WO2020017389A1 - Coating material and method for manufacturing same, composite material, and electric contact terminal - Google Patents

Abstract

A coating material (3) according to the present invention has: a metal (5) that is electroplatable; and organic fibers (2) that are arranged in a dispersed state in the metal (5) and that each include carbon and oxygen. In an arbitrarily defined surface of the coating material (3), an average area ratio of the organic fibers (2), within an observation visual field partitioned in a range of 100000 μm², is in a range of 2.5-35%.

Description

皮膜材及びその製造方法、複合材、並びに電気接点用端子Coating material and its manufacturing method, composite material, and terminal for electrical contact

　本発明は、金属自体が本来有する導電性の低下をできる限り抑制しつつ、摺動特性の向上を図ることができる皮膜材及びその製造方法、並びに該皮膜材を有する複合材及び電気接点用端子に関する。 The present invention relates to a coating material and a method for producing the coating material, which can improve the sliding characteristics while minimizing a decrease in conductivity inherent to the metal itself, and a composite material and a terminal for an electric contact having the coating material. About.

　一般に、金属材料は、導電性等の材料特性が優れていることから、様々な用途で幅広く使用されている。例えば、銅板に、銀（Ａｇ）をはじめとする貴金属類、錫（Ｓｎ）などからなるめっき層を設けた金属材料は、基材の優れた導電性及び強度と、めっき金属の良好な電気接触特性とを兼ね備えた高性能導体として各種の接点、スイッチ、端子などの電気接点材に広く用いられている。 金属 Generally, metal materials are widely used in various applications because of their excellent material properties such as conductivity. For example, a metal material provided with a plating layer made of a noble metal such as silver (Ag), tin (Sn) or the like on a copper plate has excellent conductivity and strength of the base material and good electrical contact of the plated metal. It is widely used as a high-performance conductor having characteristics and various electrical contacts such as contacts, switches, and terminals.

　一方、繰返しの挿抜、摺動を伴う電気接点材料は、摺動特性（耐摩耗性）に優れることが望ましい。このような電気接点材料の摺動特性を大きく向上させるため、金属組織中にカーボンナノチューブ（ＣＮＴ）などの高い強度を有する異種材料を取り込んだ複合材が知られている（特許文献１）。しかしながら、ＣＮＴを含む複合材の表面には、アスペクト比の大きいＣＮＴが突起物として露出してしまう。そのため、このような複合材を電気接点材料として用いる場合、接触面積が小さいことに起因する電流集中による局所的な温度上昇を引き起こす可能性がある。 On the other hand, it is desirable that electrical contact materials that involve repeated insertion and removal and sliding have excellent sliding characteristics (wear resistance). In order to greatly improve the sliding characteristics of such electrical contact materials, there is known a composite material in which a high-strength dissimilar material such as carbon nanotubes (CNT) is incorporated into a metal structure (Patent Document 1). However, CNTs having a large aspect ratio are exposed as projections on the surface of the composite material containing CNTs. Therefore, when such a composite material is used as an electrical contact material, there is a possibility that a local temperature rise due to current concentration due to a small contact area may occur.

　さらに、ＣＮＴは疎水性であるため、複合材を作製するに当たり、表面改質処理を行わなければ、複合材を構成する他の物質、溶媒等と均一に混合分散させるのが難しい場合が多い。加えて、このようなＣＮＴを含む複合材を高温に加熱すると発癌性のある有毒物質を排出するとの報告もあり、環境上の問題もある。 Furthermore, since CNTs are hydrophobic, it is often difficult to uniformly mix and disperse them with other substances, solvents, and the like constituting the composite material unless a surface modification treatment is performed in producing the composite material. In addition, there is a report that heating a composite material containing such CNTs to a high temperature releases toxic substances having carcinogenicity, and there is also an environmental problem.

　特許文献２には、めっきで形成された金属材料中に有機高分子繊維が分散されている導電性物品について開示されている。しかしながら、特許文献２には、この導電性物品の用途としてリチウム二次電池の負極材料は開示されているものの、電気接点材料としての用途は挙げられておらず、また、摺動特性に関しても言及されていない。さらに、導電性物品中に含まれる有機高分子の質量割合は２０～９０質量％と非常に高く、電気接点材料として重要な導電率が小さくなるため、このような複合材は接点材料として適さないと考えられる。 Patent Document 2 discloses a conductive article in which organic polymer fibers are dispersed in a metal material formed by plating. However, Patent Document 2 discloses a negative electrode material of a lithium secondary battery as a use of this conductive article, but does not mention a use as an electric contact material, and also mentions sliding properties. It has not been. Further, the mass ratio of the organic polymer contained in the conductive article is as high as 20 to 90% by mass, and the conductivity, which is important as an electric contact material, is low. Therefore, such a composite material is not suitable as a contact material. it is conceivable that.

　特許文献３には、セルロースと複合化した金属材料のサイズを制御する方法が開示されている。しかしながら、この方法では電気接点材料として必要な形状に加工するのに耐え得る強度を兼ね備えた複合材を得ることはできない。 Patent Document 3 discloses a method of controlling the size of a metal material composited with cellulose. However, according to this method, it is not possible to obtain a composite material having strength enough to be processed into a shape required as an electrical contact material.

特開２００７－００９３３３号公報JP 2007-00933A 特開２００８－２９３８８３号公報JP 2008-293883 A 国際公開第２０１５／１７０６１３号WO 2015/170613

　上記事情に鑑み、本発明は、金属自体が本来有する導電性の低下をできる限り抑制しつつ、摺動特性が向上した皮膜材及びその製造方法、並びにこれを有する複合材及び電気接点用端子を提供することを目的とする。 In view of the above circumstances, the present invention provides a coating material having improved sliding characteristics, a method of manufacturing the same, and a composite material and an electric contact terminal having the same, while minimizing a decrease in conductivity inherent in the metal itself as much as possible. The purpose is to provide.

　本発明者らは、炭素と酸素を有する有機物の繊維、特に、セルロース繊維を分散させためっき液中で電気めっき（分散めっき）を行うと、有機物の繊維を、熱分解等の特性変化を生じることなくマトリックス金属中に分散配置させることができるとの知見を得た。そして、一定量の有機物の繊維をマトリックス金属中に分散させ、材料表面に露出する有機物の繊維の割合を制御することにより、材料表面の動摩擦係数を低減させて摺動特性を向上させると共に、導電率の低下をできる限り抑制できることを見出した。 When electroplating (dispersion plating) is performed in a plating solution in which organic fibers having carbon and oxygen, particularly cellulose fibers are dispersed, the organic fibers cause a property change such as thermal decomposition. It has been found that they can be dispersed and arranged in a matrix metal without the need. By dispersing a certain amount of organic fibers in the matrix metal and controlling the proportion of the organic fibers exposed on the material surface, the coefficient of kinetic friction on the material surface is reduced and the sliding characteristics are improved. It has been found that a reduction in the rate can be suppressed as much as possible.

　本発明の態様は、電気めっき可能な金属と、前記金属中に分散状態で配置された、炭素と酸素とを有する有機物の繊維と、を有する皮膜材であって、前記皮膜材の任意の表面において、１０００００μｍ^２の範囲で区画した観察視野内に占める前記有機物の繊維の平均面積割合が、２．５％以上３５％以下の範囲である、皮膜材である。 An aspect of the present invention is a coating material comprising a metal that can be electroplated and fibers of an organic substance having carbon and oxygen, which are disposed in a dispersed state in the metal, and an arbitrary surface of the coating material. Wherein the average area ratio of the organic fiber in the observation visual field divided in a range of 100000 μm ^{2 is in} a range of 2.5% or more and 35% or less.

　本発明の態様は、前記皮膜材の任意の表面において、前記有機物の繊維が、１００００μｍ^２以下の範囲内に少なくとも１つ存在する、皮膜材である。 An embodiment of the present invention is a coating material in which at least one organic fiber is present in an arbitrary surface of the coating material within a range of 10,000 μm ² or less.

　本発明の態様は、前記平均面積割合が２．５％以上２５％以下である、皮膜材である。 態 様 An embodiment of the present invention is a coating material, wherein the average area ratio is 2.5% or more and 25% or less.

　本発明の態様は、前記皮膜材中に含まれる前記有機物の繊維の平均質量割合が、０．０２質量％以上１０質量％以下である、皮膜材である。 態 様 An embodiment of the present invention is a coating material in which the average mass ratio of the organic fibers contained in the coating material is 0.02% by mass or more and 10% by mass or less.

　本発明の態様は、前記皮膜材の平均厚さが５００μｍ以下である、皮膜材である。 態 様 An embodiment of the present invention is a coating material, wherein the coating material has an average thickness of 500 μm or less.

　本発明の態様は、前記金属が、Ｃｕ、Ａｇ、Ａｕ、Ｓｎ、Ｎｉ又はＰｄである、皮膜材である。 態 様 An embodiment of the present invention is a coating material, wherein the metal is Cu, Ag, Au, Sn, Ni, or Pd.

　本発明の態様は、前有機物がセルロース繊維である、皮膜材である。 態 様 An embodiment of the present invention is a coating material, wherein the pre-organic matter is a cellulose fiber.

　本発明の態様は、前記金属がＣｕ、Ａｇ又はＳｎであり、前記平均面積割合が２．５％以上２５％以下であり、前記有機物の繊維がセルロース繊維であり、かつ、前記皮膜材の任意の表面において、１０００μｍ^２以下の範囲内に少なくとも１つ存在する、皮膜材である。 According to an aspect of the present invention, the metal is Cu, Ag or Sn, the average area ratio is 2.5% or more and 25% or less, the organic fiber is a cellulose fiber, and any of the coating materials is optional. At least one coating material within the range of 1000 μm ² or less on the surface of

　本発明の態様は、前記皮膜材の表面に１００ｇｆの荷重で鋼球を摺動子として使用する往復摺動試験において、摺動回数２０～５０回の範囲内の条件下での動摩擦係数の最大値が金属そのものを基準として０．８以下である、皮膜材である。 According to an aspect of the present invention, in a reciprocating sliding test in which a steel ball is used as a slider under a load of 100 gf on the surface of the coating material, the maximum dynamic friction coefficient under the conditions of 20 to 50 times of sliding is used. It is a coating material whose value is 0.8 or less based on the metal itself.

　本発明の態様は、基材と、該基材の表面に形成された前記皮膜材と、を有する、複合材である。 態 様 An embodiment of the present invention is a composite material including a base material and the coating material formed on the surface of the base material.

　本発明の態様は、前記基材が導電性基材である、複合材である。 態 様 An embodiment of the present invention is a composite material, wherein the substrate is a conductive substrate.

　本発明の態様は、前記基材が絶縁性基材である、複合材である。 態 様 An embodiment of the present invention is a composite material, wherein the base material is an insulating base material.

　本発明の態様は、前記皮膜材を備える電気接点用端子である。 態 様 An embodiment of the present invention is a terminal for electric contact including the coating material.

　本発明の態様は、電気めっき法によって形成する前記皮膜材の製造方法である。 態 様 An embodiment of the present invention is a method for producing the film material formed by an electroplating method.

　本発明によれば、電気めっき可能な金属と、該金属中に分散状態で配置された炭素と酸素とを有する有機物の繊維と、を有する皮膜材の任意の表面において、所定の観察領域内を占める有機物の繊維の平均面積割合を特定の範囲に制御することによって、金属自体が本来有する導電性の低下をできる限り抑制しつつ、摺動特性（耐摩耗性）が向上した皮膜材及びこれを有する複合材を提供することが可能である。また、このような特性を示す皮膜材は、電気めっき法により作製することができるため、容易かつ廉価に製造することができる。さらに、このような皮膜材を電気接点用端子に用いることにより、金属材料の高い電気伝導性を保ちながら、摺動特性を向上させた電気接点を形成することができ、その結果、接点の摺動により生じる故障を抑制し、製品寿命を向上させることができる。 According to the present invention, an electroplatable metal, and an organic fiber having carbon and oxygen disposed in a dispersed state in the metal, and an arbitrary surface of a coating material having a predetermined observation area By controlling the average area ratio of the occupied organic fibers to a specific range, a coating material having improved sliding characteristics (abrasion resistance) while suppressing the decrease in conductivity inherent in the metal itself as much as possible, and It is possible to provide a composite material having: In addition, since a film material having such characteristics can be produced by an electroplating method, it can be produced easily and at low cost. Furthermore, by using such a coating material for an electrical contact terminal, an electrical contact with improved sliding characteristics can be formed while maintaining high electrical conductivity of a metal material. As a result, the sliding of the contact can be achieved. It is possible to suppress the failure caused by the movement and to prolong the product life.

図１は、本発明に従う皮膜材が、複合材の表面処理膜として形成された場合における、金属膜中に含まれる有機物の繊維の分布を示す概略断面斜視図である。FIG. 1 is a schematic cross-sectional perspective view showing a distribution of organic fibers contained in a metal film when a film material according to the present invention is formed as a surface treatment film of a composite material. 図２は、実施例４で得られた皮膜材に対して元素マッピングを行った際に得られたデータの一例であり、図２（ａ）は、取得した炭素、酸素の元素分布を表し、図２（ｂ）は、さらに判別分析法により二値化して得られた炭素、酸素の画像データを表す。FIG. 2 is an example of data obtained when element mapping was performed on the coating material obtained in Example 4, and FIG. 2A shows the obtained elemental distributions of carbon and oxygen. FIG. 2B shows image data of carbon and oxygen obtained by binarization by a discriminant analysis method.

　以下、図面を参照しながら、本発明に従う皮膜材及び複合材の実施形態について詳細に説明する。 Hereinafter, embodiments of the coating material and the composite material according to the present invention will be described in detail with reference to the drawings.

　図１に、本発明の皮膜材及び複合材の実施形態の一例を示す。図１に示されるように、本実施形態の皮膜材３は、金属（マトリックス金属）５と、金属５中に分散状態で配置された有機物の繊維２とを有し、所定量の有機物の繊維２が皮膜材３の表面に露出して存在している。また、本実施形態の複合材１は、基材４と、基材４の表面に形成された皮膜材３とを有している。尚、図１において、有機物の繊維２は、便宜上、円状、楕円状の形状で示している。 FIG. 1 shows an example of an embodiment of the coating material and the composite material of the present invention. As shown in FIG. 1, a coating material 3 of the present embodiment includes a metal (matrix metal) 5 and organic fibers 2 arranged in a dispersed state in the metal 5, and a predetermined amount of organic fibers 2. 2 is exposed on the surface of the coating material 3. Further, the composite material 1 of the present embodiment has a base material 4 and a coating material 3 formed on the surface of the base material 4. In FIG. 1, the organic fibers 2 are shown in a circular or elliptical shape for convenience.

＜有機物の繊維＞
　有機物の繊維は、炭素と酸素を有する有機物の繊維であり、生体由来の繊維であることが好ましい。ここで、有機物とは、炭素と酸素を含む化合物のうち、単位構造の複数回の繰り返しによって得られる高分子材料を意味し、好ましくは生体由来の高分子材料である。生体由来の繊維としては、セルロース繊維、キチン繊維又はキトサン繊維を使用することが好ましい。このような繊維の中でも、環境負荷が少なくかつ材料コストが安価であることから、工業的には、セルロース繊維を使用することが好ましく、セルロースミクロフィブリル又はその誘導体を使用することがより好ましい。セルロースミクロフィブリルは、セルロース分子鎖が数十本束となってできた微細な繊維であり、セルロース繊維は、このセルロースミクロフィブリルがさらに束となって構成されている。セルロース繊維の直径は、数十μｍであるのに対し、セルロースミクロフィブリルの直径は、数ｎｍ～０．１μｍである。セルロースミクロフィブリル又はその誘導体は、分散性（親水性）、他物質との親和性、微粒子の捕捉・吸着などに優れる特性を有している。また、キチン繊維又はキトサン繊維は、吸着能に優れるだけでなく、誘導体の形成により親水化処理を容易に行うことができる。 <Organic fiber>
The organic fiber is an organic fiber having carbon and oxygen, and is preferably a biological fiber. Here, the organic substance means a polymer material obtained by repeating a unit structure a plurality of times among compounds containing carbon and oxygen, and is preferably a polymer material derived from a living body. It is preferable to use cellulose fiber, chitin fiber or chitosan fiber as the biological fiber. Among such fibers, cellulose fibers are preferably used, and cellulose microfibrils or derivatives thereof are more preferably used industrially because of low environmental load and low material cost. Cellulose microfibrils are fine fibers made of bundles of dozens of cellulose molecular chains, and cellulose fibers are formed by further bundles of the cellulose microfibrils. The diameter of cellulose fibers is several tens of μm, while the diameter of cellulose microfibrils is several nm to 0.1 μm. Cellulose microfibrils or derivatives thereof have excellent properties such as dispersibility (hydrophilicity), affinity with other substances, and capture / adsorption of fine particles. Moreover, the chitin fiber or the chitosan fiber is not only excellent in the adsorptivity, but also can be easily subjected to a hydrophilization treatment by forming a derivative.

　有機物の繊維は短繊維であることが好ましく、マトリックス金属中に短繊維が分散状態、特に均一な分散状態で配置されていることがより好ましい。これにより、皮膜材は、安定した高い強度を得ることができる。また、短繊維のサイズとしては、直径が４～１０ｎｍ、長さが５～１０μｍであることが好ましい。 繊 維 The organic fibers are preferably short fibers, and more preferably the short fibers are arranged in a matrix metal in a dispersed state, particularly a uniform dispersed state. Thereby, the coating material can obtain stable high strength. The size of the short fibers is preferably 4 to 10 nm in diameter and 5 to 10 μm in length.

　さらに、特定方向の強度（特に引張強度）を有効に高める場合には、有機物の繊維、特に短繊維は、マトリックス金属中に一方向に揃った状態で分散されていることが好ましい。一方、強度（特に引張強度）を異方性なく均一に高める場合には、有機物の繊維、特に短繊維は、マトリックス金属中にランダム方向に配列した状態で分散されていることが好ましい。 Furthermore, when the strength (particularly tensile strength) in a specific direction is to be effectively increased, it is preferable that the organic fiber, particularly the short fiber, is dispersed in the matrix metal in one direction. On the other hand, when the strength (particularly, tensile strength) is to be uniformly increased without anisotropy, it is preferable that the organic fibers, particularly the short fibers, are dispersed in the matrix metal in a state of being randomly arranged.

　有機物の繊維、特にセルロース繊維は、軟化温度（２２０～２３０℃）が金属の融点よりも低い。そのため、従来の公知の加圧鋳造法または焼結法によって、金属が溶融する温度まで有機物の繊維、特に、セルロース繊維を加熱する場合、セルロース繊維が熱分解してしまい、マトリックス金属中に、セルロース繊維が取り込まれた皮膜材を製造することができない。一方、セルロース繊維は、親水性であるため、水溶液（特に酸性水溶液）からなる各種金属のめっき液にセルロース繊維を添加すると、セルロース繊維は、めっき液中において凝集することなく分散させることが可能である。次いで、セルロース繊維が分散されているめっき液中で電気めっき（分散めっき）を行うことにより、セルロース繊維が、特に熱分解等の特性変化を生じることなく、マトリックス金属中に分散状態で配置させることができる。このため、皮膜材は電気めっき法によって形成することができる。 Organic fibers, especially cellulose fibers, have a softening temperature (220 to 230 ° C) lower than the melting point of the metal. Therefore, when heating the organic fiber, particularly the cellulose fiber to a temperature at which the metal is melted by a conventionally known pressure casting method or sintering method, the cellulose fiber is thermally decomposed, and the cellulose is contained in the matrix metal. It is not possible to produce a coating material incorporating fibers. On the other hand, since cellulose fibers are hydrophilic, when cellulose fibers are added to a plating solution of various metals composed of an aqueous solution (particularly an acidic aqueous solution), the cellulose fibers can be dispersed without agglomeration in the plating solution. is there. Next, by performing electroplating (dispersion plating) in a plating solution in which the cellulose fibers are dispersed, the cellulose fibers are arranged in a dispersed state in the matrix metal without causing a characteristic change such as thermal decomposition. Can be. For this reason, the film material can be formed by the electroplating method.

　また、皮膜材の任意の表面において、１０００００μｍ^２の範囲で区画した観察視野内に占める有機物の繊維の平均面積割合が、２．５％以上３５％以下の範囲であり、好ましくは２．５％以上２５％以下の範囲である。有機物の繊維の平均面積割合が２．５％未満では、皮膜材の表面の動摩擦係数を低減させる作用が小さく、優れた摺動特性を得ることができない。一方、有機物の繊維の平均面積割合が３５％を超えると、マトリックス金属中に含まれる有機物の繊維の割合の増大に起因して、導電率の低下率が大きくなり過ぎてしまう。このように、皮膜材の表面に露出する有機物の繊維の割合を特定の範囲に制御することにより、皮膜材の表面の動摩擦係数を低減させ摺動特性を向上させると共に、導電率の低下をできる限り抑制することができる。 In addition, the average area ratio of the fibers of the organic substance in the observation visual field divided in the range of 100,000 μm ^{2 on} any surface of the coating material is in the range of 2.5% to 35%, preferably 2.5%. The range is at least 25%. If the average area ratio of the organic fibers is less than 2.5%, the effect of reducing the dynamic friction coefficient on the surface of the coating material is small, and excellent sliding characteristics cannot be obtained. On the other hand, if the average area ratio of the organic fibers exceeds 35%, the rate of decrease in the electrical conductivity becomes too large due to the increase in the ratio of the organic fibers contained in the matrix metal. Thus, by controlling the ratio of the organic fiber exposed on the surface of the coating material to a specific range, the coefficient of kinetic friction on the surface of the coating material can be reduced, the sliding characteristics can be improved, and the conductivity can be reduced. As long as it can be suppressed.

　皮膜材の表面に露出する有機物の繊維の割合を測定する方法は、特に限定されるものではないが、例えば、作製した皮膜材の任意の表面において、所定の範囲で区画した観察視野内に対し、オージェ電子分光法により元素マッピングを行い、さらに得られた元素マッピングデータを判別分析法により２値化することにより、観察視野内に占める有機物の繊維の平均面積割合を算出することができる。その際、平均面積割合は、所定の範囲で区画した観察視野の領域を任意に複数選択し、各観察視野で得られた面積割合の平均値から算出できる。観察視野内に有機物の繊維が複数存在する場合、平均面積割合は、観察視野内に占める各有機物の繊維の面積の合計で算出する。また、１０００００μｍ^２の範囲の観察視野内に占める有機物の繊維の平均面積割合は、所定の範囲で区画した観察視野の範囲を１０００００μｍ^２に換算して得た値を用いて算出してもよい。 The method for measuring the ratio of the organic fiber exposed on the surface of the coating material is not particularly limited, but, for example, on any surface of the prepared coating material, with respect to an observation visual field partitioned in a predetermined range. By performing element mapping by Auger electron spectroscopy and binarizing the obtained element mapping data by discriminant analysis, it is possible to calculate the average area ratio of organic fiber occupying in the observation visual field. At this time, the average area ratio can be calculated from an average value of the area ratios obtained in each observation visual field by arbitrarily selecting a plurality of regions of the observation visual field divided into a predetermined range. When a plurality of organic fibers are present in the observation field, the average area ratio is calculated by the total area of the fibers of each organic substance occupying the observation field. The average area ratio of the fibers of organic material occupying in the observation visual field range of 100000 ² may be calculated by using a value obtained by converting the range of the observation field of view is defined by a predetermined range 100000 ^2.

　皮膜材の任意の表面において、有機物の繊維が、１００００μｍ^２以下の範囲内に少なくとも１つ存在することが好ましく、特に、セルロース繊維が、１０００μｍ^２以下の範囲内に少なくとも１つ存在することがより好ましい。有機物の繊維が、１００００μｍ^２以下の範囲内に少なくとも１つ存在することにより、摺動特性をより向上させることができる。 On any surface of the coating material, at least one organic fiber is preferably present in a range of 10000 μm ² or less, and in particular, at least one cellulose fiber is preferably present in a range of 1000 μm ² or less. preferable. The sliding characteristics can be further improved by the presence of at least one organic fiber within the range of 10,000 μm ² or less.

　また、皮膜材中に含まれる有機物の繊維の平均質量割合は、０．０２質量％以上１０質量％以下の範囲であることが好ましく、平均質量割合の下限値は０．０２５質量％以上であることがより好ましく、平均質量割合の上限値は９質量％以下であることがより好ましい。平均質量割合が０．０２質量％未満だと、有機物の繊維による金属の補強効果が十分ではない。そのため、有機物の繊維を含有させていない皮膜材に比べて、皮膜材の摺動特性が顕著な向上を示さない傾向にある。また、皮膜材を電気めっき法で形成する場合、一定量以上の不純物（ここでは有機物の繊維）がめっき液に含まれると、めっき液の組成が崩れ、金属の析出ができなくなるおそれがある。特に、平均質量割合が１０質量％超えである場合、電気めっき法での皮膜材の製造が困難になる傾向にある。また、マトリックス金属中に含まれる有機物の繊維の割合の増大に起因して、導電率の低下率が大きくなり過ぎてしまうことを抑制する観点から、有機物の繊維の平均質量割合は９質量％以下であることが好ましい。 The average mass ratio of the organic fibers contained in the coating material is preferably in the range of 0.02% by mass or more and 10% by mass or less, and the lower limit of the average mass ratio is 0.025% by mass or more. It is more preferable that the upper limit of the average mass ratio is 9% by mass or less. If the average mass ratio is less than 0.02% by mass, the metal reinforcing effect by the organic fiber is not sufficient. Therefore, the sliding properties of the coating material tend not to show a remarkable improvement as compared with the coating material containing no organic fiber. Further, when the coating material is formed by an electroplating method, if a certain amount or more of impurities (here, organic fibers) are contained in the plating solution, the composition of the plating solution may be lost, and metal may not be deposited. In particular, when the average mass ratio is more than 10% by mass, it tends to be difficult to produce a coating material by an electroplating method. Further, from the viewpoint of suppressing the rate of decrease in conductivity from being too large due to the increase in the ratio of the organic material fiber contained in the matrix metal, the average mass ratio of the organic material fiber is 9% by mass or less. It is preferred that

＜金属＞
　金属は、電気めっき可能な金属であり、例えば、ニッケル（Ｎｉ）、銅（Ｃｕ）、パラジウム（Ｐｄ）、銀（Ａｇ）、錫（Ｓｎ）、金（Ａｕ）、コバルト（Ｃｏ）、亜鉛（Ｚｎ）、鉄（Ｆｅ）、ロジウム（Ｒｈ）又はこれらの合金等が挙げられ、特に、ニッケル、銅、パラジウム、錫、銀又は金であることが好ましい。この中でも、電気接点用材料として、優れた導電率と接触抵抗・製造コストをバランスよく実現できる、銅、銀又は錫を用いることがさらに好ましい。特に、これらの金属の中でも、高導電率と高強度の双方を備える銅が最適である。参考として、表１～表６に、ニッケル、銅、パラジウム、銀、錫及び金のめっき浴組成並びにめっき条件の例を示す。 <Metal>
The metal is a metal that can be electroplated, for example, nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), gold (Au), cobalt (Co), zinc ( Examples thereof include Zn), iron (Fe), rhodium (Rh), and alloys thereof, and particularly preferably nickel, copper, palladium, tin, silver, or gold. Among them, it is more preferable to use copper, silver or tin, which can realize excellent electrical conductivity, contact resistance and manufacturing cost in a well-balanced manner, as a material for electric contacts. In particular, among these metals, copper having both high conductivity and high strength is most suitable. For reference, Tables 1 to 6 show examples of plating bath compositions and plating conditions of nickel, copper, palladium, silver, tin and gold.

＜導電率＞
　皮膜材は、電気接点におけるジュール熱による材料の温度上昇を低減するため、皮膜材の導電率として、金属そのものの導電率に対する低下率が３５％以下であることが好ましく、３０％以下であることがより好ましく、２５％以下であることがさらに好ましい。 <Conductivity>
In order to reduce the temperature rise of the material due to the Joule heat at the electrical contact, the coating material preferably has a conductivity of the metal material in which the rate of decrease with respect to the conductivity of the metal itself is 35% or less, preferably 30% or less. Is more preferable, and it is further preferable that it is 25% or less.

＜皮膜材の製造方法＞
　皮膜材は、例えば、電気めっき法によって形成することが好ましい。皮膜材を、電気めっき法によって形成する場合、複合材は、皮膜材と、皮膜材が形成された表面をもつ基材とで構成された表面処理材として機能する。このような表面処理材において、皮膜材は、基材上に積層された表面処理被膜であることが好ましく、例えば、基材上に電気めっきにより形成しためっき被膜であることがより好ましい。 <Production method of coating material>
The film material is preferably formed by, for example, an electroplating method. When the film material is formed by an electroplating method, the composite material functions as a surface treatment material composed of the film material and a substrate having a surface on which the film material is formed. In such a surface treatment material, the film material is preferably a surface treatment film laminated on the substrate, and more preferably, for example, a plating film formed on the substrate by electroplating.

　一方、上述の実施形態では、皮膜材を、電気めっき法により製造した場合について説明してきたが、有機物の繊維の材料特性が変化しない温度（例えば２００℃以下）で皮膜材を製造できる方法であれば特に限定されるものではない。皮膜材の他の製造方法として、例えば、無電解めっき法、ゾルゲル法、各種塗布法、低融点はんだなどの低融点金属の溶湯との混合などが挙げられる。 On the other hand, in the above-described embodiment, the case where the coating material is manufactured by the electroplating method has been described. However, any method capable of manufacturing the coating material at a temperature (for example, 200 ° C. or lower) at which the material properties of the organic fiber do not change is described. It is not particularly limited. Other methods for producing the coating material include, for example, an electroless plating method, a sol-gel method, various coating methods, and mixing of a low-melting metal such as a low-melting solder with a molten metal.

＜基材＞
　基材は、表面処理材の用途に応じて、導電性基材であってもよく、絶縁性基材であってもよい。基材が導電性基材である場合、例えば、銅、銅合金、アルミニウム、アルミニウム合金、鉄、炭素鋼、ステンレス合金などの金属、又はその金属を主成分とする合金の他、炭素、導電性樹脂、或いは導電性セラミックスを含む導電性基材が挙げられる。一方、基材が絶縁性基材である場合、表面に皮膜材が形成可能であればよく、例えば、ガラス、セラミックス、エラストマのような絶縁性基材であってもよい。 <Substrate>
The substrate may be a conductive substrate or an insulating substrate depending on the use of the surface treatment material. When the base material is a conductive base material, for example, copper, a copper alloy, aluminum, an aluminum alloy, iron, carbon steel, a metal such as a stainless alloy, or an alloy containing the metal as a main component, carbon, conductive A conductive substrate containing a resin or a conductive ceramic may be used. On the other hand, when the base material is an insulating base material, it is sufficient that a coating material can be formed on the surface, and for example, an insulating base material such as glass, ceramics, and elastomer may be used.

＜摺動特性＞
　複合材を表面処理材として構成する場合、電気接点摺動時の摩耗による表面処理膜の厚さの減少を低減するため、摺動特性をあらわす動摩擦係数が低いことが好ましい。このような複合材の動摩擦係数として、例えば、皮膜材の表面に１００ｇｆの荷重で鋼球を摺動子として使用する往復摺動試験において、摺動回数２０～５０回の範囲内の条件下での動摩擦係数の最大値が、金属（皮膜材が有する金属）そのものを基準として０．８以下、すなわち、動摩擦係数比が０．８以下であること好ましく、０．３～０．６５の範囲であることがより好ましい。 <Sliding characteristics>
When the composite material is configured as a surface treatment material, it is preferable that the dynamic friction coefficient, which represents the sliding characteristics, be low in order to reduce the decrease in the thickness of the surface treatment film due to abrasion during sliding of the electric contact. For example, in a reciprocating sliding test using a steel ball as a slider with a load of 100 gf on the surface of the coating material, the dynamic friction coefficient of such a composite material is determined under the conditions of a sliding frequency of 20 to 50 times. Is preferably 0.8 or less based on the metal itself (the metal of the coating material), that is, the dynamic friction coefficient ratio is 0.8 or less, and is preferably in the range of 0.3 to 0.65. More preferably, there is.

＜皮膜材の平均厚さ＞
　皮膜材の平均厚さについては特に制限はないが、皮膜材の平均厚さが厚すぎると生産コストが大きくなりすぎるため、平均厚さの上限値は５００μｍ以下であることが好ましい。また、複合材を表面処理材として構成する場合には、基材上にわずかに表面処理されていれば摺動特性が向上する。そのため、耐久性の観点から、皮膜材の平均厚さの下限値は、０．１μｍ以上が好ましい。皮膜材の平均厚さは、皮膜材を樹脂包理させた後、皮膜材の厚さ方向の断面の形成、研磨による断面加工を経て、走査型電子顕微鏡を用いて測定できる。測定は、断面の任意の３ヶ所で行い、その平均値を平均厚さとして算出する。 <Average thickness of coating material>
There is no particular limitation on the average thickness of the coating material, but if the average thickness of the coating material is too large, the production cost becomes too large. Therefore, the upper limit of the average thickness is preferably 500 μm or less. Further, when the composite material is configured as a surface treatment material, the sliding characteristics are improved if the surface treatment is slightly performed on the base material. Therefore, from the viewpoint of durability, the lower limit of the average thickness of the coating material is preferably 0.1 μm or more. The average thickness of the coating material can be measured using a scanning electron microscope after embedding the coating material in a resin, forming a cross section in the thickness direction of the coating material, and processing the cross section by polishing. The measurement is performed at any three points on the cross section, and the average value is calculated as the average thickness.

＜皮膜材の形状＞
　皮膜材の形状については、特に制限はなく、例えば、箔、薄板又は厚板のような板材、線材、棒材、管材、角材等のような種々の形状が挙げられる。 <Shape of coating material>
The shape of the coating material is not particularly limited, and examples thereof include various shapes such as a plate material such as a foil, a thin plate or a thick plate, a wire material, a bar material, a tube material, and a square material.

＜金属結晶粒の平均粒子径＞
　また、皮膜材中の金属結晶粒の平均粒子径は、皮膜材の厚み方向の平均粒子径に対して、皮膜材の表面に平行な方向（長手方向）の平均粒子径の方が小さいことで、より高強度化の効果が得られる。皮膜材の表面に平行な方向の金属結晶粒の平均粒子径は、０．２μｍ以上５．０μｍ以下であることが好ましい。 <Average particle size of metal crystal grains>
The average particle diameter of the metal crystal grains in the coating material is smaller than the average particle diameter in the thickness direction of the coating material in the direction parallel to the surface of the coating material (longitudinal direction). The effect of higher strength can be obtained. The average particle diameter of the metal crystal grains in the direction parallel to the surface of the coating material is preferably 0.2 μm or more and 5.0 μm or less.

＜皮膜材及び複合材の用途＞
　本実施形態の皮膜材は、用途に応じて適した金属を選択することによって、金属自体が本来有する導電性等の優れた材料特性の低下をできる限り抑制しつつ、摺動特性の向上の実現を図ることができるため、様々な技術分野で種々の製品に適用することができる。 <Applications of coating materials and composite materials>
The coating material of the present embodiment realizes an improvement in sliding characteristics while suppressing a reduction in excellent material characteristics such as conductivity inherent in the metal itself as much as possible by selecting a suitable metal according to the application. Therefore, the present invention can be applied to various products in various technical fields.

　例えば銅板（導電性基板）上に、銅と有機物の繊維とで表面処理被膜（皮膜材）を形成した表面処理銅板（複合材）は、コネクタの構成部品である電気接点用端子として使用できる。このような複合材を備える電気接点用端子は、導電性を低下させることなく、電気接点用端子としての摺動特性の向上を図ることができる。さらに、コネクタの小型化に対応した、電気接点用端子の小型化、薄肉化、高強度化を図ることもできる。 For example, a surface-treated copper plate (composite material) formed by forming a surface-treated coating (film material) with copper and organic fibers on a copper plate (conductive substrate) can be used as a terminal for an electrical contact, which is a component part of a connector. An electric contact terminal including such a composite material can improve sliding characteristics as an electric contact terminal without lowering conductivity. Further, it is possible to reduce the size, thickness, and strength of the electrical contact terminal corresponding to the reduction in the size of the connector.

　また、錫と有機物の繊維とで一体形成した皮膜材も、コネクタの構成部品である電気接点用端子として使用できる。このような皮膜材を備える電気接点用端子は、導電率を低下させることなく、摺動特性の向上を図ることができる。また、端子同士の接点の摺動による故障を抑制し、製品寿命の向上を図ることもできる。 皮膜 Furthermore, a coating material integrally formed of tin and organic fibers can also be used as a terminal for an electrical contact which is a component of the connector. The electrical contact terminal including such a coating material can improve the sliding characteristics without lowering the conductivity. In addition, it is possible to suppress a failure due to sliding of the contact between the terminals, and to improve the product life.

　以上、本発明の実施形態について説明したが、本発明は上記実施形態に限定されるものではなく、本発明の概念および請求の範囲に含まれるあらゆる態様を含み、本発明の範囲内で種々に改変することができる。 As described above, the embodiments of the present invention have been described. However, the present invention is not limited to the above-described embodiments, and includes various aspects included in the concept and claims of the present invention, and various aspects are included within the scope of the present invention. Can be modified.

　次に、本発明を実施例に基づき、さらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。 Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

（実施例１～７）
　厚さ０．３ｍｍの銅板（Ｃ１１００）上に、表７に示す金属と、有機物の繊維としてセルロース繊維とを表７に示す平均質量割合で一体形成し、皮膜材（表面処理被膜）の形成が可能か否かの確認を行った。なお、セルロース繊維は、直径が約２０ｎｍ、長さが数μｍのスギノマシン社製のセルロース繊維を使用した。表２に示す銅めっき浴に、セルロース繊維を銅めっき浴に対して０．０１～３０体積％程度添加し、攪拌して銅めっき浴中に分散させた後、セルロース繊維が分散した状態の銅めっき浴中で、表２に示すめっき条件で電気銅めっきを行い、平均厚さが５μｍになるように皮膜材を作製した。 (Examples 1 to 7)
On a copper plate (C1100) having a thickness of 0.3 mm, a metal shown in Table 7 and a cellulose fiber as an organic fiber are integrally formed at an average mass ratio shown in Table 7 to form a film material (surface treatment film). We checked whether it was possible. As the cellulose fiber, a cellulose fiber having a diameter of about 20 nm and a length of several μm manufactured by Sugino Machine Co., Ltd. was used. Cellulose fiber is added to the copper plating bath shown in Table 2 in an amount of about 0.01 to 30% by volume with respect to the copper plating bath, and is stirred and dispersed in the copper plating bath. In a plating bath, electrolytic copper plating was performed under the plating conditions shown in Table 2, and a coating material was prepared so that the average thickness was 5 μm.

　皮膜材の平均厚さの測定は、皮膜材を樹脂包理させた後、皮膜材の厚さ方向の断面の形成、研磨による断面加工を経て、走査型電子顕微鏡を用いて皮膜材の厚さを測定した。測定は断面の任意の３ヵ所で行い、その平均値を平均厚さとして算出した。 The average thickness of the coating material is measured by embedding the coating material in a resin, forming a cross section in the thickness direction of the coating material, processing the cross section by polishing, and then using a scanning electron microscope to measure the thickness of the coating material. Was measured. The measurement was performed at any three points on the cross section, and the average value was calculated as the average thickness.

　皮膜材中に含まれるセルロース繊維の平均質量割合については、皮膜材の質量に対する、皮膜材を硝酸にて溶解した後に残る残留物の質量の比率から求めた。皮膜材の質量は、４５ｃｍ×１５ｃｍの区画で皮膜材試料片を３つ採取し、各片の質量を測定することで算出した。残留物の質量は、４５ｃｍ×１５ｃｍの区画で採取された各皮膜材試料片を、２０質量％硝酸溶液中に浸漬して金属を十分に溶解し、次いで、残留物を含む硝酸溶液を２５００ｒｐｍにて１０分間遠心分離することで残留物を分離・回収し、さらに回収物を乾燥させ、その質量を測定することで算出した。なお、皮膜材を硝酸にて溶解した後の残留物は、フーリエ変換赤外分光分析によりセルロースであると同定した。測定は、皮膜材の任意の３ヵ所から採取した皮膜材試料片を用いて行い、その平均値を平均質量割合として算出した。 平均 The average mass ratio of the cellulose fibers contained in the film material was determined from the ratio of the mass of the residue remaining after dissolving the film material with nitric acid to the mass of the film material. The mass of the coating material was calculated by collecting three coating material sample pieces in a section of 45 cm × 15 cm and measuring the mass of each piece. The mass of the residue was determined by immersing each coating material sample taken in a 45 cm × 15 cm section in a 20% by mass nitric acid solution to sufficiently dissolve the metal, and then reducing the nitric acid solution containing the residue to 2500 rpm. The residue was separated and recovered by centrifugation for 10 minutes, and the recovered material was further dried and calculated by measuring its mass. The residue after dissolving the coating material with nitric acid was identified as cellulose by Fourier transform infrared spectroscopy. The measurement was performed using coating material sample pieces collected from any three places of the coating material, and the average value was calculated as an average mass ratio.

　また、皮膜材（表面処理被膜）の表面におけるセルロース繊維の平均面積割合については、下記１．の平均面積割合に記載した測定方法によって、各表面の１０００００μｍ^２の面積当たりの面積割合を任意の３ヵ所の表面について取得し、その平均値を平均面積割合として算出した。 The average area ratio of the cellulose fibers on the surface of the coating material (surface-treated coating) is as follows. The area ratio per 100,000 μm ² area of each surface was obtained for three arbitrary surfaces by the measurement method described in “Average area ratio”, and the average value was calculated as the average area ratio.

（実施例８）
　有機物の繊維として、セルロース繊維の代わりにキトサン繊維を表７に示す平均質量割合で使用した皮膜材を作製したこと以外は、実施例１～７と同様の方法で作製した。 (Example 8)
Examples 1 to 7 were produced in the same manner as in Examples 1 to 7, except that a coating material using chitosan fibers at an average mass ratio shown in Table 7 instead of the cellulose fibers was used as the organic fiber.

（比較例１）
　皮膜材（表面処理被膜）の表面における１０００００μｍ^２当たりのセルロース繊維の平均面積割合が１．８％になるように皮膜材を作製したこと以外は、実施例１～７と同様の方法で作製した。 (Comparative Example 1)
The coating material was prepared in the same manner as in Examples 1 to 7, except that the coating material was prepared so that the average area ratio of cellulose fibers per 100,000 μm ^{2 on} the surface of the coating material (surface-treated coating) was 1.8%. .

（比較例２）
　皮膜材（表面処理被膜）の表面における１０００００μｍ^２当たりのセルロース繊維の平均面積割合が３８．４％になるように皮膜材を作製したこと以外は、実施例１～７と同様の方法で作製した。 (Comparative Example 2)
The film was produced in the same manner as in Examples 1 to 7, except that the film was produced so that the average area ratio of cellulose fibers per 100,000 μm ^{2 on} the surface of the film (surface-treated film) was 38.4%. .

（従来例１）
　厚さ０．３ｍｍの銅板（Ｃ１１００）上に、表２に示す銅めっき浴およびめっき条件で電気銅めっきを行い、厚さ５μｍの銅めっき被膜を形成し、銅めっき銅板を作製した。 (Conventional example 1)
Electroless copper plating was performed on a copper plate (C1100) having a thickness of 0.3 mm under the copper plating bath and plating conditions shown in Table 2 to form a copper plating film having a thickness of 5 μm, thereby producing a copper-plated copper plate.

（実施例９）
　厚さ０．３ｍｍの銅板（Ｃ１１００）上に、表７に示す金属と、セルロース繊維とを表７に示す平均質量割合で一体形成し、皮膜材（表面処理被膜）の形成が可能か否かの確認を行った。なお、セルロース繊維は、直径が約２０ｎｍ、長さが数μｍスギノマシン社製のセルロース繊維を使用した。皮膜材は、表５に示す錫めっき浴に、セルロース繊維を、錫めっき浴に対して、０．０１～３０体積％程度添加し、攪拌して錫めっき浴中に分散させた後、セルロース繊維が分散した状態の錫めっき浴中で、表５に示すめっき条件で電気錫めっきを行い、皮膜材の平均厚さが５μｍになるように作製した。また、皮膜材の平均厚さ、皮膜材中に含まれるセルロース繊維の平均質量割合、及び皮膜材の表面におけるセルロース繊維の平均面積割合は、実施例１～７と同様の方法で測定した。 (Example 9)
On a copper plate (C1100) having a thickness of 0.3 mm, a metal shown in Table 7 and a cellulose fiber are integrally formed at an average mass ratio shown in Table 7 to determine whether a coating material (surface-treated coating) can be formed. Was confirmed. As the cellulose fiber, a cellulose fiber having a diameter of about 20 nm and a length of several μm manufactured by Sugino Machine Co., Ltd. was used. As the coating material, cellulose fiber was added to the tin plating bath shown in Table 5 in an amount of about 0.01 to 30% by volume based on the tin plating bath, and the cellulose fiber was stirred and dispersed in the tin plating bath. In a tin plating bath in which is dispersed, electrotin plating was performed under the plating conditions shown in Table 5 so that the coating material had an average thickness of 5 μm. The average thickness of the coating material, the average mass ratio of the cellulose fibers contained in the coating material, and the average area ratio of the cellulose fibers on the surface of the coating material were measured in the same manner as in Examples 1 to 7.

（従来例２）
　厚さ０．３ｍｍの銅板（Ｃ１１００）上に、表５に示す錫めっき浴およびめっき条件で電気錫めっきを行い、厚さ５μｍの錫めっき被膜を形成し、錫めっき銅板を作製した。 (Conventional example 2)
Electric tin plating was performed on a 0.3 mm thick copper plate (C1100) under the tin plating bath and plating conditions shown in Table 5 to form a 5 μm thick tin plating film, thereby producing a tin plated copper plate.

（実施例１０）
　表１に示すニッケルめっき条件、および表７に示す平均質量割合以外は、実施例１～７と同様の方法で、厚さ０．３ｍｍの銅板（Ｃ１１００）上に、金属と、セルロース繊維とを一体形成し、皮膜材（表面処理被膜）の形成が可能か否かの確認を行った。また、皮膜材の平均厚さ、皮膜材中に含まれるセルロース繊維の平均質量割合、及び皮膜材の表面におけるセルロース繊維の平均面積割合は、実施例１～７と同様の方法で測定した。 (Example 10)
Except for the nickel plating conditions shown in Table 1 and the average mass ratio shown in Table 7, the metal and cellulose fibers were coated on a 0.3 mm thick copper plate (C1100) in the same manner as in Examples 1 to 7. It was integrally formed, and it was confirmed whether or not a film material (surface treatment film) could be formed. The average thickness of the coating material, the average mass ratio of the cellulose fibers contained in the coating material, and the average area ratio of the cellulose fibers on the surface of the coating material were measured in the same manner as in Examples 1 to 7.

（従来例３）
　厚さ０．３ｍｍの銅板（Ｃ１１００）上に、表１に示すニッケルめっき浴およびめっき条件で電気ニッケルめっきを行い、厚さ５μｍのニッケルめっき被膜を形成し、ニッケルめっき銅板を作製した。 (Conventional example 3)
Electric nickel plating was performed on a copper plate (C1100) having a thickness of 0.3 mm under the nickel plating bath and plating conditions shown in Table 1 to form a nickel plating film having a thickness of 5 μm, thereby producing a nickel-plated copper plate.

（実施例１１）
　表３に示すパラジウムめっき条件、および表７に示す平均質量割合以外は、実施例１～７と同様の方法で、厚さ０．３ｍｍの銅板（Ｃ１１００）上に、金属と、セルロース繊維とを一体形成し、皮膜材（表面処理被膜）の形成が可能か否かの確認を行った。また、皮膜材の平均厚さ、皮膜材中に含まれるセルロース繊維の平均質量割合、及び皮膜材の表面におけるセルロース繊維の平均面積割合は、実施例１～７と同様の方法で測定した。 (Example 11)
Except for the palladium plating conditions shown in Table 3 and the average mass ratio shown in Table 7, the metal and cellulose fibers were coated on a 0.3 mm thick copper plate (C1100) in the same manner as in Examples 1 to 7. It was integrally formed, and it was confirmed whether or not a film material (surface treatment film) could be formed. The average thickness of the coating material, the average mass ratio of the cellulose fibers contained in the coating material, and the average area ratio of the cellulose fibers on the surface of the coating material were measured in the same manner as in Examples 1 to 7.

（従来例４）
　厚さ０．３ｍｍの銅板（Ｃ１１００）上に、表３に示すパラジウムめっき浴およびめっき条件で電気パラジウムめっきを行い、厚さ５μｍのパラジウムめっき被膜を形成し、パラジウムめっき銅板を作製した。 (Conventional example 4)
Electropalladium plating was performed on a 0.3 mm-thick copper plate (C1100) under the palladium plating bath and plating conditions shown in Table 3 to form a 5 μm-thick palladium plating film, thereby producing a palladium-plated copper plate.

（実施例１２）
　表４に示す銀めっき条件、および表７に示す平均質量割合以外は、実施例１～７と同様の方法で、厚さ０．３ｍｍの銅板（Ｃ１１００）上に、金属と、セルロース繊維とを一体形成し、皮膜材（表面処理被膜）の形成が可能か否かの確認を行った。また、皮膜材の平均厚さ、皮膜材中に含まれるセルロース繊維の平均質量割合、及び皮膜材の表面におけるセルロース繊維の平均面積割合は、実施例１～７と同様の方法で測定した。 (Example 12)
Except for the silver plating conditions shown in Table 4 and the average mass ratio shown in Table 7, a metal and cellulose fibers were coated on a 0.3 mm thick copper plate (C1100) in the same manner as in Examples 1 to 7. It was integrally formed, and it was confirmed whether or not a film material (surface treatment film) could be formed. The average thickness of the coating material, the average mass ratio of the cellulose fibers contained in the coating material, and the average area ratio of the cellulose fibers on the surface of the coating material were measured in the same manner as in Examples 1 to 7.

（従来例５）
　厚さ０．３ｍｍの銅板（Ｃ１１００）上に、表４に示す銀めっき浴およびめっき条件で電気銀めっきを行い、厚さ５μｍの銀めっき被膜を形成し、銀めっき銅板を作製した。 (Conventional example 5)
Electro-silver plating was performed on a copper plate (C1100) having a thickness of 0.3 mm under a silver plating bath and plating conditions shown in Table 4 to form a silver-plated film having a thickness of 5 μm, thereby producing a silver-plated copper plate.

（実施例１３）
　表６に示す金めっき条件、および表７に示す平均質量割合以外は、実施例１～７と同様の方法で、厚さ０．３ｍｍの銅板（Ｃ１１００）上に、金属と、セルロース繊維とを一体形成し、皮膜材（表面処理被膜）の形成が可能か否かの確認を行った。また、皮膜材の平均厚さ、皮膜材中に含まれるセルロース繊維の平均質量割合、及び皮膜材の表面におけるセルロース繊維の平均面積割合は、実施例１～７と同様の方法で測定した。 (Example 13)
Except for the gold plating conditions shown in Table 6 and the average mass ratio shown in Table 7, a metal and cellulose fibers were coated on a 0.3 mm thick copper plate (C1100) in the same manner as in Examples 1 to 7. It was integrally formed, and it was confirmed whether or not a film material (surface treatment film) could be formed. The average thickness of the coating material, the average mass ratio of the cellulose fibers contained in the coating material, and the average area ratio of the cellulose fibers on the surface of the coating material were measured in the same manner as in Examples 1 to 7.

（従来例６）
　厚さ０．３ｍｍの銅板（Ｃ１１００）上に、表６に示す金めっき浴およびめっき条件で電気金めっきを行い、厚さ５μｍの金めっき被膜を形成し、金めっき銅板を作製した。 (Conventional example 6)
Electrogold plating was performed on a copper plate (C1100) having a thickness of 0.3 mm under the gold plating bath and plating conditions shown in Table 6 to form a gold-plated film having a thickness of 5 μm, thereby producing a gold-plated copper plate.

　各実施例及び比較例で作製した表面処理被膜及び各従来例で作製しためっき被膜について、皮膜材（表面処理被膜）の表面における有機物の繊維の平均面積割合、さらには、特性として、導電率及び動摩擦係数を以下の方法で測定した。 With respect to the surface-treated film produced in each of the examples and the comparative examples and the plated film produced in each of the conventional examples, the average area ratio of the organic fiber on the surface of the film material (the surface-treated film), and further, as properties, conductivity and The dynamic friction coefficient was measured by the following method.

皮膜材（表面処理被膜）の表面における有機物の繊維の平均面積割合
　図２を参照しながら、有機物の繊維の平均面積割合の測定方法を説明する。尚、図２は実施例４の皮膜材に対して評価を行った際の一例であり、その他の実施例及び比較例についても同様に測定を行った。まず、皮膜材を評価に供する大きさ（３ｃｍ×３ｃｍ）に切り出し、アセトン中に浸漬させて超音波洗浄により皮膜材の表層の油分を除去した。その後、１０％硫酸中へ３０秒間浸漬して表層の酸化被膜を除去した。さらに、イオン交換水にて水洗の後、乾燥させて評価用の試験片を得た。このように準備した評価材を走査型オージェ電子分光装置（「ＰＨ１６８０」、アルバック・ファイ社製）を用いて、倍率：３００倍、観察視野：４００μｍ×２８０μｍ、走査線数５１２本にて、水洗処理した試験片の任意の表面の３ヵ所について、炭素、酸素の元素分布を取得（評価）した（図２（ａ）参照）。なお、前述の水洗処理は、オージェ電子顕微鏡へ評価材を導入する直前の２時間以内に行った。この元素分布画像を、画像寸法計測ソフト（「Ｐｉｘｓ２０００　Ｐｒｏ」、イノテック社製）を用いて、下限閾値を１５０、上限閾値を２５５にそれぞれ設定し、二値化の設定にて、分離点は除く一方で内部は塗りつぶしを行い、画像処理後の画像を作成した。（図２（ｂ）参照）。 Average Area Ratio of Organic Fibers on Surface of Coating Material (Surface Treatment Film) A method of measuring the average area ratio of organic fibers will be described with reference to FIG. FIG. 2 is an example when the coating material of Example 4 was evaluated, and the measurements were similarly performed for the other Examples and Comparative Examples. First, the coating material was cut into a size (3 cm × 3 cm) to be used for evaluation, immersed in acetone, and ultrasonically cleaned to remove oil on the surface layer of the coating material. Then, it was immersed in 10% sulfuric acid for 30 seconds to remove the oxide film on the surface. Furthermore, after washing with ion-exchanged water, drying was performed to obtain a test piece for evaluation. The thus prepared evaluation material was washed with a scanning Auger electron spectrometer (“PH1680”, manufactured by ULVAC-PHI) at a magnification of 300 times, an observation field of view: 400 μm × 280 μm, and 512 scanning lines. Elemental distributions of carbon and oxygen were obtained (evaluated) at three points on an arbitrary surface of the treated test piece (see FIG. 2A). In addition, the above-mentioned water-washing process was performed within 2 hours immediately before introducing the evaluation material into the Auger electron microscope. The lower limit threshold value is set to 150 and the upper limit threshold value is set to 255 for this element distribution image by using image size measurement software (“Pixs2000 Pro”, manufactured by Innotech), and the separation point is excluded in the binarization setting. On the other hand, the inside was painted out to create an image after image processing. (See FIG. 2B).

　さらに、得られた画像を解析し、処理後の画像から黒塗り部の面積が占める割合と観察範囲（４００μｍ×２８０μｍ：１１２０００μｍ^２）から面積割合を算出し、さらに１０００００μｍ^２当たりの面積割合（面積率）に換算した。また、処理後の画像から黒塗り部の各領域の面積を算出し、画像の端部に設定している黒塗り部の数値と１μｍ^２以下となっている黒塗り部の数値を除いた後、各領域の面積の平均を求めることで、少なくとも１つの有機物の繊維が存在する範囲（１ヵ所当たりの面積）を算出した。このように同一箇所を炭素と酸素でそれぞれ算出し、画像処理後の画像（図２（ｂ）参照）において、炭素、酸素の検出箇所がほぼ同一であることを確認し有機物が検出されているとみなし、これらの検出箇所のうち、酸化による誤差が出にくい炭素による算出値を有機物の面積値として用いた。このように、各面積割合及び１ヵ所当たりの面積の算出を、任意の表面の３ヵ所から取得した元素分布に対して行い、その平均値を、皮膜材の各平均面積割合及び１ヵ所当たりの平均面積とした。 Furthermore, the obtained image is analyzed, the area ratio is calculated from the ratio of the area of the black-painted portion and the observation range (400 μm × 280 μm: 112000 μm ² ) from the processed image, and the area ratio per 100,000 μm ² (area) Rate). Also, after calculating the area of each region of the blackened portion from the processed image, and excluding the numerical value of the blackened portion set at the end of the image and the numerical value of the blackened portion of 1 μm ² or less, By calculating the average of the area of each region, the range (area per one place) where at least one organic fiber was present was calculated. In this way, the same location is calculated using carbon and oxygen, respectively, and in the image after the image processing (see FIG. 2B), it is confirmed that the detection locations of carbon and oxygen are substantially the same, and the organic matter is detected. Calculated value of carbon, in which an error due to oxidation hardly appears, was used as the area value of the organic matter. In this way, the calculation of each area ratio and the area per location is performed on the element distributions obtained from three locations on an arbitrary surface, and the average value is calculated for each average area ratio and the area per location of the coating material. The average area was used.

　尚、本評価法においては、厳密には元素分布像の信号強度とノイズレベルを常に一定にし、画像処理をしなければ普遍的な測定はできない。しかしながら、試料の状態、測定環境等様々な変動要因が存在するため、像の信号強度を常に一定にすることが現実的に不可能である。そこで、例えば上記のような観察手法で各平均面積割合及び１ヵ所当たりの平均面積を算出した場合において、実施例４の皮膜材について算出した値が、本実施例の値（表７に示す値）から±２０％の範囲内にあれば、適切な評価が行われているものと判断し、それと同時に取得および解析した他の試料についても、適切な評価が行われたものと判断する。 厳 密 In this evaluation method, strictly speaking, the signal intensity and the noise level of the element distribution image are always kept constant, and universal measurement cannot be performed unless image processing is performed. However, since there are various fluctuation factors such as the state of the sample and the measurement environment, it is practically impossible to always keep the signal intensity of the image constant. Therefore, for example, when the average area ratio and the average area per location are calculated by the above-described observation method, the value calculated for the coating material of Example 4 is the value of the present example (the value shown in Table 7). ) Is within ± 20%, it is determined that appropriate evaluation has been performed, and at the same time, the other samples obtained and analyzed have also been determined to have been appropriately evaluated.

　また、皮膜材の表面（表層部）に、皮膜材全体の平均的な割合よりも多くの有機物の繊維が含まれるような皮膜材を作製する方法として、例えば、実施例１～８のような例においては、皮膜材を全体厚さの８０％まで形成した後、電気めっきの電流密度を小さくして表層部の形成を行う方法が好ましい。この場合、例えば表２に記載のめっき条件で４μｍの平均厚さの皮膜材を作成した後、電流密度を２Ａ／ｄｍ^２に変更して残りの１μｍを形成することにより、表層部により多くの有機物の繊維を露出させることができる。 As a method for producing a coating material in which the surface (surface layer) of the coating material contains more organic fibers than the average ratio of the entire coating material, for example, as described in Examples 1 to 8, In the example, it is preferable to form the surface layer by forming the coating material up to 80% of the total thickness and then reducing the current density of the electroplating. In this case, for example, after forming a coating material having an average thickness of 4 μm under the plating conditions shown in Table 2, changing the current density to 2 A / dm ² and forming the remaining 1 μm, more surface layer portions are formed. Organic fibers can be exposed.

導電率の測定
　カソード電極（チタン板）上に、厚さ１０μｍの表面処理被膜（めっき被膜）を形成した後に、チタン板から表面処理被膜（めっき被膜）を剥離し、表面処理被膜（めっき被膜）の供試材をそれぞれ３枚作製した。作製した各３枚の供試材について、２０℃（±０．５℃）に保持した恒温漕中で、四端子法により、比抵抗値を測定した。測定した比抵抗値から導電率を算出し、それらの平均値を求めた。なお、端子間距離は２００ｍｍとした。 Measurement of conductivity After forming a surface treatment film (plating film) having a thickness of 10 μm on the cathode electrode (titanium plate), the surface treatment film (plating film) is peeled off from the titanium plate, and the surface treatment film (plating film) 3 specimens were prepared. The specific resistance of each of the three test specimens was measured by a four-terminal method in a thermostat maintained at 20 ° C. (± 0.5 ° C.). The conductivity was calculated from the measured specific resistance values, and the average value thereof was obtained. The distance between the terminals was 200 mm.

動摩擦係数の測定
　厚さ０．３ｍｍの銅板（Ｃ１１００）上に、表７に示す皮膜材（表面処理被膜）が形成された複合材（表面処理材）をそれぞれ３枚作製した。作製した各３枚の複合材（供試材）において、摺動試験装置（ＨＥＩＤＯＮ　Ｔｙｐｅ：１４ＦＷ、新東科学社製）を用いて、動摩擦係数測定を行った。測定条件は、Ｒ＝３．０ｍｍ　鋼球プローブ、摺動距離：１０ｍｍ、摺動速度：１００ｍｍ／分、摺動回数：往復５０回、荷重１００ｇｆである。動摩擦係数は、摺動回数２０～５０回の範囲における動摩擦係数の最大値を有機物の繊維を含有しない元の金属膜（従来例のめっき被膜）との比（動摩擦係数比）で評価した。 Measurement of Dynamic Friction Coefficient Three composite materials (surface-treated materials) each having a film material (surface-treated film) shown in Table 7 formed on a 0.3 mm-thick copper plate (C1100). The dynamic friction coefficient of each of the three composite materials (test materials) was measured using a sliding tester (HEIDON Type: 14FW, manufactured by Shinto Kagaku). The measurement conditions are as follows: R = 3.0 mm steel ball probe, sliding distance: 10 mm, sliding speed: 100 mm / min, number of times of sliding: 50 reciprocations, load of 100 gf. The coefficient of kinetic friction was evaluated by determining the maximum value of the coefficient of kinetic friction in the range of 20 to 50 times of sliding as the ratio (kinetic friction coefficient ratio) to the original metal film (conventional plating film) containing no organic fiber.

　表７の結果から、金属が銅めっきの場合（実施例１～８、従来例１及び比較例１～２）で比較すると、平均面積割合が２．５％未満である比較例１の動摩擦係数は従来例１と比べて優位性が認められなかった。一方、平均面積割合が２．５％以上３５％以下の範囲である実施例１～６は、いずれも導電率の低下率に比べて動摩擦係数比が顕著に小さい。その中でも、平均面積割合が２．５％以上２５％以下の範囲であり、且つ、１ヵ所当たりの平均面積が１０００μｍ^２以下の範囲である実施例１～５は、動摩擦係数比が０．６５より小さく、導電率の低下率が２５％以下で、特に優れていた。 From the results in Table 7, when the metal is copper-plated (Examples 1 to 8, Conventional Example 1 and Comparative Examples 1 and 2), the dynamic friction coefficient of Comparative Example 1 having an average area ratio of less than 2.5% is shown. No superiority was recognized as compared with Conventional Example 1. On the other hand, in Examples 1 to 6 in which the average area ratio was in the range of 2.5% or more and 35% or less, the dynamic friction coefficient ratio was remarkably smaller than the conductivity reduction rate. Among them, Examples 1 to 5 in which the average area ratio is in the range of 2.5% to 25% and the average area per location is in the range of 1000 μm ² or less, have the dynamic friction coefficient ratio of 0.65. It was smaller, and the rate of decrease in conductivity was 25% or less, which was particularly excellent.

　平均面積割合が３０．４％である実施例７は、平均面積割合が２．５％以上２５％以下の範囲の実施例１～５に比べると導電率の低下率は若干大きかったものの、動摩擦係数比は極めて小さかった。 In Example 7, in which the average area ratio was 30.4%, the rate of decrease in conductivity was slightly larger than in Examples 1 to 5 in which the average area ratio was in the range of 2.5% to 25%, but dynamic friction was high. The coefficient ratio was very small.

　皮膜材（表面処理被膜）中に含まれる有機物の繊維がキトサン繊維である実施例８は、導電率の低下率に比べて動摩擦係数比が顕著に小さかった。 ８ In Example 8, in which the organic fibers contained in the coating material (surface-treated coating) were chitosan fibers, the dynamic friction coefficient ratio was significantly smaller than the rate of decrease in conductivity.

　一方、平均面積割合が３８．４％であり、且つ１ヵ所当たりの平均面積が１００００μｍ^２より大きい比較例２は、動摩擦係数比に比べて導電率の低下率が顕著に大きかった。 On the other hand, in Comparative Example 2 in which the average area ratio was 38.4% and the average area per location was greater than 10000 μm ² , the rate of decrease in conductivity was significantly higher than the dynamic friction coefficient ratio.

　金属が錫めっきである実施例９と従来例２とを比較すると、実施例９は、導電率の低下率に比べて、動摩擦係数比が顕著に小さかった。 Comparing Example 9 in which the metal is tin plating with Conventional Example 2, the dynamic friction coefficient ratio of Example 9 was significantly smaller than the rate of decrease in conductivity.

　金属がニッケルめっきである実施例１０と従来例３とを比較すると、実施例１０は、導電率の低下率に比べて、動摩擦係数比が顕著に小さかった。 Comparing Example 10 in which the metal is nickel plating with Conventional Example 3, the dynamic friction coefficient ratio of Example 10 was significantly smaller than the rate of decrease in conductivity.

　金属がパラジウムめっきである実施例１１と従来例４とを比較すると、実施例１１は、導電率の低下率に比べて、動摩擦係数比が顕著に小さかった。 Comparing Example 11 in which the metal is palladium plating with Conventional Example 4, the dynamic friction coefficient ratio of Example 11 was significantly smaller than the rate of decrease in conductivity.

　金属が銀めっきである実施例１２と従来例５とを比較すると、実施例１２は、導電率の低下率に比べて、動摩擦係数比が顕著に小さかった。 Comparing Example 12 in which the metal is silver plating with Conventional Example 5, Example 12 had a remarkably smaller dynamic friction coefficient ratio than the rate of decrease in conductivity.

　金属が金めっきである実施例１３と従来例６とを比較すると、実施例１５は、導電率の低下率に比べて、動摩擦係数比が顕著に小さかった。 Comparing Example 13 in which the metal is gold plating with Conventional Example 6, Example 15 had a remarkably small dynamic friction coefficient ratio as compared with the rate of decrease in conductivity.

（実施例１４～１６）
　表８に示す平均面積割合以外は、実施例１～７と同様の方法で、厚さ０．３ｍｍの銅板（Ｃ１１００）上に、銅と、セルロース繊維とを一体形成し、平均厚さの異なる表面処理被膜（皮膜材）を形成した。また、皮膜材の平均厚さ、皮膜材中に含まれるセルロース繊維の平均質量割合、及び皮膜材の表面におけるセルロース繊維の平均面積割合は、実施例１～７と同様の方法で測定した。 (Examples 14 to 16)
Except for the average area ratio shown in Table 8, copper and cellulose fiber were integrally formed on a 0.3 mm thick copper plate (C1100) in the same manner as in Examples 1 to 7, and the average thickness was different. A surface treatment film (film material) was formed. The average thickness of the coating material, the average mass ratio of the cellulose fibers contained in the coating material, and the average area ratio of the cellulose fibers on the surface of the coating material were measured in the same manner as in Examples 1 to 7.

（従来例７）
　厚さ０．３ｍｍの銅板（Ｃ１１００）上に、表２に示す銅めっき浴およびめっき条件で電気銅めっきを行い、厚さ３０μｍの銅めっき被膜を形成し、銅めっき銅板を作製した。 (Conventional example 7)
Electroless copper plating was performed on a copper plate (C1100) having a thickness of 0.3 mm under the copper plating bath and plating conditions shown in Table 2 to form a copper plating film having a thickness of 30 μm, thereby producing a copper-plated copper plate.

　実施例１４～１６、従来例７は、実施例１～７と同様の方法で各平均面積割合、一ヵ所当たりの平均面積、導電率、動摩擦係数を測定した。 In Examples 14 to 16 and Conventional Example 7, the average area ratio, average area per location, conductivity, and dynamic friction coefficient were measured in the same manner as in Examples 1 to 7.

　表８の結果から、皮膜材の平均厚さが０．１μｍ以上５００μｍ以下の範囲でも、実施例１～７と同様に、導電率、動摩擦係数比が優れていた。 From the results shown in Table 8, even when the average thickness of the coating material was in the range of 0.1 μm or more and 500 μm or less, the conductivity and the dynamic friction coefficient ratio were excellent as in Examples 1 to 7.

　本発明によれば、金属自体が本来有する導電性の低下をできる限り抑制しつつ、摺動特性が向上した皮膜材及びその製造方法、並びにこれを有する複合材及び電気接点用端子を提供することが可能になった。 According to the present invention, it is possible to provide a coating material having improved sliding characteristics and a method of manufacturing the same, and a composite material and an electrical contact terminal having the same, while minimizing a decrease in conductivity inherent to the metal itself as much as possible. Is now possible.

　１　複合材
　２　有機物の繊維
　３　皮膜材
　４　基材
　５　金属（マトリックス金属） DESCRIPTION OF SYMBOLS 1 Composite material 2 Organic fiber 3 Coating material 4 Substrate 5 Metal (matrix metal)

Claims (14)

1. 　電気めっき可能な金属と、
   　前記金属中に分散状態で配置された、炭素と酸素とを有する有機物の繊維と、
   を有する皮膜材であって、
   　前記皮膜材の任意の表面において、１０００００μｍ^２の範囲で区画した観察視野内に占める前記有機物の繊維の平均面積割合が、２．５％以上３５％以下の範囲であることを特徴とする皮膜材。 An electroplatable metal,
   An organic fiber having carbon and oxygen, disposed in a dispersed state in the metal,
   A coating material having
   The coating material, wherein, on an arbitrary surface of the coating material, an average area ratio of the fibers of the organic material in an observation visual field partitioned in a range of 100000 μm ^{2 is in} a range of 2.5% to 35%. .
2. 　前記皮膜材の任意の表面において、前記有機物の繊維が、１００００μｍ^２以下の範囲内に少なくとも１つ存在する、請求項１に記載の皮膜材。 2. The coating material according to claim 1, wherein, on an arbitrary surface of the coating material, at least one organic fiber is present in a range of 10,000 μm ² or less. 3.
3. 　前記平均面積割合が２．５％以上２５％以下である、請求項１又は２に記載の皮膜材。 The coating material according to claim 1 or 2, wherein the average area ratio is 2.5% or more and 25% or less.
4. 　前記皮膜材中に含まれる前記有機物の繊維の平均質量割合が、０．０２質量％以上１０質量％以下である、請求項１～３までのいずれか１項に記載の皮膜材。 (4) The coating material according to any one of (1) to (3), wherein the average mass ratio of the organic fibers contained in the coating material is 0.02% by mass or more and 10% by mass or less.
5. 　前記皮膜材の平均厚さが５００μｍ以下である、請求項１～４までのいずれか１項に記載の皮膜材。 The coating material according to any one of claims 1 to 4, wherein the coating material has an average thickness of 500 μm or less.
6. 　前記金属が、Ｃｕ、Ａｇ、Ａｕ、Ｓｎ、Ｎｉ又はＰｄである、請求項１～５までのいずれか１項に記載の皮膜材。 (6) The coating material according to any one of (1) to (5), wherein the metal is Cu, Ag, Au, Sn, Ni, or Pd.
7. 　前有機物がセルロース繊維である、請求項１～６までのいずれか１項に記載の皮膜材。 (7) The coating material according to any one of (1) to (6), wherein the organic substance is a cellulose fiber.
8. 　前記金属がＣｕ、Ａｇ又はＳｎであり、
   　前記平均面積割合が２．５％以上２５％以下であり、
   　前記有機物の繊維がセルロース繊維であり、かつ、前記皮膜材の任意の表面において、１０００μｍ^２以下の範囲内に少なくとも１つ存在する、請求項１～７までのいずれか１項に記載の皮膜材。 The metal is Cu, Ag or Sn;
   The average area ratio is 2.5% or more and 25% or less;
   The coating material according to any one of claims 1 to 7, wherein the organic fiber is a cellulose fiber, and at least one of the organic fibers is present in a range of 1000 µm ² or less on an arbitrary surface of the coating material. .
9. 　前記皮膜材の表面に１００ｇｆの荷重で鋼球を摺動子として使用する往復摺動試験において、摺動回数２０～５０回の範囲内の条件下での動摩擦係数の最大値が金属そのものを基準として０．８以下である、請求項１～８までのいずれか１項に記載の皮膜材。 In a reciprocating sliding test using a steel ball as a slider under a load of 100 gf on the surface of the coating material, the maximum value of the coefficient of kinetic friction under the conditions of the number of sliding times of 20 to 50 is based on the metal itself. The coating material according to any one of claims 1 to 8, which has a value of 0.8 or less.
10. 　基材と、該基材の表面に形成された請求項１～９までのいずれか１項に記載の皮膜材と、を有する、複合材。 複合 A composite material comprising a base material and the coating material according to any one of claims 1 to 9 formed on the surface of the base material.
11. 　前記基材が導電性基材である、請求項１０に記載の複合材。 The composite according to claim 10, wherein the base is a conductive base.
12. 　前記基材が絶縁性基材である、請求項１０に記載の複合材。 The composite according to claim 10, wherein the substrate is an insulating substrate.
13. 　請求項１～９までのいずれか１項に記載の皮膜材を備える電気接点用端子。 端子 A terminal for an electrical contact, comprising the coating material according to any one of claims 1 to 9.
14. 　電気めっき法によって形成する請求項１～９までのいずれか１項に記載の皮膜材の製造方法。 (10) The method for producing a film material according to any one of (1) to (9), which is formed by an electroplating method.

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