JP2019173141A - Ag PLATED MATERIAL, METHOD FOR MANUFACTURING SAME, AND CONTACT OR TERMINAL PART - Google Patents
Ag PLATED MATERIAL, METHOD FOR MANUFACTURING SAME, AND CONTACT OR TERMINAL PART Download PDFInfo
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本発明は、Ａｇめっき材およびその製造方法、並びに当該Ａｇめっき材が用いられた接点または端子部品に関し、特に車載用や民生用の電気配線に使用されるコネクタ、スイッチ、リレーなどの接点や端子部品の材料として使用されるＡｇめっき材およびその製造方法、並びに、接点または端子部品に関する。 The present invention relates to an Ag plating material, a method for manufacturing the same, and a contact or a terminal component using the Ag plating material, and more particularly contacts and terminals such as connectors, switches, and relays used in in-vehicle and consumer electrical wiring. The present invention relates to an Ag plating material used as a material of a component, a manufacturing method thereof, and a contact or terminal component.
電気機器には、接点や端子部品等の摺動部分を有する電子部材が設けられている。そして当該摺動部分においては、当該摺動部分を構成するＣｕやＣｕ合金等の導体素材が、比較的安価でありながら、耐食性や機械的特性などに優れた基材として用いられている。電気特性や半田付け性などの必要な特性に応じて、この基材へＳｎ、Ａｕ、Ａｇ等のめっきを施しためっき材が使用されている。 An electric device is provided with an electronic member having sliding portions such as contacts and terminal parts. And in the said sliding part, conductor materials, such as Cu and Cu alloy which comprise the said sliding part, are used as a base material excellent in corrosion resistance, a mechanical characteristic, etc., although it is comparatively cheap. A plating material obtained by plating this base material with Sn, Au, Ag or the like according to necessary characteristics such as electrical characteristics and solderability is used.
ＣｕまたはＣｕ合金等の基材へＳｎめっきを施したＳｎめっき材は、安価であるが、高温環境下における耐食性に劣っている。また、これらの基材へＡｕめっきを施したＡｕめっき材は、耐食性に優れ、信頼性は高いが、コストが高くなる。これに対し、これらの基材へＡｇめっきを施したＡｇめっき材は、Ｓｎめっき材と比べて耐食性に優れ、Ａｕめっき材と比べて安価である。 An Sn plated material obtained by applying Sn plating to a base material such as Cu or Cu alloy is inexpensive, but is inferior in corrosion resistance in a high temperature environment. In addition, Au plated materials obtained by applying Au plating to these substrates are excellent in corrosion resistance and high in reliability, but cost is high. On the other hand, Ag plating materials obtained by performing Ag plating on these base materials are superior in corrosion resistance compared to Sn plating materials, and are less expensive than Au plating materials.
一方、コネクタやスイッチ等に用いられる接点や端子部品へは、コネクタの挿抜やスイッチの摺動に伴う耐磨耗性も要求される。
ところが、Ａｇめっき材は軟質で磨耗し易い為、接点や端子部品として使用すると、挿抜や摺動によりＡｇめっきが凝着し、凝着磨耗が生じ易くなったり、接続端子の挿入時にＡｇめっきの表面が削られて摩擦係数が高くなって挿入力が高くなる、という問題がある。特に、Ａｇめっき材をワイヤーハーネスなどの挿抜可能なコネクタ材料として使用した場合、繰り返しの挿抜によってＡｇめっき層が削られて下地めっき層や基材が露出することがある。そして、下地めっき層や基材が露出すると、接触抵抗が増大して、発熱や発火に至るおそれがある。
このような問題を回避する為、Ａｇめっき層の膜厚を厚くする方法や、Ａｇめっき材の表面に潤滑材を塗布する方法等が知られている。
On the other hand, contacts and terminal parts used for connectors, switches, etc. are also required to have wear resistance due to connector insertion / extraction and switch sliding.
However, since the Ag plating material is soft and easy to wear, if it is used as a contact or terminal component, Ag plating adheres due to insertion / extraction or sliding, and adhesion wear easily occurs. There is a problem that the surface is scraped to increase the friction coefficient and the insertion force. In particular, when an Ag plating material is used as a connector material that can be inserted and removed, such as a wire harness, the Ag plating layer may be scraped by repeated insertion and extraction, exposing the underlying plating layer and the substrate. And when a base plating layer and a base material are exposed, there exists a possibility that contact resistance may increase and it may lead to a heat_generation | fever and a fire.
In order to avoid such a problem, a method of increasing the thickness of the Ag plating layer, a method of applying a lubricant on the surface of the Ag plating material, and the like are known.
例えば特許文献１には、Ａｇめっき層上に脂肪酸を含む有機化合物の有機被膜が設けられ、耐食性および耐摺動性に優れているとされる電気接点材料について記載されている。
また特許文献２には、導電体の摺動部表面にＡｇめっき層が施され、さらに黒鉛とパーフロロポリエーテルからなるグリース状潤滑剤が膜厚１０μｍ以上になるように塗布され、潤滑性に優れるとされた摺動通電体について記載されている。
さらに特許文献３には、摺動接触部の表面にＡｇめっき層が形成され、当該Ａｇめっき層上に固着された黒鉛または二硫化モリブデン層を備え、耐摩耗性、摺動抵抗、耐熱性に優れるとされた可動接触装置について記載されている。
For example, Patent Document 1 describes an electrical contact material that is provided with an organic coating of an organic compound containing a fatty acid on an Ag plating layer and is excellent in corrosion resistance and sliding resistance.
In Patent Document 2, an Ag plating layer is applied to the surface of the sliding portion of the conductor, and a grease-like lubricant composed of graphite and perfluoropolyether is applied so as to have a film thickness of 10 μm or more. It describes a sliding electrical conductor that is considered excellent.
Furthermore, in Patent Document 3, an Ag plating layer is formed on the surface of the sliding contact portion, and a graphite or molybdenum disulfide layer fixed on the Ag plating layer is provided, so that the wear resistance, sliding resistance, and heat resistance are improved. A movable contact device that has been described as being superior is described.
Ａｇめっき層の膜厚を厚くすると、原料コストが高くなる。
例えば、上述した特許文献１は、Ａｇめっき層上へ有機被膜を設け、その潤滑作用により摩耗量の低減を図る提案である。しかしながら本発明者らの検討によると、特許文献１に係るＡｇめっきは、摺動等による摩耗の進行と伴にＡｇめっき上に有機堆積物が生成し、電気接点における接触抵抗上昇が懸念されるものであった。また、磨耗の進行により基材（下地金属）の例えばＣｕまたはＣｕ合金が露出し酸化して接触抵抗が上昇するなど、信頼性が低下するおそれもあった。
一方、特許文献２、３は、電気接点における接触抵抗上昇を抑制する為、Ａｇめっき層上へ設ける潤滑剤へ黒鉛を添加することを提案している。しかしながら本発明者らの検討によると、特許文献２、３に記載の潤滑剤（グリース）は、パーフロロポリエーテル等のハロゲン化合物をバインダーとして用いている。この為、特許文献２、３に係るＡｇめっき層は、めっき層表面での摩擦係数が比較的高く、接点を摩耗させる懸念があった。だからと言って潤滑剤の膜厚を厚くすると、今度は、コストの上昇と共に、接触抵抗の上昇も懸念されるものであった。
If the thickness of the Ag plating layer is increased, the raw material cost increases.
For example, Patent Document 1 described above is a proposal in which an organic coating is provided on an Ag plating layer and the amount of wear is reduced by the lubricating action. However, according to the study by the present inventors, in the Ag plating according to Patent Document 1, organic deposits are formed on the Ag plating with the progress of wear due to sliding or the like, and there is a concern that the contact resistance at the electrical contact increases. It was a thing. Further, due to the progress of wear, for example, Cu or Cu alloy of the base material (underlying metal) is exposed and oxidized to increase the contact resistance.
On the other hand, Patent Documents 2 and 3 propose to add graphite to the lubricant provided on the Ag plating layer in order to suppress an increase in contact resistance at the electrical contact. However, according to the study by the present inventors, the lubricants (grease) described in Patent Documents 2 and 3 use halogen compounds such as perfluoropolyether as a binder. For this reason, the Ag plating layers according to Patent Documents 2 and 3 have a relatively high coefficient of friction on the surface of the plating layer, and there is a concern that the contact may be worn. However, if the film thickness of the lubricant is increased, there is a concern that the contact resistance will increase as the cost increases.
本発明は上述の状況の下で為されたものであり、その解決しようとする課題は、端子（コネクタ）、接点（スイッチ）等の電子部材に用いられる、耐摩耗性を向上させたＡｇめっき材およびその製造方法、並びに、接点または端子部品を提供することである。 The present invention has been made under the above-described circumstances, and the problem to be solved is Ag plating with improved wear resistance used for electronic members such as terminals (connectors) and contacts (switches). It is to provide a material, a manufacturing method thereof, and a contact or terminal component.
ここで本発明者らは研究を続け、表層にＡｇめっき層が形成された基材を、炭素粒子、脂肪酸および水を含有する水エマルジョンに浸漬し、Ａｇめっき層の表面に炭素粒子を含む脂肪酸含有皮膜を設けるという構成に想到した。
そして、当該構成により、耐摩耗性が高く接触抵抗上昇が回避出来るＡｇめっき材を製造出来ることを見出し、本発明を完成するに至った。そして、接点（スイッチ）、端子（コネクタ）等の電子部材の摺動部分へ、当該脂肪酸含有被膜が設けられたＡｇめっき材を用いることに拠り、当該摺動部分の耐摩耗性が向上し、接触抵抗上昇が回避出来ることを知見し、本発明を完成した。
Here, the present inventors have continued research, soaking the base material on which the Ag plating layer is formed on the surface layer in a water emulsion containing carbon particles, fatty acid and water, and the fatty acid containing carbon particles on the surface of the Ag plating layer The inventors came up with a configuration in which a coating film is provided.
And by the said structure, it discovered that Ag plating material which has high abrasion resistance and can avoid a contact-resistance raise can be manufactured, and came to complete this invention. And, by using the Ag plating material provided with the fatty acid-containing coating on the sliding parts of electronic members such as contacts (switches) and terminals (connectors), the wear resistance of the sliding parts is improved, The present invention was completed by finding out that an increase in contact resistance can be avoided.
即ち、上述の課題を解決する第１の発明は、
表層にＡｇめっき層が形成された基材を、炭素粒子と脂肪酸と水とを含む水エマルジョンに浸漬し、前記Ａｇめっき層の表面に炭素粒子を含む脂肪酸含有皮膜を形成することを特徴とする、Ａｇめっき材の製造方法である。
第２の発明は、
前記炭素粒子が、湿式処理による酸化処理を施されているとを特徴とする、第１の発明に記載のＡｇめっき材の製造方法である。
第３の発明は、
前記炭素粒子として、鱗片状の黒鉛粒子を用いることを特徴とする、第１または第２の発明に記載のＡｇめっき材の製造方法である。
第４の発明は、
前記水エマルジョン中における前記炭素粒子の量を、１ｇ／Ｌ以上１０ｇ／Ｌ以下とすることを特徴とする、第１〜第３の発明のいずれかに記載のＡｇめっき材の製造方法である。
第５の発明は、
前記脂肪酸として、ステアリン酸を用いることを特徴とする、第１〜第４の発明のいずれかに記載のＡｇめっき材の製造方法である。
第６の発明は、
前記基材として、ＣｕまたはＣｕ合金を用いることを特徴とする、第１〜第５の発明のいずれかに記載のＡｇめっき材の製造方法である。
第７の発明は、
前記基材に、ＣｕまたはＮｉからなる下地層を形成した後、前記Ａｇめっき層を形成することを特徴とする、第１〜第６の発明のいずれかに記載のＡｇめっき材の製造方法である。
第８の発明は、
前記Ａｇめっき層を、電気めっきにより形成することを特徴とする、第１〜第７の発明のいずれかに記載のＡｇめっき材の製造方法である。
第９の発明は、
基材上にＡｇめっきからなる表層が形成され、前記表層上に炭素粒子を含む脂肪酸含有皮膜が形成されていることを特徴とする、Ａｇめっき材である。
第１０の発明は、
前記炭素粒子が、鱗片状の黒鉛粒子であることを特徴とする、第９の発明に記載のＡｇめっき材である。
第１１の発明は、
前記脂肪酸が、ステアリン酸であることを特徴とする、第９または第１０の発明に記載のＡｇめっき材である。
第１２の発明は、
前記基材が、ＣｕまたはＣｕ合金からなることを特徴とする、第９〜第１１の発明のいずれかに記載のＡｇめっき材である。
第１３の発明は、
前記基材と前記Ａｇめっき層の間に、ＣｕまたはＮｉからなる下地層が形成されていることを特徴とする、第９〜第１２の発明のいずれかに記載のＡｇめっき材である。
第１４の発明は、
第９〜第１３の発明のいずれかに記載のＡｇめっき材を用いていることを特徴とする、接点または端子部品である。
That is, the first invention for solving the above-described problem is
A base material on which an Ag plating layer is formed on a surface layer is immersed in a water emulsion containing carbon particles, a fatty acid and water to form a fatty acid-containing film containing carbon particles on the surface of the Ag plating layer. , A method for producing an Ag plating material.
The second invention is
The method for producing an Ag plating material according to the first aspect, wherein the carbon particles are subjected to an oxidation treatment by a wet treatment.
The third invention is
The method for producing an Ag plating material according to the first or second invention, wherein scaly graphite particles are used as the carbon particles.
The fourth invention is:
The method for producing an Ag plating material according to any one of the first to third inventions, wherein an amount of the carbon particles in the water emulsion is 1 g / L or more and 10 g / L or less.
The fifth invention is:
The method for producing an Ag-plated material according to any one of the first to fourth inventions, wherein stearic acid is used as the fatty acid.
The sixth invention is:
Cu or Cu alloy is used as said base material, It is a manufacturing method of Ag plating material in any one of the 1st-5th invention characterized by the above-mentioned.
The seventh invention
In the method for producing an Ag plating material according to any one of the first to sixth inventions, the base layer made of Cu or Ni is formed on the base material, and then the Ag plating layer is formed. is there.
The eighth invention
The method for producing an Ag plating material according to any one of the first to seventh inventions, wherein the Ag plating layer is formed by electroplating.
The ninth invention
The Ag plating material is characterized in that a surface layer made of Ag plating is formed on a base material, and a fatty acid-containing film containing carbon particles is formed on the surface layer.
The tenth invention is
The Ag plating material according to the ninth aspect, wherein the carbon particles are scaly graphite particles.
The eleventh invention is
The Ag plating material according to the ninth or tenth invention, wherein the fatty acid is stearic acid.
The twelfth invention is
The Ag plating material according to any one of the ninth to eleventh inventions, wherein the substrate is made of Cu or a Cu alloy.
The thirteenth invention is
The Ag plating material according to any one of the ninth to twelfth inventions, wherein a base layer made of Cu or Ni is formed between the base material and the Ag plating layer.
The fourteenth invention is
A contact or terminal component using the Ag plating material according to any one of the ninth to thirteenth inventions.
本発明に係る、Ａｇめっき層上に炭素粒子を含む脂肪酸含有皮膜を設けた接点（スイッチ）、端子（コネクタ）等の電子部材に用いられるＡｇめっき材により、耐摩耗性が高いＡｇめっき材およびその製造方法を提供することが出来る。 According to the present invention, the Ag plating material used for electronic members such as contacts (switches) and terminals (connectors) provided with a fatty acid-containing film containing carbon particles on the Ag plating layer, and the Ag plating material having high wear resistance and The manufacturing method can be provided.
本発明に係るＡｇめっき材の製造方法は、表層にＡｇめっき層が形成された基材を、炭素粒子と脂肪酸と水とを含む水エマルジョンに浸漬し、Ａｇめっき層の表面に炭素粒子を含む脂肪酸含有皮膜を形成するものである。
即ち、本発明に係るＡｇめっき材は、基材上にＡｇめっきからなる表層が形成され、この表層の表面に炭素粒子を含む脂肪酸含有皮膜が設けられているものである。
そして、当該構成により、優れた耐摩耗性と、接触抵抗上昇の回避とを兼ね備えたＡｇめっき材を得ることが出来た。
In the method for producing an Ag plating material according to the present invention, a base material on which an Ag plating layer is formed is immersed in a water emulsion containing carbon particles, a fatty acid, and water, and the surface of the Ag plating layer contains carbon particles. It forms a fatty acid-containing film.
That is, the Ag plating material according to the present invention is such that a surface layer made of Ag plating is formed on a base material, and a fatty acid-containing film containing carbon particles is provided on the surface of the surface layer.
And with the said structure, the Ag plating material which had the outstanding abrasion resistance and the avoidance of a contact resistance rise was able to be obtained.
以下、本発明について、（１）炭素粒子、（２）脂肪酸、（３）水エマルジョンの調製方法、（４）Ａｇめっき材に用いる基材およびＡｇめっき、（５）Ａｇめっき面への脂肪酸含有皮膜の形成方法、（６）評価、の順に説明する。 Hereinafter, regarding the present invention, (1) carbon particles, (2) fatty acid, (3) water emulsion preparation method, (4) base material and Ag plating used for Ag plating material, (5) fatty acid content on Ag plating surface The film forming method and (6) evaluation will be described in this order.
（１）炭素粒子
本発明においては炭素粒子として、平均粒径１〜１０μｍの鱗片状または土状の黒鉛（グラファイトと同義である。）粒子を好ましく使用することが出来るが、鱗片状黒鉛粒子がさらに好ましい。
これは、黒鉛粒子の平均粒径が１μｍより大きいと、耐摩耗性の向上効果を十分に得ることが出来るからである。一方、黒鉛粒子の平均粒径が１０μｍ以下であれば、Ａｇめっき層の表層をアタックすることが無く、耐摩耗性に劣化や接触抵抗上昇のおそれがないことによる。当該観点から、黒鉛粒子の平均粒径は３〜８μｍであることがより好ましい。また黒鉛粒子が鱗片状であるとへき開し易く、摩擦係数を小さくすることが出来、好ましい。
(1) Carbon particles In the present invention, scaly or earthy graphite (having the same meaning as graphite) particles having an average particle diameter of 1 to 10 μm can be preferably used. Further preferred.
This is because if the average particle diameter of the graphite particles is larger than 1 μm, the effect of improving the wear resistance can be sufficiently obtained. On the other hand, when the average particle size of the graphite particles is 10 μm or less, the surface layer of the Ag plating layer is not attacked, and there is no fear of deterioration in wear resistance or increase in contact resistance. From this viewpoint, the average particle size of the graphite particles is more preferably 3 to 8 μm. Further, it is preferable that the graphite particles have a scaly shape because they can be easily cleaved and the friction coefficient can be reduced.
本発明において、炭素粒子の平均粒径は、炭素粒子０．５ｇを０．２重量％のヘキサメタリン酸ナトリウム溶液５０ｇに分散させ、さらに超音波により分散させた後、レーザー光散乱粒度分布測定装置を用いて、当該炭素粒子の体積基準分布における粒径を測定し、累積分布で５０％の粒径を平均粒径とすることにより求めた。 In the present invention, the average particle size of the carbon particles is such that 0.5 g of carbon particles are dispersed in 50 g of a 0.2 wt% sodium hexametaphosphate solution and further dispersed by ultrasonic waves, and then a laser light scattering particle size distribution analyzer is used. It was determined by measuring the particle size of the carbon particles in the volume-based distribution and setting the 50% particle size as the average particle size in the cumulative distribution.
また、本発明者らが、炭素粒子を後述する水−脂肪酸のエマルジョンに添加したところ、当該炭素粒子が凝集してしまい、当該水−脂肪酸のエマルジョン中にうまく分散（乳濁あるいは懸濁）しないことが判明した。
本発明者らは当該現象が、炭素粒子の表面に強い親油性を有する有機物が吸着しており、水−脂肪酸エマルジョン中において当該炭素粒子が互い凝集する為、分散が悪くなることによるのではないか、と推論した。
そこで当該推論に基づき、本発明者らが種々の検討を行った結果、当該強い親油性を有する有機物として、アルカンやアルケン等の脂肪酸炭化水素や、アルキルベンゼンなどの芳香族炭化水素が炭素粒子中に含まれていることを知見した。さらに本発明者らは、酸化処理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した後、当該炭素粒子を水−脂肪酸エマルジョンに添加すると、当該炭素粒子の分散性が向上するとの知見を得た。
Further, when the present inventors added carbon particles to a water-fatty acid emulsion described later, the carbon particles aggregate and do not disperse well (emulsion or suspension) in the water-fatty acid emulsion. It has been found.
The present inventors are not due to the phenomenon that the organic particles having strong lipophilicity are adsorbed on the surface of the carbon particles, and the carbon particles aggregate with each other in the water-fatty acid emulsion, resulting in poor dispersion. I inferred.
Therefore, as a result of various studies conducted by the present inventors based on the inference, fatty acid hydrocarbons such as alkanes and alkenes and aromatic hydrocarbons such as alkylbenzenes are contained in the carbon particles as the organic material having strong lipophilicity. It was found that it was included. Furthermore, the present inventors have found that the dispersibility of the carbon particles is improved by removing the lipophilic organic substances adsorbed on the surface of the carbon particles by oxidation treatment and then adding the carbon particles to the water-fatty acid emulsion. Got.
上述した炭素粒子の酸化処理方法としては、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、当該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酸化処理することが出来る。 As the above-described carbon particle oxidation treatment method, wet oxidation treatment is preferably used from the viewpoint of mass productivity, and carbon particles having a large surface area can be uniformly oxidized by the wet oxidation treatment.
湿式酸化処理の方法としては、導電塩を含む水中に炭素粒子を懸濁させた後に、当該水中へ陰極や陽極となる白金電極などを挿入して電気分解を行う方法や、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等、を使用することが出来る。尤も、生産性を考慮すると後者の方法を使用するのが好ましく、水中に添加する炭素粒子の量を１〜２０重量％にするのが好ましい。
後者の方法を適用する場合、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出来るが、過硫酸カリウムがより好ましい。
そして、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出来る。
As a wet oxidation method, after suspending carbon particles in water containing a conductive salt, a method of performing electrolysis by inserting a platinum electrode serving as a cathode or an anode into the water, or putting carbon particles in water For example, a method of adding an appropriate amount of an oxidizing agent after suspending can be used. However, considering the productivity, the latter method is preferably used, and the amount of carbon particles added to water is preferably 1 to 20% by weight.
When the latter method is applied, an oxidizing agent such as nitric acid, hydrogen peroxide, potassium permanganate, potassium persulfate, or sodium perchlorate can be used as the oxidizing agent, but potassium persulfate is more preferable. .
And it is thought that the lipophilic organic substance adhering to the carbon particles is oxidized by the added oxidant to be easily dissolved in water and is appropriately removed from the surface of the carbon particles. Moreover, after performing this wet oxidation treatment, the effect of removing lipophilic organic substances from the surface of the carbon particles can be further enhanced by performing filtration and washing the carbon particles with water.
具体的には、上述した炭素粒子を純水中に投入し、攪拌機で撹拌した混合液中に、酸化剤を添加することにより湿式酸化による酸化処理を行った。その後、混合液をろ紙によりろ別、水洗して酸化処理された炭素粒子を得た。 Specifically, the above-described carbon particles were put into pure water, and an oxidation treatment by wet oxidation was performed by adding an oxidizing agent to a mixed solution stirred with a stirrer. Thereafter, the mixed liquid was filtered with a filter paper and washed with water to obtain oxidized carbon particles.
上述した酸化処理により、炭素粒子の表面から脂肪族炭化水素や芳香族炭化水素等の親油性有機物を除去することが出来る。ここで、上述した酸化処理後の炭素粒子を３００℃に加熱して発生したガスを分析したところ、当該ガス中にはアルカンやアルケンなどの親油性の強い脂肪族炭化水素や、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いないことも判明した。 By the oxidation treatment described above, lipophilic organic substances such as aliphatic hydrocarbons and aromatic hydrocarbons can be removed from the surface of the carbon particles. Here, when the gas generated by heating the carbon particles after the above-described oxidation treatment to 300 ° C. was analyzed, the gas contained in the gas was a highly lipophilic aliphatic hydrocarbon such as alkane or alkene, or a parent such as alkylbenzene. It was also found that oily aromatic hydrocarbons were hardly contained.
（２）脂肪酸
本発明に係る水エマルジョンに用いる脂肪酸は、ステアリン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ベヘン酸、セロチン酸、メリシン酸などの飽和脂肪酸や、ミリストレイン酸、パルミトレイン酸、オレイン酸、ネルボン酸、リノール酸、α−リノレン酸などの不飽和脂肪酸を使用することが出来るが、ステアリン酸を使用するのが好ましい。
(2) Fatty acid The fatty acid used in the water emulsion according to the present invention is a saturated fatty acid such as stearic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, behenic acid, serotic acid, melicic acid, or myristoleic acid. Unsaturated fatty acids such as palmitoleic acid, oleic acid, nervonic acid, linoleic acid, and α-linolenic acid can be used, but stearic acid is preferably used.
（３）水エマルジョンの調製方法
本発明の水エマルジョンは、純水へ、上述した本発明に係る炭素粒子と脂肪酸（必要に応じて界面活性剤と）を添加・撹拌し、炭素粒子と脂肪酸を純水中に（乳濁あるいは懸濁させて）分散させることで得ることが出来る。
(3) Preparation Method of Water Emulsion The water emulsion of the present invention is obtained by adding and stirring the above-described carbon particles and fatty acid (if necessary with a surfactant) to pure water. It can be obtained by dispersing in pure water (emulsion or suspension).
水エマルジョン中における炭素粒子の（添加）量は１〜１０ｇ／Ｌであることが好ましい。
これは、炭素粒子の量が１ｇ／Ｌ以上あれば、Ａｇめっきからなる表層の表面に炭素粒子を含む脂肪酸含有皮膜を形成した際に、十分な量の炭素粒子を表層に形成することが出来、Ａｇめっき材の耐摩耗性が担保されるからである。一方、炭素粒子が１０ｇ／Ｌ以下であれば、炭素粒子を含む脂肪酸含有皮膜の炭素粒子が多過ぎず、接触抵抗が高くなる（１ｍΩを超える）おそれがないからである。
The amount (addition) of carbon particles in the water emulsion is preferably 1 to 10 g / L.
If the amount of carbon particles is 1 g / L or more, a sufficient amount of carbon particles can be formed on the surface layer when a fatty acid-containing film containing carbon particles is formed on the surface of the surface layer made of Ag plating. This is because the wear resistance of the Ag plating material is secured. On the other hand, if the carbon particles are 10 g / L or less, there are not too many carbon particles in the fatty acid-containing coating containing the carbon particles, and there is no possibility of increasing the contact resistance (exceeding 1 mΩ).
水エマルジョン中における脂肪酸の濃度は１０〜５０ｇ／Ｌであることが好ましい。脂肪酸の濃度が１０ｇ／Ｌ以上あれば、十分な厚さ（５ｎｍ以上、好ましくは１０ｎｍ以上）の脂肪酸含有皮膜を形成するからである。一方、脂肪酸の濃度が５０ｇ／Ｌ以下であれば、脂肪酸含有皮膜が（例えば５００ｎｍより）厚くなり過ぎることが無く、接触抵抗上昇を回避出来るからである。 The concentration of the fatty acid in the water emulsion is preferably 10 to 50 g / L. This is because if the concentration of the fatty acid is 10 g / L or more, a fatty acid-containing film having a sufficient thickness (5 nm or more, preferably 10 nm or more) is formed. On the other hand, if the concentration of the fatty acid is 50 g / L or less, the fatty acid-containing film will not be too thick (for example, from 500 nm) and an increase in contact resistance can be avoided.
また、上述した各成分を純水中に分散させ、水エマルジョンとする際は攪拌機を用い、例えば１０分間以上撹拌することが好ましい。 Moreover, when each component mentioned above is disperse | distributed in pure water and it is set as a water emulsion, it is preferable to stir for 10 minutes or more using a stirrer.
（４）Ａｇめっき材に用いる基材およびＡｇめっき
Ａｇめっき材において、基材は導電性や機械強度に優れたＣｕまたはＣｕ合金を、用途に応じて適宜選択することが好ましい。
そして、当該基材にＡｇめっき層を形成する前に、当該基材をアルカリ脱脂や電解脱脂等により前処理し、酸洗により基材の表面を酸活性させるのが好ましい。
また、当該基材にＡｇめっき層を形成する前に、基材とＡｇめっき層との密着性を向上させるとともに、基材の成分のＡｇめっき層への拡散を防止する為に、Ｃｕめっき層またはＮｉめっき層からなる下地層を形成しておくことが好ましい。
(4) Substrate used for Ag plating material and Ag plating In the Ag plating material, it is preferable to appropriately select Cu or Cu alloy having excellent conductivity and mechanical strength depending on the application.
And before forming an Ag plating layer in the said base material, it is preferable to pre-process the said base material by alkali degreasing, electrolytic degreasing, etc., and to acid-activate the surface of a base material by pickling.
Further, before forming the Ag plating layer on the base material, the Cu plating layer is used to improve the adhesion between the base material and the Ag plating layer and to prevent diffusion of the components of the base material into the Ag plating layer. Or it is preferable to form the base layer which consists of a Ni plating layer.
具体的な例としては、まず、基材の表面にＣｕめっき層またはＮｉめっき層からなる下地層を形成し、その後、シアン浴などによるＡｇストライクめっきにより中間層を形成した後、シアン浴などによるＡｇめっきにより表層のＡｇめっき層を形成することが好ましい。
尚、これらのめっきは、電気めっきでも無電解めっきでもよいが、生産効率から電気めっきが好ましい。
As a specific example, first, a base layer made of a Cu plating layer or a Ni plating layer is formed on the surface of a base material, and then an intermediate layer is formed by Ag strike plating using a cyan bath or the like, followed by a cyan bath or the like. It is preferable to form a surface Ag plating layer by Ag plating.
In addition, although these plating may be electroplating or electroless plating, electroplating is preferable from production efficiency.
尚、Ａｇめっき層からなる表層は、Ａｇめっきを形成する際にＡｇめっき液へ添加される微量のＳｅやＳｂ等の添加物を含んでいてもよい。
そして、Ａｇめっき表層の厚さは、０．１〜２０μｍであるのが好ましく、０．３〜１０μｍであるのがさらに好ましく、０．５〜８μｍであるのが最も好ましい。
これは、表層の厚さが厚すぎなければ、Ａｇの使用量が多過ぎず、生産性が担保されるので、製造コストや原料コストが増大しないからである。一方、表層の厚さが薄すぎなければ、耐摩耗性の低下や基材（または下地）成分の拡散による接触抵抗上昇するおそれがないからである。
The surface layer made of the Ag plating layer may contain a trace amount of additives such as Se and Sb added to the Ag plating solution when forming the Ag plating.
The thickness of the Ag plating surface layer is preferably from 0.1 to 20 μm, more preferably from 0.3 to 10 μm, and most preferably from 0.5 to 8 μm.
This is because if the surface layer is not too thick, the amount of Ag used is not too much and the productivity is ensured, so that the manufacturing cost and raw material cost do not increase. On the other hand, if the thickness of the surface layer is not too thin, there is no risk of a decrease in wear resistance and an increase in contact resistance due to diffusion of the base material (or base) component.
ＣｕまたはＮｉからなる下地層の厚さは、０．０５〜３μｍであるのが好ましく、０．１〜２μｍであるのがさらに好ましい。
これは、ＣｕまたはＮｉからなる下地層の厚さが３μｍ以下であれば、Ａｇめっき材の曲げ加工性が担保されることによる。一方、下地層の厚さが０．０５μｍ以上であれば、基材と表層の密着性が担保されると共に、基材の成分の拡散を防止する効果が担保されることによる。
The thickness of the base layer made of Cu or Ni is preferably 0.05 to 3 μm, and more preferably 0.1 to 2 μm.
This is because the bendability of the Ag plating material is ensured if the thickness of the base layer made of Cu or Ni is 3 μm or less. On the other hand, when the thickness of the base layer is 0.05 μm or more, the adhesion between the base material and the surface layer is ensured and the effect of preventing the diffusion of the components of the base material is ensured.
（５）Ａｇめっき材への脂肪酸含有皮膜の形成方法
本発明に係るＡｇめっき材への、脂肪酸含有皮膜の形成方法としては、上述のＡｇめっき材を本発明の水エマルジョンに浸漬した後、乾燥させて水分を除去し、炭素粒子を含む脂肪酸含有皮膜を形成することが好ましい。さらに、浸漬中は水エマルジョンを撹拌することが好ましい。
(5) Method for forming fatty acid-containing film on Ag plating material As a method for forming a fatty acid-containing film on Ag plating material according to the present invention, the above-mentioned Ag plating material is immersed in the water emulsion of the present invention and then dried. It is preferable to remove water to form a fatty acid-containing film containing carbon particles. Furthermore, it is preferable to stir the water emulsion during immersion.
具体的には、攪拌機を用いて水エマルジョンを撹拌しながら、上述したＡｇめっき層を設けたＡｇめっき材を５秒間以上浸漬することが好ましい。
当該浸漬後、水エマルジョンへの浸漬を行ったＡｇめっき層を設けたＡｇめっき材を、例えば、３０〜６０℃程度の温風により乾燥し、表面の水分を除去する。その後、当該Ａｇめっき材を７０〜１３０℃程度の高温下に置き、表面の水分を除去することが好ましい。
Specifically, it is preferable to immerse the Ag plating material provided with the above-described Ag plating layer for 5 seconds or more while stirring the water emulsion using a stirrer.
After the immersion, the Ag plating material provided with the Ag plating layer that has been immersed in a water emulsion is dried by, for example, hot air of about 30 to 60 ° C. to remove moisture on the surface. Then, it is preferable to place the Ag plating material at a high temperature of about 70 to 130 ° C. to remove moisture on the surface.
また、Ａｇめっき層上の炭素粒子の付着状態について、レーザー顕微鏡によりＡｇめっき層の表面を観察したとき、観察領域の全面積に対して、１０〜８０％程度の面積率で炭素粒子が付着しているのが認められることが好ましい。面積率が小さすぎないことから耐摩耗性が十分に向上し、大きすぎないことから接触抵抗が増大する恐れがないからである。 In addition, regarding the adhesion state of the carbon particles on the Ag plating layer, when the surface of the Ag plating layer is observed with a laser microscope, the carbon particles adhere with an area ratio of about 10 to 80% with respect to the total area of the observation region. It is preferable to be recognized. This is because the wear resistance is sufficiently improved because the area ratio is not too small, and the contact resistance is not increased because it is not too large.
乾燥後のＡｇめっき材において、上述した脂肪酸含有皮膜の厚さは５〜５００ｎｍであることが好ましい。
これは、脂肪酸含有皮膜の厚さが５ｎｍ以上あれば、摩擦が小さくなり耐摩耗性が担保されるかである。一方、脂肪酸含有皮膜の厚さが５００ｎｍ以下であれば、接触抵抗上昇を回避出来好ましいからである。
In the dried Ag plating material, the thickness of the fatty acid-containing film described above is preferably 5 to 500 nm.
If the thickness of the fatty acid-containing film is 5 nm or more, friction is reduced and wear resistance is ensured. On the other hand, if the thickness of the fatty acid-containing film is 500 nm or less, an increase in contact resistance can be avoided, which is preferable.
（６）評価
本発明に係るＡｇ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（雄端子としての試験片）とすると共に、他方の試験片をインデント加工（Ｒ＝１．５ｍｍの半球状の打ち出し加工）してインデント付き試験片（雌端子としての試験片）とした。
当該インデント付き試験片を、荷重３Ｎで平板状試験片の表面に押し付けながら、摺動速度１００ｍｍ／分、摺動距離５ｍｍで３００往復および５００往復摺動させる摺動試験後において、基材が表面に露出するか否かについて評価した。
すると、本発明に係るＡｇめっき材は基材が表面に露出せず、Ａｇめっき材の耐摩耗性が高いことが判明した。
つまり、本発明に係るＡｇめっき材は実用上十分に接触抵抗が低く、さらに摺動後も基材が表面に露出しない為、摺動後の経時変化による表面に露出した基材の酸化等の変質を回避することが出来る。
以上より、本発明に係るＡｇめっき材は、接点や端子部品などの電子部材に好適であるといえる。
(6) Evaluation Two test pieces were cut out from the Ag plating material according to the present invention, and one test piece was used as a flat test piece (a test piece as a male terminal), and the other test piece was indented ( A test piece with indentation (test piece as a female terminal) was obtained by R = 1.5 mm hemispherical punching.
After the sliding test in which the indented test piece is pressed against the surface of the flat test piece with a load of 3 N and the sliding speed is 100 mm / min and the sliding distance is 5 mm, the substrate is reciprocated 300 times and 500 times. It was evaluated whether or not it was exposed.
Then, it turned out that the Ag plating material according to the present invention does not expose the substrate to the surface, and the Ag plating material has high wear resistance.
That is, the Ag plating material according to the present invention has a practically low contact resistance, and further, the base material is not exposed to the surface even after sliding. Alteration can be avoided.
From the above, it can be said that the Ag plating material according to the present invention is suitable for electronic members such as contacts and terminal parts.
以下、実施例を参照しながら本発明をより具体的に説明する。
実施例１〜３においては、（１）炭素粒子の表面への酸化処理工程、（２）水エマルジョンの調製工程、（３）基材への前処理工程、（４）被めっき材へのＮｉめっき工程、（５）被めっき材へのＡｇストライクめっき工程、（６）被めっき材へのＡｇめっき工程、（７）Ａｇめっき材の水エマルジョンへの浸漬工程、（８）摺動摩耗試験および評価、の各工程を実施した。一方、比較例１においては、（７）Ａｇめっき材の水エマルジョンへの浸漬工程、を実施しなった。また、比較例２、３においては、水エマルジョンとして炭素粒子を含まない水エマルジョンを用いた。
Hereinafter, the present invention will be described more specifically with reference to examples.
In Examples 1 to 3, (1) an oxidation treatment step on the surface of carbon particles, (2) a preparation step of a water emulsion, (3) a pretreatment step on a substrate, and (4) Ni on a material to be plated Plating step, (5) Ag strike plating step on the material to be plated, (6) Ag plating step on the material to be plated, (7) dipping step of Ag plating material in water emulsion, (8) sliding wear test and Each process of evaluation was implemented. On the other hand, in the comparative example 1, (7) the immersion process to the water emulsion of Ag plating material was not implemented. In Comparative Examples 2 and 3, a water emulsion containing no carbon particles was used as the water emulsion.
［実施例１］
（１）炭素粒子の表面への酸化処理工程
炭素粒子として、平均粒径５μｍの鱗片状の黒鉛粒子（エスイーシー社製のカーボンＳＮ−５）を用意した。
[Example 1]
(1) Oxidation treatment process to the surface of carbon particles As carbon particles, scaly graphite particles having an average particle diameter of 5 μm (carbon SN-5 manufactured by ESC Corporation) were prepared.
次に、黒鉛粒子１８０ｇを３Ｌの純水中に投入し、この混合液を撹拌しながら５０℃に昇温させた。次いで酸化剤として０．１モルの過硫酸カリウム水溶液１．２Ｌを徐々に滴下した後、さらに２時間攪拌して、湿式酸化による酸化処理を行った。その後、ろ紙によりろ別を行い、ろ別された黒鉛粒子を水洗し、実施例１に係る酸化処理済み黒鉛粒子を得た。
尚、黒鉛粒子の平均粒径は、黒鉛粒子０．５ｇを０．２重量％のヘキサメタリン酸ナトリウム溶液５０ｇに分散させ、さらに超音波により分散させた後、レーザー光散乱粒度分布測定装置を用いて体積基準分布の粒径を測定し、累積分布で５０％の粒径を平均粒径とすることにより求めた。
Next, 180 g of graphite particles were put into 3 L of pure water, and the mixture was heated to 50 ° C. while stirring. Next, 1.2 L of a 0.1 mol potassium persulfate aqueous solution as an oxidizing agent was gradually added dropwise, and the mixture was further stirred for 2 hours to perform an oxidation treatment by wet oxidation. Then, it filtered with the filter paper, the graphite particle filtered off was washed with water, and the oxidation-treated graphite particle which concerns on Example 1 was obtained.
The average particle size of the graphite particles was determined by dispersing 0.5 g of graphite particles in 50 g of a 0.2 wt% sodium hexametaphosphate solution and further dispersing with ultrasonic waves, and then using a laser light scattering particle size distribution measuring device. The particle size was determined by measuring the particle size of the volume-based distribution and setting the particle size of 50% in the cumulative distribution as the average particle size.
（２）水エマルジョンの調製工程
３１ｇのステアリン酸（脂肪酸）を含む水エマルジョン浴１Ｌ中に、２ｇの酸化処理済み黒鉛粒子を添加した。そして、当該水エマルジョン浴をスターラーにて５００ｒｐｍで攪拌して分散させ、酸化処理済み黒鉛粒子を含む水エマルジョンを調製し、実施例１に係る水エマルジョン（潤滑剤）を得た。
尚、実施例１に係る水エマルジョン中の黒鉛粒子量を表２に記載する。
(2) Preparation Step of Water Emulsion 2 g of oxidized graphite particles was added to 1 L of water emulsion bath containing 31 g of stearic acid (fatty acid). Then, the water emulsion bath was stirred and dispersed at 500 rpm with a stirrer to prepare a water emulsion containing oxidized graphite particles, and a water emulsion (lubricant) according to Example 1 was obtained.
The amount of graphite particles in the water emulsion according to Example 1 is shown in Table 2.
（３）基材への前処理工程
基材（被めっき材）として、７０ｍｍ×５０ｍｍ×０．６ｍｍの純銅金属基板を用意した。
当該被めっき材とＳＵＳ板とをアルカリ脱脂液に入れ、被めっき材を陰極、ＳＵＳ板を陽極として電圧５Ｖを印加し、３０秒間電解脱脂を行った。
当該電解脱脂の後、被めっき材を水洗し、さらに３％硫酸水溶液中で１５秒間酸洗を行って、電解脱脂と酸洗とを施した被めっき材を得た。
(3) Pretreatment process to base material A 70 mm × 50 mm × 0.6 mm pure copper metal substrate was prepared as a base material (material to be plated).
The material to be plated and the SUS plate were put in an alkaline degreasing solution, and a voltage of 5 V was applied using the material to be plated as a cathode and the SUS plate as an anode, and electrolytic degreasing was performed for 30 seconds.
After the electrolytic degreasing, the material to be plated was washed with water, and further pickled in a 3% sulfuric acid aqueous solution for 15 seconds to obtain a material to be plated subjected to electrolytic degreasing and pickling.
（４）被めっき材へのＮｉめっき工程
濃度５０４ｇ／Ｌのスルファミン酸ニッケル四水和物と、濃度２５ｇ／Ｌの塩化ニッケルと、濃度３５ｇ／Ｌのホウ酸とを含む、Ｎｉめっき水溶液を調製した。
前記Ｎｉめっき水溶液中において、前記電解脱脂と酸洗とを施した被めっき材を陰極、ＳＫニッケル電極板を陽極とした。そして、スターラを用いて前記Ｎｉめっき水溶液を５００ｒｐｍで撹拌しつつ、電流密度５Ａ／ｄｍ２、液温５５℃で、前記被めっき材へＮｉめっきを行い、膜厚１μｍのＮｉめっきを施した被めっき材を得た。
(4) Ni plating step on the material to be plated An Ni plating aqueous solution containing nickel sulfamate tetrahydrate having a concentration of 504 g / L, nickel chloride having a concentration of 25 g / L, and boric acid having a concentration of 35 g / L is prepared. did.
In the Ni plating aqueous solution, the plated material subjected to the electrolytic degreasing and pickling was used as a cathode, and the SK nickel electrode plate was used as an anode. Then, while stirring the Ni plating aqueous solution at 500 rpm using a stirrer, Ni plating was performed on the material to be plated at a current density of 5 A / dm 2 and a liquid temperature of 55 ° C., and Ni plating with a thickness of 1 μm was applied. A plating material was obtained.
（５）被めっき材へのＡｇストライクめっき工程
濃度３ｇ／Ｌのシアン化銀カリウムと、濃度９０ｇ／Ｌのシアン化カリウムとを含む、Ａｇストライクめっき水溶液を調製した。
前記Ｎｉめっきを施した被めっき材を陰極、白金で被覆したチタン電極板を陽極とした。そして、スターラを用いて前記Ａｇストライクめっき水溶液を５００ｒｐｍで撹拌しつつ、電流密度２Ａ／ｄｍ２、液温１８℃で１０秒間、前記Ｎｉめっきを施した被めっき材へＡｇストライクめっきを行い、Ａｇストライクめっきを施した被めっき材を得た。
(5) Ag Stroke Plating Step for Plated Material An aqueous solution of Ag strike plating containing silver potassium cyanide at a concentration of 3 g / L and potassium cyanide at a concentration of 90 g / L was prepared.
The material to be plated with Ni was used as a cathode, and a titanium electrode plate coated with platinum was used as an anode. Then, while stirring the Ag strike plating aqueous solution at 500 rpm using a stirrer, Ag strike plating is performed on the plated material subjected to the Ni plating at a current density of 2 A / dm 2 and a liquid temperature of 18 ° C. for 10 seconds. A material to be plated that was subjected to strike plating was obtained.
（６）被めっき材へのＡｇめっき工程
濃度１７５ｇ／Ｌのシアン化銀カリウムと、濃度９５ｇ／Ｌのシアン化カリウムと、濃度１００ｍｇ／Ｌのセレノシアン酸カリウム（５５ｍｇ／Ｌのセレン含有）とを含む、Ａｇめっき水溶液を調製した。
上述したＡｇストライクめっきを施した被めっき材を陰極、銀電極板を陽極として、当該Ａｇめっき水溶液に浸漬した。そして、スターラを用いてＡｇめっき水溶液を５００ｒｐｍで撹拌しつつ、電流密度５Ａ／ｄｍ２、液温１８℃で、前記Ａｇストライクめっきを施した被めっき材へＡｇめっきを行い、膜厚５μｍのＡｇめっきを施したＡｇめっき材を得た。
(6) Ag plating step on the material to be plated, including silver potassium cyanide having a concentration of 175 g / L, potassium cyanide having a concentration of 95 g / L, and potassium selenocyanate having a concentration of 100 mg / L (containing 55 mg / L of selenium). An aqueous Ag plating solution was prepared.
The above-described material subjected to Ag strike plating was immersed in the Ag plating aqueous solution using the cathode and the silver electrode plate as the anode. Then, while stirring the Ag plating aqueous solution at 500 rpm using a stirrer, Ag plating is performed on the plated material subjected to the Ag strike plating at a current density of 5 A / dm 2 and a liquid temperature of 18 ° C. A plated Ag material was obtained.
（７）Ａｇめっき材の水エマルジョンへの浸漬工程
上述した実施例１に係る水エマルジョン（潤滑剤）をスターラにより５００ｒｐｍで攪拌している浴中へ、上述したＡｇめっき材を１２０秒間浸漬した。尚、当該後処理時間を表２に記載する。
そして当該浸漬後、Ａｇめっき材を浴から引き上げ、その表面に対してドライヤーで温風を当て、表面の水分を完全に除去した。その後、Ａｇめっき材を、加熱乾燥機（アズワン株式会社製のスチール強制対流乾燥機）により大気中において１１０℃で４５秒間加熱して乾燥させ、Ａｇめっき材の表面に黒鉛粒子とステアリン酸を含む脂肪酸含有皮膜を形成して、実施例１に係るＡｇめっき材試料を得た。
(7) Immersion Step of Ag Plating Material in Water Emulsion The above-described Ag plating material was immersed in a bath in which the water emulsion (lubricant) according to Example 1 described above was stirred at 500 rpm with a stirrer for 120 seconds. The post-processing time is shown in Table 2.
And after the said immersion, the Ag plating material was pulled up from the bath, the hot air was applied with the dryer with respect to the surface, and the water | moisture content of the surface was removed completely. Thereafter, the Ag plating material is dried by heating at 110 ° C. for 45 seconds in the atmosphere with a heating dryer (steel forced convection dryer manufactured by As One Co., Ltd.), and the surface of the Ag plating material contains graphite particles and stearic acid. A fatty acid-containing film was formed, and an Ag plating material sample according to Example 1 was obtained.
（８）摺動摩耗試験および評価
上述した実施例１に係るＡｇめっき材試料から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（雄端子としての試験片）とし、他方の試験片をインデント加工（Ｒ＝１．５ｍｍの半球状の打ち出し加工）してインデント付き試験片（雌端子としての試験片）とした。
摺動試験装置である精密摺動試験機（株式会社山崎精機研究所製のＣＲＳ−Ｇ２０５０−ＤＷＡ型）のステージに平板状試験片を固定し、その平板状試験片へインデント付き試験片を接触させた。そして、荷重３Ｎでインデント付き試験片を平板状試験片の表面に押しつけながら、平板状試験片を固定したステージを水平方向に摺動速度１００ｍｍ／分、摺動距離５ｍｍで、３００往復および５００往復させる摺動試験を行なった。尚、当該摺動試験条件を表１に示す。
(8) Sliding wear test and evaluation Two test pieces were cut out from the Ag plating material sample according to Example 1 described above, and one test piece was used as a flat test piece (test piece as a male terminal), and the other The test piece was indented (R = 1.5 mm hemispherical punching process) to obtain a test piece with indent (a test piece as a female terminal).
A flat test piece is fixed to the stage of a precision sliding tester (CRS-G2050-DWA type manufactured by Yamazaki Seiki Laboratory Co., Ltd.), which is a sliding test device, and the indented test piece is brought into contact with the flat test piece. I let you. Then, while pressing the indented test piece against the surface of the flat test piece with a load of 3N, the stage on which the flat test piece is fixed is horizontally reciprocated at a sliding speed of 100 mm / min, a sliding distance of 5 mm, and 300 reciprocations and 500 reciprocations. A sliding test was performed. The sliding test conditions are shown in Table 1.
摺動試験後の実施例１に係るＡｇめっき材試料の平板状試験片の表面を、デジタルマイクロスコープ（（株）キーエンス製：ＶＨＸ−１０００）を用い、（×４００）倍率にて観察した。そして、当該観察において銅素地露出の有無を観察し耐摩耗性を評価した。
そして、銅素地露出が無ければ耐摩耗性が〇、銅素地露出が有れば耐摩耗性が×と評価したところ、３００往復後、５００往復後のいずれも銅素地露出が無く、耐摩耗性は〇であった。尚、当該評価結果を表２に記載する。
The surface of the flat test piece of the Ag plating material sample according to Example 1 after the sliding test was observed at a magnification of (× 400) using a digital microscope (manufactured by Keyence Corporation: VHX-1000). And the presence or absence of copper base exposure was observed in the said observation, and abrasion resistance was evaluated.
And, when there is no copper substrate exposure, the wear resistance is ◯, and when there is copper substrate exposure, the wear resistance is evaluated as x. After 300 reciprocations and after 500 reciprocations, there is no copper substrate exposure and wear resistance. Was 〇. The evaluation results are shown in Table 2.
一方、上述した摺動摩耗試験中において、実施例１に係るＡｇめっき材試料の接触抵抗を測定した。そして当該摺動期間中における接触抵抗の最大値をもって、実施例１に係るＡｇめっき材試料の接触抵抗とした。その結果、３００往復後および５００往復後の接触抵抗は、０．９１ｍΩ（３００往復）、０．８９ｍΩ（５００往復）であり良好であった。尚、当該測定結果を表２に記載する。
また、Ａｇめっき層上の炭素粒子の付着状態について、レーザー顕微鏡によりＡｇめっき層の表面を観察した結果、観察領域（６５０μｍ×４９０μｍ）の全面積に対して炭素粒子の付着が認められる領域の面積率は７０％であった。
On the other hand, the contact resistance of the Ag plating material sample according to Example 1 was measured during the above-described sliding wear test. The maximum value of the contact resistance during the sliding period was taken as the contact resistance of the Ag plating material sample according to Example 1. As a result, the contact resistances after 300 reciprocations and 500 reciprocations were 0.91 mΩ (300 reciprocations) and 0.89 mΩ (500 reciprocations), which were favorable. The measurement results are shown in Table 2.
Moreover, about the adhesion state of the carbon particle on Ag plating layer, as a result of observing the surface of Ag plating layer with a laser microscope, the area of the area | region where carbon particle adhesion is recognized with respect to the total area of an observation area | region (650 micrometers x 490 micrometers) The rate was 70%.
［実施例２］
上述した「（７）Ａｇめっき材の水エマルジョンへの浸漬工程」におけるＡｇめっき材の浸漬時間を１０秒間とした以外は、実施例１と同様の操作を行って、実施例２に係るＡｇめっき材試料を得た。
そして、実施例２に係るＡｇめっき材試料へ、実施例１と同様に摺動試験を行い、摺動摩耗試験後の接触抵抗測定を行った。
[Example 2]
The same operation as in Example 1 was performed except that the immersion time of the Ag plating material in the “(7) immersion process of Ag plating material in water emulsion” described above was set to 10 seconds, and Ag plating according to Example 2 was performed. A material sample was obtained.
And the sliding test was done to the Ag plating material sample which concerns on Example 2 similarly to Example 1, and the contact resistance measurement after a sliding wear test was performed.
その結果、３００往復後および５００往復後も基材の表面の露出はなく耐摩耗性は〇であった。接触抵抗は０．６６ｍΩ（３００往復）、０．６６ｍΩ（５００往復）であり良好であった。また、実施例１と同様にＡｇめっき層の表面を観察した結果、観察領域の全面積に対して炭素粒子の付着が認められる領域の面積率は２０％であった。尚、当該作製条件および評価・測定結果を表２に記載する。 As a result, the surface of the substrate was not exposed even after 300 reciprocations and 500 reciprocations, and the wear resistance was ◯. The contact resistance was 0.66 mΩ (300 reciprocations) and 0.66 mΩ (500 reciprocations). Moreover, as a result of observing the surface of the Ag plating layer in the same manner as in Example 1, the area ratio of the region where the adhesion of the carbon particles was recognized with respect to the entire area of the observation region was 20%. The production conditions and evaluation / measurement results are shown in Table 2.
また、得られたＡｇめっき材について、熱分解型ガスクロマトグラフ質量分析計によりＡｇめっき皮膜の表面の定性分析を行ったところ、Ａｇめっき皮膜の表面にステアリン酸を含む脂肪酸含有が確認された。
また、本発明の脂肪酸含有皮膜の膜厚の測定として、アルゴンイオンを照射することによりＡｇめっき皮膜の表面（の直径１００μｍの分析エリア、黒鉛粒子の存在しない部分）をスパッタし、オージェ電子分光分析装置（日本電子株式会社製のＪＡＭＰ−７８００）を使用してオージェ電子分光法（ＡＥＳ）による深さプロファイル分析を行った。すると、Ａｇめっき皮膜の表面に脂肪酸含有皮膜が付着しているのが確認された。当該脂肪酸含有皮膜の厚さを、上述したスパッタリング時間からＳｉＯ２の標準試料のスパッタリング速度（５ｎｍ／分）に換算して求めたところ、１２ｎｍであった。
Moreover, about the obtained Ag plating material, when the qualitative analysis of the surface of Ag plating film was performed with the thermal decomposition type gas chromatograph mass spectrometer, fatty acid containing stearic acid was confirmed in the surface of Ag plating film.
In addition, as a measurement of the film thickness of the fatty acid-containing film of the present invention, the surface of the Ag plating film (analysis area with a diameter of 100 μm, a portion where no graphite particles exist) is sputtered by irradiating argon ions, and Auger electron spectroscopy analysis Depth profile analysis by Auger electron spectroscopy (AES) was performed using an apparatus (JAMP-7800 manufactured by JEOL Ltd.). Then, it was confirmed that the fatty acid containing film has adhered to the surface of the Ag plating film. The thickness of the fatty acid-containing coating, was determined by converting from the sputtering time above the sputtering rate of the standard sample of SiO 2 (5 nm / min) was 12 nm.
［実施例３］
上述した「（１）炭素粒子の表面への酸化処理工程」の酸化処理済み黒鉛粒子を含む水エマルジョン液中における黒鉛粒子の添加量を５ｇとし、後処理工程におけるＡｇめっき材の水エマルジョンへの浸漬時間を１０秒間とした以外は、実施例１と同様の操作を行って、実施例３に係るＡｇめっき材試料を得た。
[Example 3]
The added amount of graphite particles in the water emulsion liquid containing the oxidized graphite particles in “(1) Oxidation treatment process on the surface of carbon particles” described above is 5 g, and the Ag plating material in the water treatment emulsion in the post-treatment process is added to the water emulsion. An Ag plating material sample according to Example 3 was obtained by performing the same operation as in Example 1 except that the immersion time was 10 seconds.
そして、実施例３に係るＡｇめっき材試料へ実施例１と同様に摺動試験を行い、摺動摩耗試験後の接触抵抗測定を行った。
その結果、３００往復後および５００往復後も基材の表面の露出はなく、耐摩耗性は〇であった。接触抵抗は０．５８ｍΩ（３００往復）、０．７３ｍΩ（５００往復）であり良好であった。また、実施例１と同様にＡｇめっき層の表面を観察した結果、観察領域の全面積に対して炭素粒子の付着が認められる領域の面積率は５０％であった。尚、当該作製条件および評価・測定結果を表２に記載する。
And the sliding test was done to the Ag plating material sample which concerns on Example 3 similarly to Example 1, and the contact resistance measurement after a sliding wear test was performed.
As a result, the surface of the substrate was not exposed even after 300 reciprocations and 500 reciprocations, and the wear resistance was ◯. The contact resistance was 0.58 mΩ (300 reciprocations) and 0.73 mΩ (500 reciprocations). Moreover, as a result of observing the surface of the Ag plating layer in the same manner as in Example 1, the area ratio of the region where the adhesion of the carbon particles was recognized with respect to the entire area of the observation region was 50%. The production conditions and evaluation / measurement results are shown in Table 2.
また、実施例２と同様の方法で、実施例３に係る脂肪酸含有皮膜の厚さを測定したところ１２ｎｍであった。
また、５００回往復摺動後における実施例３に係るめっき面の（×４００）倍率の外観写真を図１に示す。図１より５００回往復摺動後におけるＡｇめっき面において、基材（銅）の露出がないことが確認出来た。
Moreover, it was 12 nm when the thickness of the fatty-acid containing film | membrane which concerns on Example 3 was measured by the method similar to Example 2. FIG.
Moreover, the external appearance photograph of (x400) magnification of the plating surface which concerns on Example 3 after 500 times reciprocating sliding is shown in FIG. From FIG. 1, it was confirmed that the substrate (copper) was not exposed on the Ag plating surface after 500 reciprocating slides.
［比較例１］
上述した「（７）Ａｇめっき材の水エマルジョンへの浸漬工程」を実施しなかった以外は、実施例１と同様の操作を行って、比較例１に係るＡｇめっき材試料を得た。
そして、比較例１に係るＡｇめっき材試料へ、実施例１と同様に摺動試験を行い、摺動摩耗試験後の接触抵抗測定を行った。
その結果、３００往復後および５００往復後のどちらにおいても、基材（Ｃｕ）の表面が露出していて耐摩耗性は×であった。接触抵抗は０．３５ｍΩ（３００往復）、０．４０ｍΩ（５００往復）であり良好であった。尚、当該作製条件および評価・測定結果を表２に記載する。
[Comparative Example 1]
An Ag plating material sample according to Comparative Example 1 was obtained by performing the same operation as in Example 1 except that the above-described “(7) Step of immersing Ag plating material in water emulsion” was not performed.
And the sliding test was done to the Ag plating material sample which concerns on the comparative example 1 similarly to Example 1, and the contact resistance measurement after a sliding wear test was done.
As a result, both after 300 reciprocations and after 500 reciprocations, the surface of the substrate (Cu) was exposed and the wear resistance was x. The contact resistance was good, 0.35 mΩ (300 reciprocations) and 0.40 mΩ (500 reciprocations). The production conditions and evaluation / measurement results are shown in Table 2.
［比較例２］
上述した「（７）Ａｇめっき材の水エマルジョンへの浸漬工程」において、酸化処理済み黒鉛粒子を含まないエマルジョン液中へ、Ａｇめっき材を１２０秒間浸漬した以外は、実施例１と同様の操作を行って、比較例２に係るＡｇめっき材試料を得た。
そして、比較例２に係るＡｇめっき材試料へ、実施例１と同様に摺動試験を行い、摺動摩耗試験後の接触抵抗測定を行った。
その結果、３００往復後には基材の表面の露出はなく耐摩耗性は〇であったが、５００往復後に基材の表面の露出が観察され耐摩耗性は×であった。接触抵抗は１．３７ｍΩ（３００往復）、１．９８ｍΩ（５００往復）であり高かった。尚、当該作製条件および評価・測定結果を表２に記載する。
[Comparative Example 2]
In the above-mentioned “(7) Step of immersing Ag plating material in water emulsion”, the same operation as in Example 1 except that the Ag plating material was immersed for 120 seconds in an emulsion solution containing no oxidized graphite particles. The Ag plating material sample which concerns on the comparative example 2 was obtained.
And the sliding test was done to the Ag plating material sample which concerns on the comparative example 2 similarly to Example 1, and the contact resistance measurement after a sliding wear test was done.
As a result, the surface of the base material was not exposed after 300 reciprocations and the wear resistance was ◯. However, the exposure of the surface of the base material was observed after 500 reciprocations, and the wear resistance was x. The contact resistance was 1.37 mΩ (300 reciprocations) and 1.98 mΩ (500 reciprocations), which was high. The production conditions and evaluation / measurement results are shown in Table 2.
［比較例３］
上述した「（７）Ａｇめっき材の水エマルジョンへの浸漬工程」において、酸化処理済み黒鉛粒子を含まないエマルジョン液中へ、Ａｇめっき材を１０秒間浸漬した以外は、実施例１と同様の操作を行って、比較例３に係るＡｇめっき材試料を得た。
そして、比較例３に係るＡｇめっき材試料へ、実施例１と同様に摺動試験を行い、摺動摩耗試験後の接触抵抗測定を行った。
その結果、３００往復後、５００往復後のいずれも基材の表面の露出が観察され耐摩耗性は×であった。接触抵抗は１．１７ｍΩ（３００往復）、１．５０ｍΩ（５００往復）であり高かった。尚、当該作製条件および評価・測定結果を表２に記載する。
[Comparative Example 3]
In the above-mentioned “(7) Step of immersing Ag plating material in water emulsion”, the same operation as in Example 1 except that the Ag plating material was immersed for 10 seconds in an emulsion solution containing no oxidized graphite particles. The Ag plating material sample which concerns on the comparative example 3 was obtained.
And the sliding test was done to the Ag plating material sample which concerns on the comparative example 3 similarly to Example 1, and the contact resistance measurement after a sliding wear test was done.
As a result, after 300 reciprocations and 500 reciprocations, the surface of the substrate was exposed and the wear resistance was x. The contact resistance was 1.17 mΩ (300 reciprocations) and 1.50 mΩ (500 reciprocations), which were high. The production conditions and evaluation / measurement results are shown in Table 2.
また、実施例２と同様の方法で脂肪酸含有皮膜の厚さを測定したところ１２ｎｍであった。
また、５００回往復摺動後における比較例３に係るめっき面の（×４００）倍率の外観写真を図２に示す。図２より、５００回往復摺動後におけるめっき面では、めっきが完全に摩耗し、下地の基材（銅）が露出していた。
Moreover, it was 12 nm when the thickness of the fatty acid containing membrane | film | coat was measured by the method similar to Example 2. FIG.
Moreover, the external appearance photograph of (x400) magnification of the plating surface which concerns on the comparative example 3 after 500 times reciprocating sliding is shown in FIG. From FIG. 2, the plating was completely worn on the plated surface after 500 reciprocating slides, and the underlying base material (copper) was exposed.
［まとめ］
実施例１〜３、表２、および図１より、本発明に係るＡｇめっき材に炭素粒子を含む脂肪酸含有皮膜が形成されたＡｇめっき素材においては、３００回および５００回の摺動摩耗試験後においても、銅素地露出が無く耐摩耗性は良好であった。また、３００回および５００回の摺動摩耗試験中における接触抵抗の上昇も回避されており良好であった。
[Summary]
From Examples 1 to 3, Table 2, and FIG. 1, in the Ag plating material in which the fatty acid-containing film containing carbon particles is formed on the Ag plating material according to the present invention, after the sliding wear test of 300 times and 500 times Also, the copper substrate was not exposed and the wear resistance was good. In addition, an increase in contact resistance during the 300 and 500 sliding wear tests was also avoided, which was good.
Claims (14)
A contact or terminal component using the Ag plating material according to claim 9.
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| JPS59126465A (en) * | 1983-01-08 | 1984-07-21 | Toshiba Silicone Co Ltd | Pressure-sensitive electrically conductive silicone rubber composition |
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