JP2021025133A - Composite plated material and method for producing the same - Google Patents
Composite plated material and method for producing the same Download PDFInfo
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本発明は、複合めっき材およびその製造方法に関し、特に、スイッチやコネクタなどの摺動接点部品などの材料として使用される複合めっき材およびその製造方法に関する。 The present invention relates to a composite plating material and a method for manufacturing the same, and more particularly to a composite plating material used as a material for sliding contact parts such as switches and connectors, and a method for manufacturing the same.
従来、スイッチやコネクタなどの摺動接点部品などの材料として、摺動過程における加熱による銅や銅合金などの導体素材の酸化を防止するために、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。 Conventionally, as a material for sliding contact parts such as switches and connectors, a silver-plated material in which the conductor material is silver-plated in order to prevent oxidation of the conductor material such as copper or copper alloy due to heating in the sliding process has been used. It is used.
しかし、銀めっきは、軟質で摩耗し易く、一般に摩擦係数が高いため、摺動により剥離し易いという問題がある。この問題を解消するため、耐熱性、磨耗性、潤滑性などに優れた黒鉛やカーボンブラックなどの炭素粒子のうち、黒鉛粒子を銀マトリクス中に分散させた複合材の皮膜を電気めっきにより導体素材上に形成して耐摩耗性を向上させる方法が提案されている（例えば、特許文献１参照）。また、黒鉛粒子の分散に適した湿潤剤が添加されためっき浴を使用することにより、黒鉛粒子を含む銀めっき皮膜を製造する方法が提案されている（例えば、特許文献２参照）。さらに、ゾル−ゲル法によって炭素粒子を金属酸化物などでコーティングして、銀と炭素粒子の複合めっき液中における炭素粒子の分散性を高め、めっき皮膜中に複合化する炭素粒子の量を増大する方法が提案されている（例えば、特許文献３参照）。 However, silver plating is soft and easily worn, and generally has a high friction coefficient, so that there is a problem that it is easily peeled off by sliding. In order to solve this problem, among carbon particles such as graphite and carbon black, which have excellent heat resistance, wear resistance, lubricity, etc., a composite material film in which graphite particles are dispersed in a silver matrix is electroplated to form a conductor material. A method of forming on top to improve wear resistance has been proposed (see, for example, Patent Document 1). Further, a method of producing a silver plating film containing graphite particles by using a plating bath to which a wetting agent suitable for dispersing graphite particles is added has been proposed (see, for example, Patent Document 2). Furthermore, the carbon particles are coated with a metal oxide or the like by the sol-gel method to improve the dispersibility of the carbon particles in the composite plating solution of silver and carbon particles, and increase the amount of carbon particles to be composited in the plating film. A method has been proposed (see, for example, Patent Document 3).
しかし、特許文献１〜３の方法により製造された複合めっき材は、摩擦係数が比較的高く、接点や端子の高寿命化に対応することができないという問題があり、特許文献１〜３の方法により製造された複合めっき材よりも炭素粒子の含有量や表面の炭素粒子が占める割合を増大させて、さらに優れた耐摩耗性の複合めっき材を提供することが望まれている。 However, the composite plating material produced by the methods of Patent Documents 1 to 3 has a problem that the friction coefficient is relatively high and it is not possible to cope with the extension of the life of contacts and terminals. It is desired to provide a composite plating material having even better wear resistance by increasing the content of carbon particles and the proportion of carbon particles on the surface as compared with the composite plating material produced by.
このような複合めっき材を製造する方法として、酸化処理を行った炭素粒子を添加したシアン系銀めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子を含有する複合材からなる皮膜を素材上に形成する方法（例えば、特許文献４参照）、酸化処理を行った後にシランカップリング処理を施した炭素粒子を硝酸銀と硝酸アンモニウムを含む銀めっき液に添加した複合めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子を含む複合材からなる皮膜を素材上に形成する方法（例えば、特許文献５参照）などが提案されている。 As a method for producing such a composite plating material, an oxidation-treated carbon particle-added cyan-based silver plating solution is used for electroplating to perform electroplating from the composite material containing carbon particles in the silver layer. A method of forming a film on a material (see, for example, Patent Document 4), using a composite plating solution in which carbon particles subjected to silane coupling treatment after oxidation treatment are added to a silver plating solution containing silver nitrate and ammonium nitrate. Then, a method of forming a film made of a composite material containing carbon particles in the silver layer on the material by performing electroplating (see, for example, Patent Document 5) has been proposed.
しかし、特許文献４の方法により製造した複合めっき材をスイッチやコネクタなどの摺動接点部品などの材料として使用すると、複合めっき材をプレス加工する際に、表層の炭素粒子が脱落して、プレス油に混入することにより設備を汚す可能性があり、また、脱落した炭素粒子により、（その摺動接点部品などを使用した）電子機器の短絡が生じる可能性がある。 However, when the composite plating material manufactured by the method of Patent Document 4 is used as a material for sliding contact parts such as switches and connectors, carbon particles on the surface layer fall off when the composite plating material is pressed, and the press is performed. Mixing with oil can contaminate equipment, and shed carbon particles can cause short circuits in electronic equipment (using its sliding contact components, etc.).
また、特許文献５の方法では、複合めっき材の複合めっき皮膜上にさらに銀めっき皮膜を形成する必要があり、製造コストが高くなる。また、複合めっき皮膜上に形成した銀めっき皮膜が剥離して、電子機器の短絡が生じる可能性がある。また、銀めっき皮膜の剥離により、露出した炭素粒子が脱落して、プレス油に混入することにより設備を汚す可能性がある。 Further, in the method of Patent Document 5, it is necessary to further form a silver plating film on the composite plating film of the composite plating material, which increases the manufacturing cost. In addition, the silver plating film formed on the composite plating film may peel off, causing a short circuit in the electronic device. In addition, the peeling of the silver plating film may cause the exposed carbon particles to fall off and be mixed with the press oil to contaminate the equipment.
したがって、本発明は、このような従来の問題点に鑑み、銀層中に炭素粒子を含有する複合材からなる複合めっき皮膜が素材上に形成された複合めっき材において、複合めっき皮膜中の炭素粒子の脱落が少ない複合めっき材およびその製造方法を提供することを目的とする。 Therefore, in view of such conventional problems, the present invention relates to a composite plating material in which a composite plating film made of a composite material containing carbon particles in the silver layer is formed on the material, and carbon in the composite plating film. An object of the present invention is to provide a composite plating material in which particles are less likely to fall off and a method for producing the same.
本発明者らは、上記課題を解決するために鋭意研究した結果、炭素粒子を添加した銀めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子を含有する複合材からなる複合めっき皮膜を素材上に形成した後、表面の炭素粒子の一部を除去する処理を行うことにより、銀層中に炭素粒子を含有する複合材からなる複合めっき皮膜が素材上に形成された複合めっき材において、複合めっき皮膜中の炭素粒子の脱落が少ない複合めっき材を製造す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 diligent research to solve the above problems, the present inventors have made a composite material containing carbon particles in the silver layer by performing electroplating using a silver plating solution to which carbon particles are added. After forming the composite plating film on the material, a treatment for removing a part of the carbon particles on the surface was performed to form a composite plating film composed of the composite material containing carbon particles in the silver layer on the material. We have found that it is possible to produce a composite plating material in which carbon particles in the composite plating film are less likely to fall off, and have completed the present invention.
すなわち、本発明による複合めっき材の製造方法は、炭素粒子を添加した銀めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子を含有する複合材からなる複合めっき皮膜を素材上に形成した後、表面の炭素粒子の一部を除去する処理を行うことを特徴とする。 That is, in the method for producing a composite plating material according to the present invention, a composite plating film made of a composite material containing carbon particles in a silver layer is used as a material by performing electroplating using a silver plating solution to which carbon particles are added. After being formed on the surface, a treatment for removing a part of carbon particles on the surface is performed.
この複合めっき材の製造方法において、炭素粒子の一部を除去する処理が、複合めっき皮膜の表面を超音波洗浄または電解洗浄する処理であるのが好ましい。この場合、超音波洗浄が２０〜１００ｋＨｚで１〜３００秒間行われるのが好ましく、電解洗浄が１〜３０Ａ／ｄｍ２で１０〜３００秒間行われるのが好ましい。また、表面の炭素粒子の一部を除去する処理による炭素粒子の除去率が、２０〜７５面積％であるのが好ましく、炭素粒子が、平均粒径１〜１５μｍのグラファイト粒子であるのが好ましい。また、銀めっき液がスルホン酸系銀めっき液であるのが好ましく、銀めっき液に添加する炭素粒子の量が１０〜１００ｇ／Ｌであるのが好ましく、電気めっきが電流密度０．５〜１０Ａ／ｄｍ２で行われるのが好ましい。また、素材が銅または銅合金からなるのが好ましい。さらに、複合材からなる皮膜を形成する前に、素材上にニッケルめっき皮膜を形成するのが好ましい。 In this method for producing a composite plating material, it is preferable that the treatment for removing a part of carbon particles is a treatment for ultrasonic cleaning or electrolytic cleaning of the surface of the composite plating film. In this case, ultrasonic cleaning is preferably performed at 20 to 100 kHz for 1 to 300 seconds, and electrolytic cleaning is preferably performed at 1 to 30 A / dm 2 for 10 to 300 seconds. Further, the removal rate of carbon particles by a treatment for removing a part of carbon particles on the surface is preferably 20 to 75 area%, and the carbon particles are preferably graphite particles having an average particle size of 1 to 15 μm. .. Further, the silver plating solution is preferably a sulfonic acid-based silver plating solution, the amount of carbon particles added to the silver plating solution is preferably 10 to 100 g / L, and the current density of electroplating is 0.5 to 10 A. It is preferably performed at / dm 2. Further, the material is preferably made of copper or a copper alloy. Further, it is preferable to form a nickel plating film on the material before forming the film made of the composite material.
また、本発明による複合めっき材は、銀層中に炭素粒子を含有する複合材からなる複合めっき皮膜が素材上に形成され、複合めっき皮膜の表面の炭素粒子が占める割合が１〜５０面積％であり、複合めっき皮膜の表面に粘着力４．０２Ｎ／１０ｍｍの粘着テープを貼り付けた後に剥がしたときに、粘着テープに付着した炭素粒子の数が３５，０００個／ｍｍ２以下であることを特徴とする。 Further, in the composite plating material according to the present invention, a composite plating film made of a composite material containing carbon particles in the silver layer is formed on the material, and the ratio of carbon particles on the surface of the composite plating film is 1 to 50 area%. Therefore, when the adhesive tape having an adhesive strength of 4.02 N / 10 mm is attached to the surface of the composite plating film and then peeled off, the number of carbon particles attached to the adhesive tape is 35,000 / mm 2 or less. It is characterized by.
この複合めっき材において、複合めっき皮膜の厚さが０．５〜１５μｍであるのが好ましい。また、この複合めっき材の表面粗さＲａが０．２〜１．７μｍであるのが好ましく、摩擦係数が０．８以下であるのが好ましい。さらに、複合めっき皮膜と素材との間にニッケルめっき皮膜が形成されているのが好ましい。 In this composite plating material, the thickness of the composite plating film is preferably 0.5 to 15 μm. Further, the surface roughness Ra of this composite plating material is preferably 0.2 to 1.7 μm, and the friction coefficient is preferably 0.8 or less. Further, it is preferable that a nickel plating film is formed between the composite plating film and the material.
さらに、本発明による端子は、上記の複合めっき材を材料として用いたことを特徴とする。 Further, the terminal according to the present invention is characterized in that the above-mentioned composite plating material is used as a material.
本発明によれば、銀層中に炭素粒子を含有する複合材からなる複合めっき皮膜が素材上に形成された複合めっき材において、複合めっき皮膜中の炭素粒子の脱落が少ない複合めっき材を製造することができる。 According to the present invention, in a composite plating material in which a composite plating film made of a composite material containing carbon particles in a silver layer is formed on the material, a composite plating material in which carbon particles in the composite plating film are less likely to fall off is produced. can do.
本発明による複合めっき材の製造方法の実施の形態では、炭素粒子を添加した銀めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子を含有する複合材からなる複合めっき皮膜を（好ましくは銅または銅合金からなる）素材上に形成した後、表面の炭素粒子の一部を除去する処理を行う。 In the embodiment of the method for producing a composite plating material according to the present invention, a composite plating film composed of a composite material containing carbon particles in a silver layer is performed by electroplating using a silver plating solution to which carbon particles are added. Is formed on a material (preferably made of copper or a copper alloy), and then a treatment for removing a part of carbon particles on the surface is performed.
この複合めっき材の製造方法において、複合めっき皮膜の表面の炭素粒子の一部を除去する処理として、超音波洗浄、電解洗浄、高圧洗浄、バフ処理などの処理を行うことができるが、複合めっき皮膜の表面を超音波洗浄または電解洗浄する処理を行うのが好ましい。超音波洗浄の場合、２０〜１００ｋＨｚで１〜３００秒間行われるのが好ましく、２５〜５０ｋＨｚで２〜２７０秒間行われるのがさらに好ましい。電解洗浄の場合、１〜３０Ａ／ｄｍ２で１０〜３００秒間行われるのが好ましく、２〜２５Ａ／ｄｍ２で２０〜２７０秒間行われるのがさらに好ましい。また、表面の炭素粒子の一部を除去する処理による炭素粒子の除去率は、２０〜７５面積％であるのが好ましく、２５〜７０面積％であるのがさらに好ましい。 In this method for producing a composite plating material, as a treatment for removing a part of carbon particles on the surface of the composite plating film, treatments such as ultrasonic cleaning, electrolytic cleaning, high pressure cleaning, and buffing can be performed. It is preferable to perform a treatment of ultrasonic cleaning or electrolytic cleaning of the surface of the film. In the case of ultrasonic cleaning, it is preferably performed at 20 to 100 kHz for 1 to 300 seconds, and more preferably performed at 25 to 50 kHz for 2 to 270 seconds. In the case of electrolytic cleaning, it is preferably performed at 1 to 30 A / dm 2 for 10 to 300 seconds, and more preferably 2 to 25 A / dm 2 for 20 to 270 seconds. Further, the removal rate of carbon particles by the treatment of removing a part of the carbon particles on the surface is preferably 20 to 75 area%, more preferably 25 to 70 area%.
炭素粒子は、グラファイト粒子であるのが好ましく、このグラファイト粒子の平均粒径は、０．５〜１５μｍであるのが好ましく、１〜１０μｍであるのがさらに好ましい。また、この炭素粒子を酸化処理することにより、炭素粒子の表面に吸着している親油性有機物を除去するのが好ましい。このような親油性有機物として、アルカンやアルケンなどの脂肪族炭化水素や、アルキルベンゼンなどの芳香族炭化水素が含まれる。炭素粒子の酸化処理として、湿式酸化処理の他、Ｏ２ガスなどによる乾式酸化処理を使用することができるが、量産性の観点から湿式酸化処理を使用するのが好ましく、湿式酸化処理によって表面積が大きい炭素粒子を均一に処理することができる。湿式酸化処理の方法としては、炭素粒子を水中に懸濁させた後に適量の酸化剤を添加する方法などを使用することができる。酸化剤としては、硝酸、過酸化水素、過マンガン酸カリウム、過硫酸カリウム、過塩素酸ナトリウムなどの酸化剤を使用することができる。炭素粒子に付着している親油性有機物は、添加された酸化剤により酸化されて水に溶けやすい形態になり、炭素粒子の表面から適宜除去されると考えられる。また、この湿式酸化処理を行った後、ろ過を行い、さらに炭素粒子を水洗することにより、炭素粒子の表面から親油性有機物を除去する効果をさらに高めることができる。炭素粒子の酸化処理により、炭素粒子の表面から脂肪族炭化水素や芳香族炭化水素などの親油性有機物を除去することができ、３００℃加熱ガスによる分析によれば、酸化処理後の炭素粒子を３００℃で加熱して発生したガス中には、アルカンやアルケンなどの親油性脂肪族炭化水素や、アルキルベンゼンなどの親油性芳香族炭化水素が殆ど含まれてない。酸化処理後の炭素粒子中に脂肪族炭化水素や芳香族炭化水素が若干含まれていても、炭素粒子を銀めっき液に分散させることができるが、炭素粒子中に分子量１６０以上の炭化水素が含まれず且つ炭素粒子中の分子量１６０未満の炭化水素の３００℃加熱発生ガス強度（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５，０００，０００以下になるのが好ましい。 The carbon particles are preferably graphite particles, and the average particle size of the graphite particles is preferably 0.5 to 15 μm, more preferably 1 to 10 μm. Further, it is preferable to remove the lipophilic organic matter adsorbed on the surface of the carbon particles by oxidizing the carbon particles. Such lipophilic organic substances include aliphatic hydrocarbons such as alkanes and alkenes, and aromatic hydrocarbons such as alkylbenzene. As the oxidation treatment of carbon particles, in addition to the wet oxidation treatment, a dry oxidation treatment using O 2 gas or the like can be used, but from the viewpoint of mass productivity, the wet oxidation treatment is preferably used, and the surface area is increased by the wet oxidation treatment. Large carbon particles can be treated uniformly. As a method of the wet oxidation treatment, a method of suspending carbon particles in water and then adding an appropriate amount of an oxidizing agent can be used. As the oxidizing agent, an oxidizing agent such as nitric acid, hydrogen peroxide, potassium permanganate, potassium persulfate, and sodium perchlorate can be used. It is considered that the lipophilic organic matter adhering to the carbon particles is oxidized by the added oxidizing agent to become easily soluble in water, and is appropriately removed from the surface of the carbon particles. Further, by performing this wet oxidation treatment, filtering, and further washing the carbon particles with water, the effect of removing lipophilic organic substances from the surface of the carbon particles can be further enhanced. By the oxidation treatment of carbon particles, lipophilic organic substances such as aliphatic hydrocarbons and aromatic hydrocarbons can be removed from the surface of the carbon particles. According to the analysis with a heating gas at 300 ° C., the carbon particles after the oxidation treatment can be removed. The gas generated by heating at 300 ° C. contains almost no lipophilic aliphatic hydrocarbons such as alkanes and alkanes and lipophilic aromatic hydrocarbons such as alkylbenzene. Even if the carbon particles after the oxidation treatment contain a small amount of aliphatic hydrocarbons or aromatic hydrocarbons, the carbon particles can be dispersed in the silver plating solution, but the carbon particles contain hydrocarbons having a molecular weight of 160 or more. It is preferable that the intensity of the hydrocarbon generated by heating at 300 ° C. (purge and trap gas chromatograph mass analysis intensity) of the hydrocarbon not contained and having a molecular weight of less than 160 in the carbon particles is 5,000,000 or less.
銀めっき液としてスルホン酸系銀めっき液を使用するのが好ましく、このスルホン酸系銀めっき液は、Ａｇイオン源としてのスルホン酸銀と、錯化剤としてのスルホン酸を含み、光沢剤などの添加剤を含んでもよい。この銀めっき液中のＡｇ濃度は、５〜１５０ｇ／Ｌであるのが好ましく、１０〜１２０ｇ／Ｌであるのがさらに好ましく、２０〜１００ｇ／Ｌであるのが最も好ましい。このスルホン酸系銀めっき液に含まれるスルホン酸銀として、メタンスルホン酸銀、アルカノールスルホン酸銀、フェノールスルホン酸銀などを使用することができる。 It is preferable to use a sulfonic acid-based silver plating solution as the silver plating solution, and this sulfonic acid-based silver plating solution contains silver sulfonic acid as an Ag ion source and sulfonic acid as a complexing agent, and contains a brightener or the like. Additives may be included. The Ag concentration in the silver plating solution is preferably 5 to 150 g / L, more preferably 10 to 120 g / L, and most preferably 20 to 100 g / L. As the silver sulfonate contained in this sulfonic acid-based silver plating solution, silver methanesulfonate, silver alkanol sulfonate, silver phenol sulfonate and the like can be used.
また、銀めっき液に添加する炭素粒子の量は、１０〜１００ｇ／Ｌであるのが好ましく、１５〜９０ｇ／Ｌであるのがさらに好ましく、２０〜７０ｇ／Ｌであるのが最も好ましい。銀めっき液中の炭素粒子の量が１０ｇ／Ｌ未満であると、複合めっき皮膜中の炭素粒子の含有量を十分に多くすることができないおそれがあり、１００ｇ／Ｌより多くしても、複合めっき皮膜中の炭素粒子の含有量を多くすることはできない。 The amount of carbon particles added to the silver plating solution is preferably 10 to 100 g / L, more preferably 15 to 90 g / L, and most preferably 20 to 70 g / L. If the amount of carbon particles in the silver plating solution is less than 10 g / L, the content of carbon particles in the composite plating film may not be sufficiently increased, and even if it is more than 100 g / L, the composite The content of carbon particles in the plating film cannot be increased.
また、複合めっき皮膜を形成する際の電気めっきを電流密度０．５〜１０Ａ／ｄｍ２で行うのが好ましく、１〜５Ａ／ｄｍ２で行うのがさらに好ましく、２〜４Ａ／ｄｍ２で行うのが最も好ましい。Ａｇ濃度や電流密度が低過ぎると、複合めっき皮膜の形成が遅くなって効率的でなく、Ａｇ濃度や電流密度が高過ぎると、複合めっき皮膜の外観にムラが生じ易い。 Further, preferably to carry out electroplating for forming the composite coating at a current density 0.5~10A / dm 2, more preferably conducted at 1-5A / dm 2, carried out in 2~4A / dm 2 Is the most preferable. If the Ag concentration or current density is too low, the formation of the composite plating film is slow and inefficient, and if the Ag concentration or current density is too high, the appearance of the composite plating film tends to be uneven.
本発明による複合めっき材の製造方法の実施の形態のように、炭素粒子を添加した銀めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子が分散した複合材からなる皮膜が素材上に形成され、表面の炭素粒子が占める割合が多く、耐摩耗性に優れた複合めっき材を製造することができる。また、複合材からなる皮膜の表面の炭素粒子の一部（脱落し易い炭素粒子）を除去する処理（好ましくは複合めっき皮膜の表面を超音波洗浄または電解洗浄する処理）を行うことにより、銀層中に炭素粒子を含有する複合材からなる複合めっき皮膜が素材上に形成された複合めっき材において、複合めっき皮膜中の炭素粒子の脱落が少ない複合めっき材を製造することができる。 A film composed of a composite material in which carbon particles are dispersed in a silver layer by performing electroplating using a silver plating solution to which carbon particles are added, as in the embodiment of the method for producing a composite plating material according to the present invention. Is formed on the material, and the carbon particles on the surface occupy a large proportion, so that a composite plating material having excellent wear resistance can be produced. Further, silver is obtained by performing a treatment (preferably a treatment of ultrasonic cleaning or electrolytic cleaning of the surface of the composite plating film) for removing a part of carbon particles (carbon particles that easily fall off) on the surface of the film made of a composite material. In a composite plating material in which a composite plating film made of a composite material containing carbon particles in the layer is formed on the material, it is possible to produce a composite plating material in which carbon particles in the composite plating film are less likely to fall off.
また、本発明による複合めっき材の実施の形態では、銀層中に炭素粒子を含有する複合材からなる複合めっき皮膜が（好ましくは銅または銅合金からなる）素材上に形成された複合めっき材において、複合めっき皮膜の表面の炭素粒子が占める割合が１〜５０面積％であり、複合めっき皮膜の表面に粘着力４．０２Ｎ／１０ｍｍの粘着テープを貼り付けた後に剥がしたときに、粘着テープに付着した炭素粒子の数が３５，０００個／ｍｍ２以下（好ましくは１０，０００個／ｍｍ２以下）である。複合めっき皮膜の表面の炭素粒子が占める割合が１面積％未満であると、複合めっき材の耐摩耗性が十分でなく、５０面積％を超えると、複合めっき材の接触抵抗が高くなる。 Further, in the embodiment of the composite plating material according to the present invention, the composite plating material in which a composite plating film made of a composite material containing carbon particles in the silver layer is formed on the material (preferably made of copper or a copper alloy). The ratio of carbon particles on the surface of the composite plating film is 1 to 50 area%, and when the adhesive tape having an adhesive strength of 4.02 N / 10 mm is attached to the surface of the composite plating film and then peeled off, the adhesive tape is used. The number of carbon particles adhering to the plating is 35,000 / mm 2 or less (preferably 10,000 / mm 2 or less). If the proportion of carbon particles on the surface of the composite plating film is less than 1 area%, the wear resistance of the composite plating material is not sufficient, and if it exceeds 50 area%, the contact resistance of the composite plating material increases.
複合めっき皮膜の厚さは、０．５〜１５μｍであるのが好ましく、１〜１０μｍであるのが好ましく、３〜８μｍであるのが最も好ましい。複合めっき皮膜の厚さが０．５μｍ未満であると、複合めっき材の耐摩耗性が十分でなく、１５μｍを超えると、銀の量が多くなり、複合めっき材の製造コストが高くなる。また、複合めっき材の耐熱性を向上させるために、これらの間に（好ましくは厚さ０．５〜５μｍの）ニッケルめっき皮膜を形成してもよい。また、この複合めっき材の表面粗さＲａは、０．２〜１．７μｍであるのが好ましく、０．２〜１．３μｍであるのがさらに好ましい。また、複合めっき材の摩擦係数は、が０．８以下であるのが好ましく、０．６以下であるのがさらに好ましく、０．１〜０．５であるのが最も好ましい。 The thickness of the composite plating film is preferably 0.5 to 15 μm, preferably 1 to 10 μm, and most preferably 3 to 8 μm. If the thickness of the composite plating film is less than 0.5 μm, the wear resistance of the composite plating material is not sufficient, and if it exceeds 15 μm, the amount of silver increases and the production cost of the composite plating material increases. Further, in order to improve the heat resistance of the composite plating material, a nickel plating film (preferably having a thickness of 0.5 to 5 μm) may be formed between them. Further, the surface roughness Ra of this composite plating material is preferably 0.2 to 1.7 μm, and more preferably 0.2 to 1.3 μm. The coefficient of friction of the composite plating material is preferably 0.8 or less, more preferably 0.6 or less, and most preferably 0.1 to 0.5.
なお、本発明による複合めっき材の実施の形態から２枚の試験片を切り出して、一方の試験片を平板状試験片（評価試料）とするとともに、他方の試験片をインデント加工（内側Ｒ＝１．０ｍｍの半球状の打ち出し加工）してインデント付き試験片（圧子）とし、摺動摩耗試験機により、平板状試験片にインデント付き試験片を一定の加重（２Ｎ）で押し当てながら、素材が露出するまで往復摺動動作（摺動距離１０ｍｍ、摺動速度３ｍｍ／ｓ）を継続して、平板状試験片の磨耗状態を確認する磨耗試験を行うことにより、耐摩耗性の評価を行ったときに、５００回の往復摺動動作後に、素材が露出することがないのが好ましい。また、上記の往復摺動動作中に水平方向にかかる力を測定してその平均値Ｆを算出し、平板状試験片とインデント付き試験片との間の動摩擦係数（μ）をμ＝Ｆ／Ｎから算出すると、動摩擦係数が０．８以下であるのが好ましく、０．６以下であるのがさらに好ましい。 Two test pieces are cut out from the embodiment of the composite plating material according to the present invention, one test piece is used as a flat plate-shaped test piece (evaluation sample), and the other test piece is indented (inside R =). A 1.0 mm hemispherical embossing process is performed to obtain an indented test piece (indenter), and the material is pressed against the flat plate-shaped test piece with a constant load (2N) by a sliding wear tester. The wear resistance is evaluated by continuing the reciprocating sliding operation (sliding distance 10 mm, sliding speed 3 mm / s) until the plate-shaped test piece is exposed, and performing a wear test to confirm the wear state of the flat plate-shaped test piece. At that time, it is preferable that the material is not exposed after 500 reciprocating sliding operations. Further, the force applied in the horizontal direction during the reciprocating sliding operation is measured, the average value F is calculated, and the coefficient of dynamic friction (μ) between the flat plate-shaped test piece and the indented test piece is μ = F /. When calculated from N, the coefficient of kinetic friction is preferably 0.8 or less, and more preferably 0.6 or less.
以下、本発明による複合めっき材およびその製造方法の実施例について詳細に説明する。 Hereinafter, examples of the composite plating material according to the present invention and the method for producing the same will be described in detail.
［実施例１］
炭素粒子として平均粒径５μｍの鱗片状黒鉛粒子６重量％を３Ｌの純水中に添加し、この混合溶液を攪拌しながら５０℃に昇温させた。次に、この混合溶液に酸化剤として０．１モル／Ｌの過硫酸カリウム水溶液１．２Ｌを徐々に滴下した後、２時間攪拌して酸化処理を行い、その後、ろ紙によりろ別を行ない、水洗を行った。
[Example 1]
As carbon particles, 6% by weight of scaly graphite particles having an average particle size of 5 μm was added to 3 L of pure water, and the mixed solution was heated to 50 ° C. with stirring. Next, 1.2 L of a 0.1 mol / L potassium persulfate aqueous solution as an oxidizing agent was gradually added dropwise to this mixed solution, followed by stirring for 2 hours for oxidation treatment, and then filtering with a filter paper. Washed with water.
この酸化処理の前後の炭素粒子について、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）（島津製作所製のＧＣＭＡＳ ＱＰ−５０５０Ａ）を使用して、３００℃加熱発生ガスの分析を行ったところ、上記の酸化処理により、炭素粒子に付着していた（ノナン、デカン、３−メチル−２−ヘプテンなどの）親油性脂肪族炭化水素や、（キシレンなどの）親油性芳香族炭化水素が除去されているのがわかった。 For carbon particles before and after this oxidation treatment, a purge-and-trap gas chromatograph mass analyzer (Nippon Analytical Industry JHS-100) (GCMAS QP-5050A manufactured by Shimadzu Corporation) was used to heat the gas generated at 300 ° C. Analysis revealed that the above-mentioned oxidation treatment resulted in the lipophilic aliphatic hydrocarbons (such as nonane, decane, 3-methyl-2-heptene) and the lipophilic aroma (such as xylene) attached to the carbon particles. It was found that the group hydrocarbons had been removed.
また、素材として厚さ０．２ｍｍのＣｕ−Ｎｉ−Ｓｎ−Ｐ合金からなる板材（１．０質量％のＮｉと０．９質量％のＳｎと０．０５質量％のＰを含み、残部がＣｕである銅合金の板材）（ＤＯＷＡメタルテック株式会社製のＮＢ１０９ＥＨ）を用意し、この素材をカソード、（チタンのメッシュ素材を白金めっきした）チタン白金メッシュ電極板をアノードとして使用して、錯化剤としてスルホン酸を含むスルホン酸系Ａｇストライクめっき液（大和化成株式会社製のダインシルバーＧＰＥ−ＳＴ）中において、電流密度５Ａ／ｄｍ２で３０秒間電気めっき（Ａｇストライクめっき）を行った。 Further, as a material, a plate material made of a Cu-Ni-Sn-P alloy having a thickness of 0.2 mm (containing 1.0 mass% Ni, 0.9 mass% Sn and 0.05 mass% P, and the balance is Prepare a copper alloy plate material that is Cu) (NB109EH manufactured by DOWA Metal Tech Co., Ltd.), and use this material as the cathode and the titanium platinum mesh electrode plate (platinum-plated titanium mesh material) as the anode. Electroplating (Ag strike plating) was performed for 30 seconds at a current density of 5 A / dm 2 in a sulfonic acid-based Ag strike plating solution (Dyne Silver GPE-ST manufactured by Daiwa Kasei Co., Ltd.) containing sulfonic acid as an agent.
また、錯化剤としてスルホン酸を含むＡｇ濃度３０ｇ／Ｌのスルホン酸系銀めっき液（大和化成株式会社製のダインシルバーＧＰＥ−ＰＬ（無光沢））に、上記の酸化処理を行った炭素粒子（黒鉛粒子）を添加して、３０ｇ／Ｌの炭素粒子と３０ｇ／ＬのＡｇを含むスルホン酸系銀めっき液を用意した。 Further, carbon particles obtained by subjecting the above oxidation treatment to a sulfonic acid-based silver plating solution (Dyne Silver GPE-PL (matte) manufactured by Daiwa Kasei Co., Ltd.) containing sulfonic acid as a complexing agent and having an Ag concentration of 30 g / L. (Graphic particles) were added to prepare a sulfonic acid-based silver plating solution containing 30 g / L of carbon particles and 30 g / L of Ag.
次に、上記のＡｇストライクめっきした素材をカソード、Ａｇ電極板をアノードとして使用して、上記の炭素粒子を添加したスルホン酸系銀めっき液中において、スターラにより５００ｒｐｍで撹拌しながら、温度２５℃、電流密度３Ａ／ｄｍ２で２５０秒間電気めっき（電流効率９５％）を行い、銀めっき層中に炭素粒子を含有する複合めっき皮膜（Ａｇ−Ｃめっき皮膜）を素材上に形成した。この複合めっき皮膜（の中央部分の直径１．０ｍｍの範囲）の厚さを蛍光Ｘ線膜厚計（株式会社日立ハイテクサイエンス製のＦＴ９４５０）で測定したところ、５．２μｍであった。 Next, using the above-mentioned Ag strike-plated material as a cathode and the Ag electrode plate as an anode, the temperature is 25 ° C. while stirring at 500 rpm with a stirrer in the above-mentioned carbon particle-added sulfonic acid-based silver plating solution. Electroplating (current efficiency 95%) was performed for 250 seconds at a current density of 3 A / dm 2 , and a composite plating film (Ag—C plating film) containing carbon particles in the silver plating layer was formed on the material. The thickness of this composite plating film (within a range of 1.0 mm in diameter at the center) was measured with a fluorescent X-ray film thickness meter (FT9450 manufactured by Hitachi High-Tech Science Corporation) and found to be 5.2 μm.
次に、この複合めっき皮膜を超音波洗浄器（アズワン株式会社製のＵＳＫ−５）により純水中において３８ｋＨｚで５秒間超音波洗浄して、表面の炭素の一部を除去する処理を行った後、純水で洗浄し、エアブローで乾燥して、複合めっき材を作製した。 Next, this composite plating film was ultrasonically cleaned in pure water at 38 kHz for 5 seconds with an ultrasonic cleaner (USK-5 manufactured by AS ONE Co., Ltd.) to remove a part of carbon on the surface. After that, it was washed with pure water and dried with an air blow to prepare a composite plating material.
このようにして得られた複合めっき材から切り出した試験片の表面を観察することにより、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率（面積％））を算出した。この複合めっき皮膜の表面の炭素粒子の面積率は、試験片の表面に卓上電子顕微鏡（株式会社日立ハイテクノロジーズ製のＴＭ４０００Ｐｌｕｓ）により加速電圧５ｋＶで電子線を照射して反射電子検出器から得られた（倍率１０００倍の）反射電子組成（ＣＯＭＰＯ）像を、画像解析アプリケーション（画像編集・加工ソフトＧＩＭＰ２．１０．６）を使用して、（全ピクセルのうち最も高い輝度を２５５、最も低い輝度を０とすると、輝度が１２７以下のピクセルが黒、輝度が１２７を超えるピクセルが白になるように）階調を二値化し、銀の部分（白い部分）と炭素粒子の部分（黒い部分）に分離して、画像全体のピクセル数Ｘに対する炭素粒子の部分のピクセル数Ｙの比Ｙ／Ｘとして算出した。その結果、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）は、３２面積％であった。なお、表面の炭素の一部を除去する処理を行う前の複合めっき材について、同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出したところ、６４面積％であり、表面の炭素の一部を除去する処理による面積率の変化は、３２面積％（＝６４面積％−３２面積％）、その面積率の変化率（表面の炭素の一部を除去する処理による炭素粒子の除去率）は、５０面積％（＝（６４−３２）面積％×１００／６４面積％）であった。 By observing the surface of the test piece cut out from the composite plating material thus obtained, the ratio of the area occupied by the carbon particles on the surface of the composite plating film (area ratio (area%)) was calculated. The area ratio of carbon particles on the surface of this composite plating film is obtained from a reflected electron detector by irradiating the surface of the test piece with an electron beam at an acceleration voltage of 5 kV with a desktop electron microscope (TM4000Plus manufactured by Hitachi High-Technologies Co., Ltd.). Using an image analysis application (image editing / processing software GIMP2.10.6), a reflected electron composition (COMPO) image (at a magnification of 1000 times) was used to obtain the highest brightness of all pixels of 255 and the lowest brightness. When is 0, the gradation is binarized (so that pixels with a brightness of 127 or less are black and pixels with a brightness of more than 127 are white), and the silver part (white part) and the carbon particle part (black part). It was calculated as the ratio Y / X of the number of pixels Y of the carbon particle portion to the number of pixels X of the entire image. As a result, the ratio of the area occupied by the carbon particles on the surface of the composite plating film (area ratio) was 32 area%. When the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method for the composite plating material before the treatment for removing a part of the carbon on the surface, 64 areas were calculated. The change in area ratio due to the treatment of removing a part of the carbon on the surface is 32 area% (= 64 area% -32 area%), and the change rate of the area ratio (remove a part of the carbon on the surface). The removal rate of carbon particles by the treatment was 50 area% (= (64-32) area% × 100/64 area%).
また、得られた複合めっき材について、レーザー顕微鏡（株式会社キーエンス製のＶＫ−Ｘ１０００）により倍率１００倍で撮影した複合めっき皮膜の表面の画像を解析アプリケーション（株式会社キーエンス製のＶＫ−ＨＩＸＡバージョン３．８．０．０）によりＪＩＳ Ｂ０６０１（２００１年）に基づいて（銅合金板材の圧延方向に垂直な方向における）表面粗さを表すパラメータである算術平均粗さＲａを算出したところ、０．７５μｍであった。 In addition, the obtained composite plating material was photographed with a laser microscope (VK-X1000 manufactured by KEYENCE CORPORATION) at a magnification of 100 times, and the surface image of the composite plating film was analyzed by an analysis application (VK-HIXA version 3 manufactured by KEYENCE CORPORATION). 8.0.0) was used to calculate the arithmetic average roughness Ra, which is a parameter representing the surface roughness (in the direction perpendicular to the rolling direction of the copper alloy plate), based on JIS B0601 (2001). It was 75 μm.
また、この複合めっき材から２枚の試験片を切り出して、一方の試験片を平板状試験片（評価試料）とするとともに、他方の試験片をインデント加工（内側Ｒ＝１．０ｍｍの半球状の打ち出し加工）してインデント付き試験片（圧子）とし、摺動摩耗試験機（株式会社山崎精機研究所製）により、平板状試験片にインデント付き試験片を一定の加重（２Ｎ）で押し当てながら、素材が露出するまで往復摺動動作（摺動距離１０ｍｍ、摺動速度３ｍｍ／ｓ）を継続して、平板状試験片の磨耗状態を確認する磨耗試験を行うことにより、耐摩耗性の評価を行った。その結果、５００回の往復摺動動作後に、マイクロスコープ（株式会社キーエンス製のＶＨＸ−１０００）により平板状試験片の摺動痕の中心部を倍率２００倍で観察したところ、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。また、上記の往復摺動動作中に水平方向にかかる力を測定してその平均値Ｆを算出し、平板状試験片とインデント付き試験片との間の動摩擦係数（μ）をμ＝Ｆ／Ｎから算出したところ、動摩擦係数は０．２４であった。 In addition, two test pieces are cut out from this composite plating material, one test piece is used as a flat plate-shaped test piece (evaluation sample), and the other test piece is indented (inner R = 1.0 mm hemispherical shape). Indented test piece (indenter), and the indented test piece is pressed against the flat plate-shaped test piece with a constant load (2N) by a sliding wear tester (manufactured by Yamasaki Seiki Laboratory Co., Ltd.). However, by continuing the reciprocating sliding operation (sliding distance 10 mm, sliding speed 3 mm / s) until the material is exposed and performing a wear test to confirm the wear state of the flat plate-shaped test piece, the wear resistance is improved. Evaluation was performed. As a result, after 500 reciprocating sliding operations, the central part of the sliding marks of the flat plate-shaped test piece was observed with a microscope (VHX-1000 manufactured by KEYENCE CORPORATION) at a magnification of 200 times, and the (brown) material was observed. It was confirmed that was not exposed, and it was found that it had excellent wear resistance. Further, the force applied in the horizontal direction during the reciprocating sliding operation is measured, the average value F is calculated, and the coefficient of dynamic friction (μ) between the flat plate-shaped test piece and the indented test piece is μ = F /. When calculated from N, the coefficient of dynamic friction was 0.24.
また、得られた複合めっき材から切出した試料片の表面に粘着テープ（ニチバン株式会社製のセロテープ（登録商標）ＣＴ−１８（粘着力４．０２Ｎ／１０ｍｍ））を貼り付けた後に粘着テープを剥して、複合めっき皮膜の密着性の評価を行ったところ、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、剥がした粘着テープに付着した炭素粒子をレーザー顕微鏡（株式会社キーエンス製のＶＫＸ−１６０）により１０００倍で観察して、粘着テープに付着した炭素粒子（複合めっき皮膜から脱落した炭素粒子）を数えたところ、９６００個／ｍｍ２であった。 In addition, an adhesive tape (cellotape (registered trademark) CT-18 (adhesive strength 4.02N / 10mm) manufactured by Nichiban Co., Ltd.) was attached to the surface of the sample piece cut out from the obtained composite plating material, and then the adhesive tape was applied. When the composite plating film was peeled off and the adhesion was evaluated, the composite plating film was not peeled off and the adhesion was good. In addition, the carbon particles attached to the peeled adhesive tape were observed with a laser microscope (VKX-160 manufactured by Keyence Co., Ltd.) at a magnification of 1000, and the carbon particles attached to the adhesive tape (carbon particles removed from the composite plating film) were observed. When counted, it was 9600 pieces / mm 2 .
［実施例２］
超音波洗浄時間を２５０秒間とした以外は、実施例１と同様の方法により、複合めっき材を作製した。
[Example 2]
A composite plating material was produced by the same method as in Example 1 except that the ultrasonic cleaning time was 250 seconds.
得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出した。その結果、面積率は２６面積％、表面の炭素の一部を除去する処理を行う前の複合めっき材の面積率は６４面積％であり、表面の炭素の一部を除去する処理による面積率の変化は３８面積％（＝６４面積％−２６面積％）、その面積率の変化率は５９面積％（＝（６４−２６）面積％×１００／６４面積％）であった。 With respect to the obtained composite plating material, the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method as in Example 1. As a result, the area ratio is 26 area%, the area ratio of the composite plating material before the treatment for removing a part of the carbon on the surface is 64 area%, and the area ratio by the treatment for removing a part of the carbon on the surface. The change rate was 38 area% (= 64 area% -26 area%), and the change rate of the area rate was 59 area% (= (64-26) area% x 100/64 area%).
また、得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．５５μｍであった。 Further, when the arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1, it was 0.55 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行い、動摩擦係数を算出した。その結果、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。また、動摩擦係数は０．５２であった。 Further, the obtained composite plating material was evaluated for wear resistance by the same method as in Example 1, and the coefficient of dynamic friction was calculated. As a result, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance. The coefficient of dynamic friction was 0.52.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は４８００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles shed from the composite plating film was 4800 particles / mm 2 .
［実施例３］
実施例１と同様の素材をカソード、Ｎｉ電極板をアノードとして使用して、８０ｇ／Ｌのスルファミン酸ニッケルと４５ｇ／Ｌのホウ酸からなるニッケルめっき浴中において、液温４５℃、電流密度４Ａ／ｄｍ２で攪拌しながら３０秒間電気めっき（Ｎｉめっき）を行って、素材上に厚さ０．３μｍのＮｉめっき皮膜を形成した後にＡｇストライクめっきを行った以外は、実施例１と同様の方法により、複合めっき材を作製した。
[Example 3]
Using the same material as in Example 1 as the cathode and the Ni electrode plate as the anode, in a nickel plating bath consisting of 80 g / L nickel sulfamate and 45 g / L boric acid, the liquid temperature is 45 ° C. and the current density is 4A. The same as in Example 1 except that electroplating (Ni plating) was performed for 30 seconds while stirring at / dm 2 , a Ni plating film having a thickness of 0.3 μm was formed on the material, and then Ag strike plating was performed. A composite plating material was produced by the method.
得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出した。その結果、面積率は３２面積％、表面の炭素の一部を除去する処理を行う前の複合めっき材の面積率は６４面積％であり、表面の炭素の一部を除去する処理による面積率の変化は３２面積％（＝６４面積％−３２面積％）、その面積率の変化率は５０面積％（＝（６４−５０）面積％×１００／６４面積％）であった。 With respect to the obtained composite plating material, the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method as in Example 1. As a result, the area ratio is 32 area%, the area ratio of the composite plating material before the treatment for removing a part of the carbon on the surface is 64 area%, and the area ratio by the treatment for removing a part of the carbon on the surface. The change was 32 area% (= 64 area% −32 area%), and the change rate of the area ratio was 50 area% (= (64-50) area% × 100/64 area%).
また、得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．７５μｍであった。 Further, when the arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1, it was 0.75 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行い、動摩擦係数を算出した。その結果、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。また、動摩擦係数は０．２４であった。 Further, the obtained composite plating material was evaluated for wear resistance by the same method as in Example 1, and the coefficient of dynamic friction was calculated. As a result, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance. The coefficient of dynamic friction was 0.24.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は９６００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles shed from the composite plating film was 9600 / mm 2 .
［実施例４］
炭素粒子として平均粒径２μｍの鱗片状黒鉛粒子を使用し、複合めっき皮膜を形成する際の電気めっき時間を２５秒間とした以外は、実施例１と同様の方法により、複合めっき材を作製した。この複合めっき材の表面の炭素の一部を除去する処理を行う前の複合めっき皮膜の厚さを実施例１と同様の方法により測定したところ、０．５μｍであった。
[Example 4]
A composite plating material was prepared by the same method as in Example 1 except that scaly graphite particles having an average particle size of 2 μm were used as carbon particles and the electroplating time for forming the composite plating film was 25 seconds. .. The thickness of the composite plating film before the treatment for removing a part of carbon on the surface of the composite plating material was measured by the same method as in Example 1 and found to be 0.5 μm.
得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出した。その結果、面積率は２面積％、表面の炭素の一部を除去する処理を行う前の複合めっき材の面積率は５面積％であり、表面の炭素の一部を除去する処理による面積率の変化は３面積％（＝５面積％−２面積％）、その面積率の変化率は６０面積％（＝（５−２）面積％×１００／５面積％）であった。 With respect to the obtained composite plating material, the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method as in Example 1. As a result, the area ratio is 2 area%, the area ratio of the composite plating material before the treatment for removing a part of the carbon on the surface is 5 area%, and the area ratio by the treatment for removing a part of the carbon on the surface is 5 area%. The change was 3 area% (= 5 area% -2 area%), and the change rate of the area rate was 60 area% (= (5-2) area% x 100/5 area%).
また、得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．２３μｍであった。 Further, when the arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1, it was 0.23 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行い、動摩擦係数を算出した。その結果、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。また、動摩擦係数は０．１３であった。 Further, the obtained composite plating material was evaluated for wear resistance by the same method as in Example 1, and the coefficient of dynamic friction was calculated. As a result, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance. The coefficient of dynamic friction was 0.13.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は８４００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles dropped from the composite plating film was 8400 particles / mm 2 .
［実施例５］
炭素粒子として平均粒径１０μｍの鱗片状黒鉛粒子を使用し、複合めっき皮膜を形成する際の電気めっき時間を５００秒間とした以外は、実施例１と同様の方法により、複合めっき材を作製した。この複合めっき材の表面の炭素の一部を除去する処理を行う前の複合めっき皮膜の厚さを実施例１と同様の方法により測定したところ、１０．６μｍであった。
[Example 5]
A composite plating material was produced by the same method as in Example 1 except that scaly graphite particles having an average particle size of 10 μm were used as carbon particles and the electroplating time for forming the composite plating film was 500 seconds. .. The thickness of the composite plating film before the treatment for removing a part of carbon on the surface of the composite plating material was measured by the same method as in Example 1 and found to be 10.6 μm.
得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出した。その結果、面積率は３４面積％、表面の炭素の一部を除去する処理を行う前の複合めっき材の面積率は６２面積％であり、表面の炭素の一部を除去する処理による面積率の変化は２８面積％（＝６２面積％−３４面積％）、その面積率の変化率は４５面積％（＝（６２−３４）面積％×１００／６２面積％）であった。 With respect to the obtained composite plating material, the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method as in Example 1. As a result, the area ratio is 34 area%, the area ratio of the composite plating material before the treatment for removing a part of the carbon on the surface is 62 area%, and the area ratio by the treatment for removing a part of the carbon on the surface. The change rate was 28 area% (= 62 area% -34 area%), and the change rate of the area rate was 45 area% (= (62-34) area% x 100/62 area%).
また、得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、１．２８μｍであった。 Further, when the arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1, it was 1.28 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行い、動摩擦係数を算出した。その結果、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。また、動摩擦係数は０．４７であった。 Further, the obtained composite plating material was evaluated for wear resistance by the same method as in Example 1, and the coefficient of dynamic friction was calculated. As a result, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance. The coefficient of dynamic friction was 0.47.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は７６００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles shed from the composite plating film was 7600 / mm 2 .
［実施例６］
超音波洗浄機（アズワン株式会社製のＶＳ−１００ＩＩＩ）を使用して２８ｋＨｚで３０秒間超音波洗浄した以外は、実施例１と同様の方法により、複合めっき材を作製した。
[Example 6]
A composite plating material was produced by the same method as in Example 1 except that ultrasonic cleaning was performed at 28 kHz for 30 seconds using an ultrasonic cleaner (VS-100III manufactured by AS ONE Corporation).
得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出した。その結果、面積率は１９面積％、表面の炭素の一部を除去する処理を行う前の複合めっき材の面積率は６４面積％であり、表面の炭素の一部を除去する処理による面積率の変化は４５面積％（＝６４面積％−１９面積％）、その面積率の変化率は７０面積％（＝（６４−１９）面積％×１００／６４面積％）であった。 With respect to the obtained composite plating material, the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method as in Example 1. As a result, the area ratio is 19 area%, the area ratio of the composite plating material before the treatment for removing a part of the carbon on the surface is 64 area%, and the area ratio by the treatment for removing a part of the carbon on the surface. The change was 45 area% (= 64 area% -19 area%), and the change rate of the area rate was 70 area% (= (64-19) area% × 100/64 area%).
また、得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．３７μｍであった。 Further, when the arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1, it was 0.37 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行い、動摩擦係数を算出した。その結果、算５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。また、動摩擦係数は０．３１であった。 Further, the obtained composite plating material was evaluated for wear resistance by the same method as in Example 1, and the coefficient of dynamic friction was calculated. As a result, it was confirmed that the (brown) material was not exposed after a total of 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance. The coefficient of dynamic friction was 0.31.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は３２００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles shed from the composite plating film was 3200 particles / mm 2 .
［実施例７］
超音波洗浄の代わりに、（弱アルカリ性の液状のスプレー用）洗浄防錆剤（ヘンケルジャパン株式会社製のＢＯＮＤＥＲＩＴＥ Ｃ−ＡＫ ＰＺ）１０質量％を純水に溶かした電解液中において、ＳＵＳ３０４からなるアノード板を使用し、複合めっき皮膜を形成した素材をカソード板として使用し、４Ａ／ｄｍ２で３０秒間電解洗浄して、表面の炭素の一部を除去する処理を行った以外は、実施例１と同様の方法により、複合めっき材を作製した。
[Example 7]
Instead of ultrasonic cleaning, it consists of SUS304 in an electrolytic solution in which 10% by mass of a cleaning rust preventive (for a weakly alkaline liquid spray) (BONDERITE C-AK PZ manufactured by Henkel Japan Ltd.) is dissolved in pure water. Examples except that an anode plate was used, a material having a composite plating film formed was used as a cathode plate, and electrolytic cleaning was performed at 4 A / dm 2 for 30 seconds to remove a part of carbon on the surface. A composite plating material was produced by the same method as in 1.
得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出した。その結果、面積率は４７面積％、表面の炭素の一部を除去する処理を行う前の複合めっき材の面積率は６４面積％であり、表面の炭素の一部を除去する処理による面積率の変化は１７面積％（＝６４面積％−４７面積％）、その面積率の変化率は２７面積％（＝（６４−４７）面積％×１００／６４面積％）であった。 With respect to the obtained composite plating material, the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method as in Example 1. As a result, the area ratio is 47 area%, the area ratio of the composite plating material before the treatment for removing a part of the carbon on the surface is 64 area%, and the area ratio by the treatment for removing a part of the carbon on the surface. The change rate was 17 area% (= 64 area% -47 area%), and the change rate of the area rate was 27 area% (= (64-47) area% x 100/64 area%).
また、得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．７９μｍであった。 Further, when the arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1, it was 0.79 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行った。その結果、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。 Further, the wear resistance of the obtained composite plating material was evaluated by the same method as in Example 1. As a result, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は２８０００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles dropped from the composite plating film was 28,000 / mm 2 .
［実施例８］
電解洗浄時間を２５０秒間とした以外は、実施例７と同様の方法により、複合めっき材を作製した。
[Example 8]
A composite plating material was produced by the same method as in Example 7 except that the electrolytic cleaning time was 250 seconds.
得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出した。その結果、面積率は４４面積％、表面の炭素の一部を除去する処理を行う前の複合めっき材の面積率は６４面積％であり、表面の炭素の一部を除去する処理による面積率の変化は２０面積％（＝６４面積％−４４面積％）、その面積率の変化率は３１面積％（＝（６４−４４）面積％×１００／６４面積％）であった。 With respect to the obtained composite plating material, the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method as in Example 1. As a result, the area ratio is 44 area%, the area ratio of the composite plating material before the treatment for removing a part of the carbon on the surface is 64 area%, and the area ratio by the treatment for removing a part of the carbon on the surface. The change rate was 20 area% (= 64 area% -44 area%), and the change rate of the area rate was 31 area% (= (64-44) area% x 100/64 area%).
また、得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．７２μｍであった。 Further, when the arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1, it was 0.72 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行った。その結果、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。 Further, the wear resistance of the obtained composite plating material was evaluated by the same method as in Example 1. As a result, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は１９６００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles that fell off from the composite plating film was 19,600 / mm 2 .
［実施例９］
電解洗浄を２０Ａ／ｄｍ２で行った以外は、実施例７と同様の方法により、複合めっき材を作製した。
[Example 9]
A composite plating material was produced by the same method as in Example 7 except that the electrolytic cleaning was performed at 20 A / dm 2.
得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出した。その結果、面積率は４３面積％、表面の炭素の一部を除去する処理を行う前の複合めっき材の面積率は６４面積％であり、表面の炭素の一部を除去する処理による面積率の変化は２１面積％（＝６４面積％−４３面積％）、その面積率の変化率は３３面積％（＝（６４−４３）面積％×１００／６４面積％）であった。 With respect to the obtained composite plating material, the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method as in Example 1. As a result, the area ratio is 43 area%, the area ratio of the composite plating material before the treatment for removing a part of the carbon on the surface is 64 area%, and the area ratio by the treatment for removing a part of the carbon on the surface. The change rate was 21 area% (= 64 area% -43 area%), and the change rate of the area rate was 33 area% (= (64-43) area% x 100/64 area%).
また、得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．７４μｍであった。 Further, when the arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1, it was 0.74 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行った。その結果、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。 Further, the wear resistance of the obtained composite plating material was evaluated by the same method as in Example 1. As a result, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は２３６００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles that fell off from the composite plating film was 23,600 particles / mm 2 .
［実施例１０］
電解洗浄を２０Ａ／ｄｍ２で行った以外は、実施例８と同様の方法により、複合めっき材を作製した。
[Example 10]
A composite plating material was prepared by the same method as in Example 8 except that the electrolytic cleaning was performed at 20 A / dm 2.
得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出した。その結果、面積率は３９面積％、表面の炭素の一部を除去する処理を行う前の複合めっき材の面積率は６４面積％であり、表面の炭素の一部を除去する処理による面積率の変化は２５面積％（＝６４面積％−３９面積％）、その面積率の変化率は３９面積％（＝（６４−３９）面積％×１００／６４面積％）であった。 With respect to the obtained composite plating material, the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method as in Example 1. As a result, the area ratio is 39 area%, the area ratio of the composite plating material before the treatment for removing a part of the carbon on the surface is 64 area%, and the area ratio by the treatment for removing a part of the carbon on the surface. The change was 25 area% (= 64 area% -39 area%), and the change rate of the area rate was 39 area% (= (64-39) area% x 100/64 area%).
また、得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．６３μｍであった。 Further, when the arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1, it was 0.63 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行った。その結果、算術平均粗さＲａは０．６３μｍであった。また、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。 Further, the wear resistance of the obtained composite plating material was evaluated by the same method as in Example 1. As a result, the arithmetic mean roughness Ra was 0.63 μm. In addition, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は１４０００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles shed from the composite plating film was 14,000 / mm 2 .
［比較例１］
表面の炭素の一部を除去する処理を行わなかった以外は、実施例１と同様の方法により、複合めっき材を作製した。
[Comparative Example 1]
A composite plating material was produced by the same method as in Example 1 except that the treatment for removing a part of carbon on the surface was not performed.
得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、１．７８μｍであった。 The arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1 and found to be 1.78 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行い、動摩擦係数を算出した。その結果、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。また、動摩擦係数は０．１９であった。 Further, the obtained composite plating material was evaluated for wear resistance by the same method as in Example 1, and the coefficient of dynamic friction was calculated. As a result, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance. The coefficient of dynamic friction was 0.19.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は５１２００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles shed from the composite plating film was 51200 particles / mm 2 .
［比較例２］
表面の炭素の一部を除去する処理を行わなかった以外は、実施例４と同様の方法により、複合めっき材を作製した。
[Comparative Example 2]
A composite plating material was produced by the same method as in Example 4 except that the treatment for removing a part of carbon on the surface was not performed.
得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．３４μｍであった。 The arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1 and found to be 0.34 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行い、動摩擦係数を算出した。その結果、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。また、動摩擦係数は０．１２であった。 Further, the obtained composite plating material was evaluated for wear resistance by the same method as in Example 1, and the coefficient of dynamic friction was calculated. As a result, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance. The coefficient of dynamic friction was 0.12.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜の剥がれはなく、密着性は良好であった。また、複合めっき皮膜から脱落した炭素粒子は３５６００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the composite plating film was not peeled off, and the adhesion was good. The number of carbon particles shed from the composite plating film was 35,600 particles / mm 2 .
［比較例３］
複合めっき皮膜を形成した後、この複合めっき皮膜上に銀めっき皮膜を形成し、表面の炭素の一部を除去する処理を行わなかった以外は、実施例１と同様の方法により、複合めっき材を作製した。なお、銀めっき皮膜は、錯化剤としてスルホン酸を含むＡｇ濃度３０ｇ／Ｌのスルホン酸系銀めっき液（大和化成株式会社製のダインシルバーＧＰＥ−ＰＬ（無光沢））を使用して、液温２５℃、電流密度３Ａ／ｄｍ２で６０秒間電気めっきを行うことにより形成した。
[Comparative Example 3]
After forming the composite plating film, a silver plating film was formed on the composite plating film, and the composite plating material was formed by the same method as in Example 1 except that a treatment for removing a part of carbon on the surface was not performed. Was produced. The silver plating film uses a sulfonic acid-based silver plating solution containing sulfonic acid as a complexing agent and having an Ag concentration of 30 g / L (Dyne Silver GPE-PL (matte) manufactured by Daiwa Kasei Co., Ltd.). It was formed by electroplating at a temperature of 25 ° C. and a current density of 3 A / dm 2 for 60 seconds.
得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の表面の炭素粒子が占める面積の割合（面積率）を算出した。その結果、面積率は３６面積％であり、銀めっき皮膜を形成した後の面積率は６４面積％であった。 With respect to the obtained composite plating material, the ratio (area ratio) of the area occupied by the carbon particles on the surface of the composite plating film was calculated by the same method as in Example 1. As a result, the area ratio was 36 area%, and the area ratio after forming the silver plating film was 64 area%.
また、得られた複合めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．７６μｍであった。 Further, when the arithmetic average roughness Ra of the obtained composite plating material was calculated by the same method as in Example 1, it was 0.76 μm.
また、得られた複合めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行い、動摩擦係数を算出した。その結果、５００回の往復摺動動作後に、（茶色の）素材が露出していないことが確認され、耐摩耗性に優れていることがわかった。また、動摩擦係数は０．１９であった。 Further, the obtained composite plating material was evaluated for wear resistance by the same method as in Example 1, and the coefficient of dynamic friction was calculated. As a result, it was confirmed that the (brown) material was not exposed after 500 reciprocating sliding operations, and it was found that the material was excellent in wear resistance. The coefficient of dynamic friction was 0.19.
また、得られた複合めっき材について、実施例１と同様の方法により、複合めっき皮膜の密着性の評価を行い、複合めっき皮膜から脱落した炭素粒子を数えた。その結果、複合めっき皮膜上に形成した銀めっき皮膜が剥がれ、密着性は良好でなかった。また、複合めっき皮膜から脱落した炭素粒子は２１２００個／ｍｍ２であった。 Further, with respect to the obtained composite plating material, the adhesion of the composite plating film was evaluated by the same method as in Example 1, and the carbon particles that fell off from the composite plating film were counted. As a result, the silver plating film formed on the composite plating film was peeled off, and the adhesion was not good. The number of carbon particles shed from the composite plating film was 21,200 / mm 2 .
［比較例４］
複合めっき皮膜に代えて、銀めっき皮膜を形成し、表面の炭素の一部を除去する処理を行わなかった以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、銀めっき皮膜は、錯化剤としてスルホン酸を含むＡｇ濃度３０ｇ／Ｌのスルホン酸系銀めっき液（大和化成株式会社製のダインシルバーＧＰＥ−ＰＬ（無光沢））を使用して、液温２５℃、電流密度３Ａ／ｄｍ２で２５０秒間電気めっきを行うことにより形成した。この銀めっき材の銀めっき皮膜の厚さを実施例１と同様の方法により測定したところ、５．６μｍであった。
[Comparative Example 4]
A silver plating material was produced by the same method as in Example 1 except that a silver plating film was formed instead of the composite plating film and a treatment for removing a part of carbon on the surface was not performed. The silver plating film uses a sulfonic acid-based silver plating solution containing sulfonic acid as a complexing agent and having an Ag concentration of 30 g / L (Dyne Silver GPE-PL (matte) manufactured by Daiwa Kasei Co., Ltd.). It was formed by electroplating at a temperature of 25 ° C. and a current density of 3 A / dm 2 for 250 seconds. The thickness of the silver-plated film of this silver-plated material was measured by the same method as in Example 1 and found to be 5.6 μm.
得られた銀めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．１９μｍであった。 The arithmetic average roughness Ra of the obtained silver-plated material was calculated by the same method as in Example 1 and found to be 0.19 μm.
また、得られた銀めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行い、動摩擦係数を算出した。その結果、５７回の往復摺動動作後に、（茶色の）素材が露出していることが確認され、耐摩耗性が良好でないことがわかった。また、動摩擦係数は１．８５であった。 Further, the obtained silver-plated material was evaluated for wear resistance by the same method as in Example 1, and the coefficient of dynamic friction was calculated. As a result, it was confirmed that the (brown) material was exposed after 57 reciprocating sliding operations, and it was found that the wear resistance was not good. The coefficient of dynamic friction was 1.85.
また、得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜の密着性の評価を行ったところ、銀めっき皮膜の剥がれはなく、密着性は良好であった。 Further, when the adhesion of the silver plating film was evaluated for the obtained silver plating material by the same method as in Example 1, the silver plating film was not peeled off and the adhesion was good.
［比較例５］
Ａｇストライクめっきを電流密度３Ａ／ｄｍ２で１０秒間を行い、複合めっき皮膜に代えて、アンチモンを含む銀めっき皮膜を形成し、表面の炭素の一部を除去する処理を行わなかった以外は、実施例１と同様の方法により、銀めっき材を作製した。なお、アンチモンを含む銀めっき皮膜は、アンチモンを含む銀めっき液（日進化成株式会社製）を使用して、液温２５℃、電流密度１Ａ／ｄｍ２で４００秒間電気めっきを行うことにより形成した。この銀めっき材の銀めっき皮膜の厚さを実施例１と同様の方法により測定したところ、５．３μｍであった。
[Comparative Example 5]
Ag strike plating was performed at a current density of 3 A / dm 2 for 10 seconds, and a silver plating film containing antimony was formed instead of the composite plating film, except that a treatment for removing a part of carbon on the surface was not performed. A silver-plated material was produced by the same method as in Example 1. The silver plating film containing antimony is formed by electroplating for 400 seconds at a liquid temperature of 25 ° C. and a current density of 1 A / dm 2 using a silver plating solution containing antimony (manufactured by Nikkei Seisei Co., Ltd.). did. The thickness of the silver-plated film of this silver-plated material was measured by the same method as in Example 1 and found to be 5.3 μm.
得られた銀めっき材について、実施例１と同様の方法により、算術平均粗さＲａを算出したところ、０．１０μｍであった。 The arithmetic average roughness Ra of the obtained silver-plated material was calculated by the same method as in Example 1 and found to be 0.10 μm.
また、得られた銀めっき材について、実施例１と同様の方法により、耐摩耗性の評価を行い、動摩擦係数を算出した。その結果、３７０回の往復摺動動作後に、（茶色の）素材が露出していることが確認され、耐摩耗性が良好でないことがわかった。また、動摩擦係数は０．８２であった。 Further, the obtained silver-plated material was evaluated for wear resistance by the same method as in Example 1, and the coefficient of dynamic friction was calculated. As a result, it was confirmed that the (brown) material was exposed after 370 reciprocating sliding operations, and it was found that the wear resistance was not good. The coefficient of dynamic friction was 0.82.
また、得られた銀めっき材について、実施例１と同様の方法により、銀めっき皮膜の密着性の評価を行ったところ、銀めっき皮膜の剥がれはなく、密着性は良好であった。 Further, when the adhesion of the silver plating film was evaluated for the obtained silver plating material by the same method as in Example 1, the silver plating film was not peeled off and the adhesion was good.
これらの実施例および比較例のめっき材の製造条件および特性について表１〜表３に示す。なお、表３において、めっき皮膜の密着性が良好であった場合を○、良好でなかった場合を×で示している。 Tables 1 to 3 show the production conditions and characteristics of the plating materials of these Examples and Comparative Examples. In Table 3, the case where the adhesion of the plating film is good is indicated by ◯, and the case where the adhesion is not good is indicated by ×.
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