じ条件及び手順で、複合めっき材を製造した。複合めっき皮膜中の炭素粒子の含有量は、１．６質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、１６面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数は、２８万回程度であった。
[比較例６]
複合めっき皮膜に用いる炭素粒子として平均粒径５μmの塊状黒鉛粒子（エスイーシー社製のカーボンＳＧＬ−５）を用いたことと、電気めっきを行う際に電流密度を３Ａ／ｄｍ２に設定して電気めっきを行ったこと以外は、実施例１と同じ条件及び手順で複合めっき材を製造した。複合めっき皮膜中の炭素粒子の含有量は、１.１質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、１８面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数は、１５万回程度であった。
[Comparative Example 5]
A composite plating material was produced under the same conditions and procedures as in Example 1 except that the electroplating was performed with the current density set to 3 A / dm 2 when electroplating. The carbon particle content in the composite plating film was 1.6% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 16 area%. Furthermore, the number of sliding operations (until exposure) showing wear resistance was about 280,000 times.
[Comparative Example 6]
The use of massive graphite particles (carbon SGL-5 manufactured by ESC Corporation) having an average particle size of 5 μm as carbon particles used in the composite plating film, and the current density was set to 3 A / dm 2 when electroplating. A composite plating material was produced under the same conditions and procedures as in Example 1 except that plating was performed. The content of carbon particles in the composite plating film was 1.1% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 18 area%. Further, the number of sliding operations (until exposure) showing wear resistance was about 150,000 times.
[比較例７]
複合めっき皮膜に用いる炭素粒子として平均粒径１２μmの塊状黒鉛粒子（エスイーシー社製のカーボンＳＧＬ−１２）を用いたことと、電気めっきを行う際に電流密度を３Ａ／ｄｍ２に設定して電気めっきを行ったこと以外は、実施例１と同じ条件及び手順で複合めっき材を製造した。複合めっき皮膜中の炭素粒子の含有量は、０.６質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、１９面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数は、６万回程度であった。
[Comparative Example 7]
The use of massive graphite particles having an average particle size of 12 μm (carbon SGL-12 manufactured by ESC Corporation) as the carbon particles used in the composite plating film, and the current density was set to 3 A / dm 2 when electroplating. A composite plating material was produced under the same conditions and procedures as in Example 1 except that plating was performed. The carbon particle content in the composite plating film was 0.6% by mass. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 19 area%. Further, the number of sliding operations (until exposure) showing wear resistance was about 60,000 times.
[比較例８]
複合めっき皮膜に用いる炭素粒子として平均粒径５μmの塊状黒鉛粒子（エスイーシー社製のカーボンＳＧＬ−５）を用いて比較例１と概ね同様の条件及び手順で複合めっき材を製造した。但し、銀マトリクス配向調整剤としてのＫＳｅＣＮを添加せず、銀−炭素粒子複合めっき液を作成した。また、電気めっきを行う際に電流密度を６Ａ／ｄｍ２に設定して電気めっきを行った。複合めっき皮膜中の炭素粒子の含有量は、０．０質量％であった。また、複合めっき皮膜表面における炭素粒子の面積占有率は、５面積％であった。さらに、耐摩耗性を示す（露出までの）摺動回数は、１万回程度であった。
[Comparative Example 8]
A composite plating material was produced under substantially the same conditions and procedures as in Comparative Example 1 using massive graphite particles (carbon SGL-5 manufactured by ESC Corporation) having an average particle size of 5 μm as carbon particles used for the composite plating film. However, a silver-carbon particle composite plating solution was prepared without adding KSeCN as a silver matrix alignment regulator. Moreover, when performing electroplating, the current density was set to 6 A / dm 2 and electroplating was performed. Content of the carbon particle in a composite plating film was 0.0 mass%. Moreover, the area occupation rate of the carbon particle in the composite plating film surface was 5 area%. Furthermore, the number of sliding operations (until exposure) showing wear resistance was about 10,000 times.
上記表１の比較例１〜８のデータが示すように、従来公知の複合めっき製造技術を用いて複合めっき材を製造する際に、電気めっきする際の電流密度を３Ａ／ｄｍ２から例えば６Ａ／ｄｍ２に上昇させ、複合めっき材の生産効率を向上させると、製造される複合めっき材の耐摩耗性を示す（露出までの）摺動回数はいずれも非常に低下し、製造される複合めっき材の耐摩耗性が低下してしまっている。これに対して、上記表１の実施例１〜７のデータが示すように本発明の製造方法を用いて複合めっき材を製造した場合には、電気めっきする際の電流密度を３Ａ／ｄｍ２から例えば６Ａ／ｄｍ２又は９Ａ／ｄｍ２に上昇させ、複合めっき材の生産効率を向上させた場合において、耐摩耗性を示す（露出までの）摺動回数が５０万回以上であり、耐摩耗性が非常に優れた複合めっき材を製造することができている。即ち、本発明によれば、複合めっき材を製造する際に、被めっき材上に形成される複合めっき皮膜の耐摩耗性を高く維持したまま、電気めっき処理を行う際の電流密度を高くして生産性を向上させることができていることが分かる。 As shown in the data of Comparative Examples 1 to 8 in Table 1 above, when a composite plating material is manufactured using a conventionally known composite plating manufacturing technique, the current density at the time of electroplating is reduced from 3 A / dm 2 to, for example, 6 A. / Dm 2 to improve the production efficiency of the composite plating material, the number of sliding times (until the exposure) showing the wear resistance of the composite plating material to be produced is greatly reduced. The wear resistance of the plating material has deteriorated. On the other hand, when the composite plating material was manufactured using the manufacturing method of the present invention as shown in the data of Examples 1 to 7 in Table 1, the current density at the time of electroplating was 3 A / dm 2. For example, when the production efficiency of the composite plating material is improved by increasing to 6 A / dm 2 or 9 A / dm 2 , the number of sliding operations (until exposure) is 500,000 times or more, A composite plating material having very excellent wearability can be produced. That is, according to the present invention, when producing a composite plating material, the current density during the electroplating process is increased while maintaining the high wear resistance of the composite plating film formed on the material to be plated. It can be seen that productivity can be improved.
本発明は、例えばスイッチやコネクタなどの接点や端子部品などの材料として使用される銀めっき材に特に有用である。 The present invention is particularly useful for a silver plating material used as a material for contacts and terminal components such as switches and connectors.
１０ 評価試料としての複合めっき材
１１ 圧子としての複合めっき材
１２ 摺動方向
10 Composite Plating Material as
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| JP2012162775A (en) * | 2011-02-08 | 2012-08-30 | Dowa Metaltech Kk | Silver plated material and method for manufacturing the same |
| JP2013189681A (en) * | 2012-03-14 | 2013-09-26 | Dowa Metaltech Kk | Silver plating material |
| JP2013189680A (en) * | 2012-03-14 | 2013-09-26 | Dowa Metaltech Kk | Silver plating material |
| JP2016166396A (en) * | 2015-03-10 | 2016-09-15 | 三菱マテリアル株式会社 | Copper terminal material with silver platting and terminal |
| JP2017190473A (en) * | 2016-04-11 | 2017-10-19 | 新日鐵住金株式会社 | Slide member, method for producing slide member and plating solution for producing slide member |
| CN109881222A (en) * | 2015-01-30 | 2019-06-14 | 同和金属技术有限公司 | Silver coating material and its manufacturing method |
| JP7341871B2 (en) | 2019-11-28 | 2023-09-11 | Ｄｏｗａメタルテック株式会社 | Composite plating material and its manufacturing method |
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| JP2016166396A (en) * | 2015-03-10 | 2016-09-15 | 三菱マテリアル株式会社 | Copper terminal material with silver platting and terminal |
| JP2017190473A (en) * | 2016-04-11 | 2017-10-19 | 新日鐵住金株式会社 | Slide member, method for producing slide member and plating solution for producing slide member |
| JP7341871B2 (en) | 2019-11-28 | 2023-09-11 | Ｄｏｗａメタルテック株式会社 | Composite plating material and its manufacturing method |
| JP7458800B2 (en) | 2020-01-30 | 2024-04-01 | Ｄｏｗａメタルテック株式会社 | Composite plating material and its manufacturing method |
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