JP2007277715A

JP2007277715A - Plated material and electric/electronic component using the same

Info

Publication number: JP2007277715A
Application number: JP2007068018A
Authority: JP
Inventors: Kazuo Yoshida; 和生吉田; Kyota Suzai; 京太須齋; Yoshiaki Ogiwara; 吉章荻原; Gakuo Uno; 岳夫宇野
Original assignee: Furukawa Electric Co Ltd
Current assignee: Furukawa Electric Co Ltd
Priority date: 2006-03-17
Filing date: 2007-03-16
Publication date: 2007-10-25
Anticipated expiration: 2027-03-16
Also published as: JP4653133B2

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plated material suitable for the sliding part of a connection terminal and an electric/electronic component such as a fitting type multipolar connector whose inserting/extracting properties are improved by using the plated material. <P>SOLUTION: The plated material 7 is obtained by arranging a base layer 2 composed of Ni or the like on an electrically-conductive substrate 1, a copper-based layer 3 composed of Cu or a Cu alloy on the base layer, an intermediate layer 4 composed of a Cu-Sn intermetallic compound on the copper-based layer, a tin-based layer 5 composed of Sn or a Sn alloy on the intermediate layer, in this order, and an outermost layer 6 composed of the Cu-Sn intermetallic compound on the tin-based layer. When the plated material 7 is used as a material for the sliding surface of a terminal or the like, the inserting/extracting properties of the terminal can be improved advantageously since the outermost layer 6 is composed of the hard Cu-Sn intermetallic compound and a fretting phenomenon is hardly caused even when the contact pressure between terminals is made low. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、接続端子の摺動部などに好適なめっき材料、および前記めっき材料を用いて挿抜性を改善した、嵌合型多極コネクタなどの電気電子部品に関する。 The present invention relates to a plating material suitable for a sliding portion of a connection terminal and the like, and an electrical / electronic component such as a fitting-type multipolar connector whose insertion / removability is improved by using the plating material.

銅（Ｃｕ）、銅合金などの導電性基体（以下、適宜、基体と記す。）上に錫（Ｓｎ）、錫合金などのめっき層を設けためっき材料は、基体の優れた導電性と強度、およびめっき層の優れた電気接続性、耐食性およびはんだ付け性を備えた高性能導体として知られており、各種の端子やコネクタなどに広く用いられている。このめっき材料は、通常、亜鉛（Ｚｎ）などの基体の合金成分（以下、適宜、基体成分と記す。）が前記めっき層に拡散するのを防止するため、基体上にバリア機能を有するニッケル（Ｎｉ）、コバルト（Ｃｏ）、鉄（Ｆｅ）などが下地めっきされる。 A plating material in which a plating layer such as tin (Sn) or tin alloy is provided on a conductive substrate such as copper (Cu) or a copper alloy (hereinafter referred to as a substrate as appropriate) has excellent conductivity and strength of the substrate. In addition, it is known as a high-performance conductor having excellent electrical connectivity, corrosion resistance, and solderability of the plating layer, and is widely used for various terminals and connectors. This plating material is usually nickel (which has a barrier function on the substrate) in order to prevent the alloy component of the substrate such as zinc (Zn) (hereinafter, appropriately referred to as a substrate component) from diffusing into the plating layer. Ni), cobalt (Co), iron (Fe), and the like are subjected to base plating.

自動車のエンジンルーム内などの高温環境下では、端子表面のＳｎめっき層はＳｎが易酸化性のため表面に酸化皮膜が形成されるが、この酸化皮膜は脆いため端子接続時に破れ、その下の未酸化Ｓｎめっき層が露出して良好な電気接続性が得られる。 In a high temperature environment such as in an automobile engine room, the Sn plating layer on the surface of the terminal has an oxide film formed on the surface because Sn is easily oxidizable, but this oxide film is brittle and breaks when the terminal is connected. The unoxidized Sn plating layer is exposed and good electrical connectivity is obtained.

ところで近年、電子制御化が進む中で嵌合型コネクタが多極化したため、オス端子群とメス端子群を挿抜する際に多大な力が必要になり、特に、自動車のエンジンルーム内などの狭い空間では挿抜作業が困難なため前記挿抜力の低減が強く求められている。 By the way, in recent years, with the progress of electronic control, the mating connector has become multipolar, so a great deal of force is required when inserting and removing the male terminal group and the female terminal group, especially in a narrow space such as in the engine room of an automobile. Since insertion / extraction work is difficult, reduction of the insertion / extraction force is strongly demanded.

前記挿抜力を低減する方法として、コネクタ端子表面のＳｎめっき層を薄くして端子間の接触圧力を弱める方法が考えられるが、この方法はＳｎめっき層が軟質のため端子の接触面間にフレッティング現象が起きて端子間が導通不良になることがある。 As a method of reducing the insertion / extraction force, a method of reducing the contact pressure between the terminals by thinning the Sn plating layer on the surface of the connector terminal is conceivable, but this method causes the flapping between the contact surfaces of the terminals because the Sn plating layer is soft. Tinging phenomenon may occur, resulting in poor continuity between terminals.

前記フレッティング現象とは、振動や温度変化などが原因で端子の接触面間に起きる微摺動により、端子表面の軟質のＳｎめっき層が摩耗し酸化して、比抵抗の大きい摩耗粉になる現象で、この現象が端子間に発生すると接続不良が起きる。そして、この現象は端子間の接触圧力が低いほど起き易い。 The fretting phenomenon is that the soft Sn plating layer on the surface of the terminal wears and oxidizes due to fine sliding that occurs between the contact surfaces of the terminal due to vibration, temperature change, etc., and becomes a wear powder having a large specific resistance. When this phenomenon occurs between terminals, a connection failure occurs. This phenomenon is more likely to occur as the contact pressure between the terminals is lower.

前記フレッティング現象を防止するため、基材上に、フレッティング現象が起き難い硬質のＣｕ_６Ｓｎ_５などのＣｕ−Ｓｎ金属間化合物層を形成する方法（特許文献１、２）が提案されたが、この方法はＣｕ−Ｓｎ金属間化合物層にＣｕなどの基材成分が大量に拡散してＣｕ−Ｓｎ金属間化合物層が脆化するという問題があった。 In order to prevent the fretting phenomenon, a method (Patent Documents 1 and 2) for forming a Cu—Sn intermetallic compound layer such as hard Cu ₆ Sn ₅ on which a fretting phenomenon hardly occurs has been proposed. However, this method has a problem that a base material component such as Cu diffuses in a large amount in the Cu—Sn intermetallic compound layer and the Cu—Sn intermetallic compound layer becomes brittle.

前記基体とＣｕ−Ｓｎ金属間化合物層間にＮｉ層を設けて基体成分の拡散を防止しためっき材料（特許文献３）はＮｉ層とＣｕ−Ｓｎ金属間化合物層間にＳｎ層もＣｕ層も存在しないため、この材料を、基体上にＮｉ、Ｃｕ、Ｓｎをこの順に層状にめっきし、これを熱処理して製造する際に、めっき積層体のめっき厚みをＣｕとＳｎの化学量論比を踏まえて厳密に設計し、かつその熱処理を徹底した管理の基で行う必要があり、製造に多大な労力を要した。 The plating material (Patent Document 3) in which the Ni layer is provided between the base and the Cu—Sn intermetallic compound layer to prevent the diffusion of the base component does not exist between the Ni layer and the Cu—Sn intermetallic compound layer. Therefore, when this material is produced by plating Ni, Cu, and Sn in this order on a substrate and heat-treating them, the plating thickness of the plated laminate is determined based on the stoichiometric ratio of Cu and Sn. It was necessary to design strictly and perform the heat treatment based on thorough management, and much labor was required for manufacturing.

特開２０００−２１２７２０号公報JP 2000-212720 A 特開２０００−２２６６４５号公報JP 2000-226645 A 特開２００４−６８０２６号公報JP 2004-68026 A

本発明は、接続端子の摺動部などに好適なめっき材料、および前記めっき材料を用いて挿抜性を改善した嵌合型多極コネクタなどの電気電子部品の提供を目的とする。 An object of the present invention is to provide a plating material suitable for a sliding portion of a connection terminal and the like, and an electric / electronic component such as a fitting type multipolar connector whose insertion / removability is improved by using the plating material.

請求項１に記載した発明は、導電性基体上にニッケル、ニッケル合金、コバルト、コバルト合金、鉄、鉄合金のいずれか１種からなる下地層、その上に銅または銅合金からなる銅系層、その上にＣｕ−Ｓｎ金属間化合物からなる中間層、その上に錫または錫合金からなる錫系層、その上にＣｕ−Ｓｎ金属間化合物からなる最外層が設けられていることを特徴とするめっき材料である。 The invention described in claim 1 is a base layer made of any one of nickel, nickel alloy, cobalt, cobalt alloy, iron, and iron alloy on a conductive substrate, and a copper-based layer made of copper or a copper alloy thereon. And an intermediate layer made of a Cu—Sn intermetallic compound, a tin-based layer made of tin or a tin alloy thereon, and an outermost layer made of a Cu—Sn intermetallic compound thereon. Plating material to be used.

請求項２に記載した発明は、導電性基体上にニッケル、ニッケル合金、コバルト、コバルト合金、鉄、鉄合金のいずれか１種からなる下地層、その上にＣｕ−Ｓｎ金属間化合物からなる中間層、その上に錫または錫合金からなる錫系層、その上にＣｕ−Ｓｎ金属間化合物からなる最外層が設けられていることを特徴とするめっき材料である。 According to the second aspect of the present invention, there is provided a base layer made of any one of nickel, nickel alloy, cobalt, cobalt alloy, iron, and iron alloy on a conductive substrate, and an intermediate made of a Cu—Sn intermetallic compound thereon. A plating material comprising: a layer, a tin-based layer made of tin or a tin alloy thereon, and an outermost layer made of a Cu—Sn intermetallic compound thereon.

請求項３に記載した発明は、前記中間層および最外層のＣｕ−Ｓｎ金属間化合物がＣｕ_３Ｓｎ化合物を主体とすることを特徴とする請求項１または２に記載のめっき材料である。 The invention described in claim 3 is a plating material according to claim 1 or 2, wherein the intermediate layer and the outermost layer of the Cu-Sn intermetallic compound is characterized by mainly comprising Cu 3 _Sn compound.

請求項４に記載した発明は、前記中間層および最外層のＣｕ−Ｓｎ金属間化合物がＣｕ_６Ｓｎ_５化合物を主体とすることを特徴とする請求項１または２に記載のめっき材料である。 The invention described in claim 4 is a plating material according to claim 1 or 2, wherein the intermediate layer and the outermost layer of the Cu-Sn intermetallic compound is characterized by mainly containing Cu ₆ Sn ₅ compound.

請求項５に記載した発明は、前記中間層が上下２層からなり、下側（基体側）の中間層がＣｕ_３Ｓｎ化合物を主体とし、上側の中間層がＣｕ_６Ｓｎ_５化合物を主体とし、前記最外層が上下２層からなり、下側（基体側）の最外層がＣｕ_６Ｓｎ_５化合物を主体とし、上側の最外層がＣｕ_３Ｓｎ化合物を主体とすることを特徴とする請求項１または２に記載のめっき材料である。 In the invention described in claim 5, the intermediate layer is composed of two upper and lower layers, the lower (base side) intermediate layer is mainly composed of a Cu ₃ Sn compound, and the upper intermediate layer is mainly composed of a Cu ₆ Sn ₅ compound. The outermost layer is composed of two upper and lower layers, and the lower (substrate side) outermost layer is mainly composed of a Cu ₆ Sn ₅ compound, and the upper outermost layer is mainly composed of a Cu ₃ Sn compound. The plating material according to 1 or 2.

請求項６に記載した発明は、前記Ｃｕ_６Ｓｎ_５化合物にＳｎ相またはＳｎ合金相が分散していることを特徴とする請求項４または５に記載のめっき材料である。 The invention described in claim 6 is the plating material according to claim 4 or 5, wherein an Sn phase or an Sn alloy phase is dispersed in the Cu ₆ Sn ₅ compound.

請求項７に記載した発明は、導電性基体上にニッケル、ニッケル合金、コバルト、コバルト合金、鉄、鉄合金のいずれか１種からなる下地層、その上に銅または銅合金からなる銅系層、その上にＣｕ−Ｓｎ金属間化合物からなる最外層が設けられており、前記最外層のＣｕ−Ｓｎ金属間化合物がＣｕ_６Ｓｎ_５化合物を主体とし、前記Ｃｕ_６Ｓｎ_５化合物にＳｎ相またはＳｎ合金相が分散していることを特徴とするめっき材料である。 The invention described in claim 7 is a base layer made of any one of nickel, nickel alloy, cobalt, cobalt alloy, iron and iron alloy on a conductive substrate, and a copper-based layer made of copper or a copper alloy thereon. , thereon and the outermost layer is provided consisting of Cu-Sn intermetallic compound, the Cu-Sn intermetallic compound of the outermost layer is composed mainly of _Cu 6 Sn ₅ compound, Sn phase in the _Cu 6 Sn ₅ compound or The plating material is characterized in that the Sn alloy phase is dispersed.

請求項８に記載した発明は、導電性基体上にニッケル、ニッケル合金、コバルト、コバルト合金、鉄、鉄合金のいずれか１種からなる下地層、その上にＣｕ−Ｓｎ金属間化合物からなる最外層が設けられており、前記最外層のＣｕ−Ｓｎ金属間化合物がＣｕ_６Ｓｎ_５化合物を主体とし、前記Ｃｕ_６Ｓｎ_５化合物にＳｎ相またはＳｎ合金相が分散していることを特徴とするめっき材料である。 According to the eighth aspect of the present invention, a base layer made of any one of nickel, nickel alloy, cobalt, cobalt alloy, iron and iron alloy is formed on a conductive substrate, and a Cu—Sn intermetallic compound is further formed thereon. the outer layer is provided, Cu-Sn intermetallic compound of said outermost layer is composed mainly of _Cu 6 Sn ₅ compound, Sn phase or Sn alloy phase in the _Cu 6 Sn ₅ compound, characterized in that the dispersed It is a plating material.

請求項９に記載した発明は、前記導電性基体上に、下地層が少なくとも２層設けられていることを特徴とする請求項１乃至８のいずれかに記載のめっき材料である。 The invention described in claim 9 is the plating material according to any one of claims 1 to 8, wherein at least two underlayers are provided on the conductive substrate.

請求項１０に記載した発明は、電気電子部品の少なくとも摺動部が請求項１乃至９のいずれかに記載のめっき材料からなることを特徴とする電気電子部品である。 According to a tenth aspect of the present invention, there is provided an electric / electronic component characterized in that at least a sliding portion of the electric / electronic component is made of the plating material according to any one of the first to ninth aspects.

請求項１１に記載した発明は、嵌合型コネクタまたは接触子に用いられることを特徴とする請求項１０に記載の電気電子部品である。 An eleventh aspect of the present invention is an electrical / electronic component according to the tenth aspect, which is used for a fitting-type connector or a contact.

本発明のめっき材料は最外層が硬質のＣｕ−Ｓｎ金属間化合物からなるため、めっき層を薄くして端子間の接触圧力を小さくしても、フレッティング現象が起き難い。従って本発明のめっき材料を摺動部に用いた端子などの電気電子部品は良好な挿抜性および電気接続性が安定して得られる。 Since the outermost layer is made of a hard Cu—Sn intermetallic compound, the fretting phenomenon is unlikely to occur even if the plating layer is thinned to reduce the contact pressure between terminals. Therefore, electrical / electronic parts such as terminals using the plating material of the present invention for the sliding portion can stably obtain good insertion / extraction and electrical connectivity.

本発明のめっき材料は、導電性基体上にＮｉなどからなる下地層が設けられるので基体成分が最外層に拡散するのが防止される。
請求項１に記載した発明では前記下地層上にＣｕなどからなる銅系層、Ｃｕ−Ｓｎ金属間化合物層からなる中間層、Ｓｎなどからなる錫系層が設けられているので、また請求項２に記載した発明では前記下地層上にＣｕ−Ｓｎ金属間化合物層からなる中間層およびＳｎなどからなる錫系層が設けられているので、請求項７に記載した発明では前記下地層上にＣｕなどからなる銅系層が設けられているので、いずれもＮｉなどの下地層成分が最外層に拡散するのが防止される。従って、良好な電気接続性がより安定して得られる。 In the plating material of the present invention, since the base layer made of Ni or the like is provided on the conductive base, the base component is prevented from diffusing into the outermost layer.
In the invention described in claim 1, since the copper-based layer made of Cu or the like, the intermediate layer made of Cu-Sn intermetallic compound layer, or the tin-based layer made of Sn or the like is provided on the underlayer, the invention is also claimed. In the invention described in 2, since an intermediate layer made of a Cu—Sn intermetallic compound layer and a tin-based layer made of Sn or the like are provided on the foundation layer, in the invention described in claim 7, the interlayer is formed on the foundation layer. Since the copper-based layer made of Cu or the like is provided, any of the underlayer components such as Ni is prevented from diffusing into the outermost layer. Therefore, good electrical connectivity can be obtained more stably.

本発明のめっき材料を、基体上に、例えば、Ｎｉ、Ｃｕ（内）、Ｓｎ、Ｃｕ（外）をこの順に層状にめっきしてめっき積層体とし、このめっき積層体を熱処理して製造する際に、前記積層体のＣｕ（内）層とＳｎ層、或いはＳｎ層のみを残存させるので、または前記めっき材料の最外層または中間層にＳｎ相またはＳｎ合金相が分散した状態にするので、めっき積層体の設計および前記めっき積層体の熱処理が容易に行える。従って本発明のめっき材料は生産性に優れる。 When the plating material of the present invention is produced by plating, for example, Ni, Cu (inner), Sn, Cu (outer) in this order on a substrate to form a plating laminate, and heat-treating the plating laminate In addition, the Cu (inner) layer and the Sn layer or only the Sn layer of the laminate are left, or the Sn phase or the Sn alloy phase is dispersed in the outermost layer or the intermediate layer of the plating material. The design of the laminate and the heat treatment of the plated laminate can be easily performed. Therefore, the plating material of the present invention is excellent in productivity.

本発明のめっき材料７は、図１（イ）に示すように、導電性基体１上に、Ｎｉなどからなる下地層２、その上にＣｕなどからなる銅系層３、その上にＣｕ−Ｓｎ金属間化合物からなる中間層４、その上にＳｎなどからなる錫系層５、その上にＣｕ−Ｓｎ金属間化合物からなる最外層６を設けたもの（請求項１）、図１（ロ）に示すように、導電性基体１上に、Ｎｉなどからなる下地層２、その上にＣｕ−Ｓｎ金属間化合物からなる中間層４、その上にＳｎなどからなる錫系層５、その上にＣｕ−Ｓｎ金属間化合物からなる最外層６を設けたもの（請求項２）、前記請求項１または２に記載しためっき材料のＣｕ−Ｓｎ金属間化合物からなる最外層または／および中間層にＳｎ相またはＳｎ合金相が分散したもの（請求項６）、図１（ハ）に示すように、導電性基体１上に、Ｎｉなどからなる下地層２、その上にＣｕなどからなる銅系層３、その上にＣｕ_６Ｓｎ_５化合物を主体としＳｎ相またはＳｎ合金相９が分散したＣｕ−Ｓｎ金属間化合物からなる最外層６を設けたもの（請求項７）、図１（ニ）に示すように、導電性基体１上に、Ｎｉなどからなる下地層２、その上にＣｕ_６Ｓｎ_５化合物を主体としＳｎ相またはＳｎ合金相９が分散したＣｕ−Ｓｎ金属間化合物からなる最外層６を設けたもの（請求項８）などである。 As shown in FIG. 1 (a), the plating material 7 of the present invention has a base layer 2 made of Ni or the like on a conductive substrate 1, a copper-based layer 3 made of Cu or the like thereon, and a Cu-- An intermediate layer 4 made of an Sn intermetallic compound, a tin-based layer 5 made of Sn or the like thereon, and an outermost layer 6 made of a Cu—Sn intermetallic compound thereon (Claim 1), FIG. ), A base layer 2 made of Ni or the like, an intermediate layer 4 made of a Cu—Sn intermetallic compound thereon, a tin-based layer 5 made of Sn or the like thereon, and a conductive layer 1. The outermost layer 6 made of a Cu—Sn intermetallic compound is provided on the outermost layer or / and the intermediate layer made of a Cu—Sn intermetallic compound of the plating material according to claim 1 or 2. Sn phase or Sn alloy phase dispersed (Claim 6), as shown in FIG. As, on the conductive substrate 1, an underlayer 2 made of Ni, a copper-based layer 3 made of Cu is formed thereon, Sn phase or Sn alloy phase 9 mainly composed of Cu ₆ Sn ₅ compound thereon dispersion The outermost layer 6 made of the Cu—Sn intermetallic compound is provided (Claim 7), and as shown in FIG. 1 (d), the base layer 2 made of Ni, etc. And an outermost layer 6 made of a Cu—Sn intermetallic compound mainly composed of a Cu ₆ Sn ₅ compound and having a Sn phase or an Sn alloy phase 9 dispersed therein (Claim 8).

請求項１に記載した発明のめっき材料は、例えば、図２に示すように、導電性基体１上にＮｉ層２’、Ｃｕ層３’、Ｓｎ層４’、Ｃｕ層５’をこの順にめっきしてめっき積層体８を作製し、これを熱処理して、前記Ｃｕ層３’とＳｎ層４’をＣｕ−Ｓｎ金属間化合物層（中間層）に反応させ、さらにＳｎ層４’とＣｕ層５’をＣｕ−Ｓｎ金属間化合物層（最外層）に反応させて製造される。この反応の間、基体の合金成分の熱拡散はNｉ層２’により阻止される。 The plating material according to the first aspect of the present invention is, for example, as shown in FIG. 2, on a conductive substrate 1, a Ni layer 2 ′, a Cu layer 3 ′, a Sn layer 4 ′, and a Cu layer 5 ′ are plated in this order. Then, the plated laminated body 8 is produced, and this is heat-treated to cause the Cu layer 3 ′ and the Sn layer 4 ′ to react with the Cu—Sn intermetallic compound layer (intermediate layer), and further, the Sn layer 4 ′ and the Cu layer. It is produced by reacting 5 ′ with a Cu—Sn intermetallic compound layer (outermost layer). During this reaction, thermal diffusion of the alloy components of the substrate is blocked by the Ni layer 2 '.

めっき積層体８のＣｕ層３’、Ｓｎ層４’、Ｃｕ層５’の体積比は、請求項１に記載した発明ではめっき材料７の最外層６のＣｕ−Ｓｎ金属間化合物層の必要厚みを考慮し、さらに熱処理後のめっき材料７に銅系層３と錫系層５が形成されるように決める。また請求項２に記載した発明では錫系層が形成されるように決める。前記熱処理後のめっき材料７に形成される銅系層３や錫系層５の厚みは特に厳密に規定する必要がないため、めっき積層体８の設計およびその熱処理が容易に行える。従って本発明のめっき材料は生産性に優れる。 In the invention described in claim 1, the volume ratio of the Cu layer 3 ′, the Sn layer 4 ′, and the Cu layer 5 ′ of the plating laminate 8 is the required thickness of the Cu—Sn intermetallic compound layer of the outermost layer 6 of the plating material 7. In consideration of the above, it is further determined that the copper-based layer 3 and the tin-based layer 5 are formed on the plating material 7 after the heat treatment. In the invention described in claim 2, the tin-based layer is determined to be formed. Since the thickness of the copper-based layer 3 and the tin-based layer 5 formed on the plating material 7 after the heat treatment does not need to be particularly strictly defined, the plating laminate 8 can be easily designed and heat-treated. Therefore, the plating material of the present invention is excellent in productivity.

めっき積層体８のＣｕ層（内）３’の厚みは通常０．０１μｍ以上とする。上限は実用面、材料費、製造コストなどを考慮して５．０μｍ程度が望ましい。なおＣｕ層（内）３’がＣｕのとき、その厚みが薄いと熱処理後のめっき材料７の銅系層３に微細孔が多数存在しバリア機能が失われることがあるので、めっき積層体８のＣｕ層（内）３’の厚みはＣｕ合金の場合より若干厚めにする。 The thickness of the Cu layer (inner) 3 ′ of the plated laminate 8 is usually 0.01 μm or more. The upper limit is preferably about 5.0 μm in consideration of practical aspects, material costs, manufacturing costs, and the like. When the Cu layer (inner) 3 ′ is Cu, if the thickness is thin, the copper-based layer 3 of the plating material 7 after the heat treatment has many fine holes and the barrier function may be lost. The thickness of the Cu layer (inner) 3 ′ is made slightly thicker than that of the Cu alloy.

本発明において、Ｃｕ層（外）５’が熱処理で完全にＣｕ−Ｓｎ金属間化合物に反応するのには長時間を要するため、熱処理後に、めっき材料７の最外層６の表面にＣｕまたはＣｕ化合物が若干残存することがあるが、このことでめっき材料７の機能が低下することは殆どなく、従ってめっき材料７の最外層６の表面にＣｕまたはＣｕ合金が残存するものも本発明のめっき材料である。前記ＣｕまたはＣｕ化合物は薬品などを用いて除去するのが望ましい。 In the present invention, since it takes a long time for the Cu layer (outer) 5 ′ to completely react with the Cu—Sn intermetallic compound by the heat treatment, Cu or Cu is formed on the surface of the outermost layer 6 of the plating material 7 after the heat treatment. Although some of the compound may remain, this hardly reduces the function of the plating material 7, so that the Cu or Cu alloy remains on the surface of the outermost layer 6 of the plating material 7. Material. The Cu or Cu compound is desirably removed using a chemical or the like.

本請求項２、８に記載した発明のめっき材料は、前記熱処理後のめっき材料７の下地層２上に銅系層３が存在しないものであるが、銅系層３が存在しないからといって、このめっき材料の端子挿抜性などの特性が低下することは殆どない。 In the plating materials of the present invention described in claims 2 and 8, the copper-based layer 3 is not present on the base layer 2 of the plated material 7 after the heat treatment, but the copper-based layer 3 is not present. Thus, characteristics such as terminal insertion / extraction of the plating material are hardly deteriorated.

本発明において、最外層をＣｕ−Ｓｎ金属間化合物層とする端子摺動部と、最外層をＳｎ層とする電線圧着部を含むめっき材料は、例えば自動車用端子として使用されるが、このようなめっき材料は、前記電線圧着部となる箇所のみＣｕ層（外）のめっき時にマスキングを施したうえで、熱処理することにより電線圧着部にのみ最表面にＳｎ層を残しためっき材料を製造できる。この方法によれば、最外層の材質が部位ごとに異なるめっき材料を容易に製造できる。 In the present invention, a plating material including a terminal sliding portion whose outermost layer is a Cu-Sn intermetallic compound layer and a wire crimping portion whose outermost layer is a Sn layer is used as, for example, an automobile terminal. The plating material can produce a plating material in which the Sn layer is left on the outermost surface only in the wire crimping part by performing heat treatment after masking the Cu layer (outside) only at the portion to be the wire crimping part. . According to this method, it is possible to easily manufacture a plating material in which the material of the outermost layer is different for each part.

前記めっき積層体８の熱処理をリフロー処理（連続処理）により施す場合は、めっき積層体の実体温度を好ましくは２３２〜５００℃にして０．１秒以上１０分以下、より好ましくは１００秒以下、さらに好ましくは１０秒以下加熱して施す。このリフロー処理は、たとえばリフロー炉内の温度を５００℃〜９００℃に保ち１０分以下、好ましくは１００秒以下、より好ましくは１０秒以下で加熱を施すことで実現される。実際には実体温度による温度よりリフロー炉内の温度のほうが計測しやすいため、リフロー炉内の温度管理を行うことによりリフロー処理を施すことが望ましい。なお、熱処理をバッチ処理により施す場合は前記めっき積層体８を好ましくは５０〜２５０℃の炉内に数１０分乃至数時間保持して施す。なお、熱処理をリフロー処理により施す場合の温度や加熱時間は、めっき積層体の厚みなどに適合した条件に設定する必要があるが、後述する実施例において説明するように、個々の具体的条件は、適宜設定することができる。 When the heat treatment of the plating laminate 8 is performed by reflow treatment (continuous treatment), the actual temperature of the plating laminate is preferably 232 to 500 ° C. and is 0.1 second or longer and 10 minutes or shorter, more preferably 100 seconds or shorter, More preferably, it is heated for 10 seconds or less. This reflow treatment is realized, for example, by maintaining the temperature in the reflow furnace at 500 ° C. to 900 ° C. and heating for 10 minutes or less, preferably 100 seconds or less, more preferably 10 seconds or less. Actually, since the temperature in the reflow furnace is easier to measure than the temperature due to the actual temperature, it is desirable to perform the reflow process by managing the temperature in the reflow furnace. In addition, when performing heat processing by batch processing, the said plating laminated body 8 is preferably hold | maintained for several 10 minutes thru | or several hours in a 50-250 degreeC furnace. It should be noted that the temperature and heating time when heat treatment is performed by reflow treatment must be set to conditions suitable for the thickness of the plated laminate, etc., but as described in the examples described later, individual specific conditions are Can be set as appropriate.

本発明において、導電性基体１には、端子に要求される導電性、機械的強度および耐熱性を有する銅、リン青銅、黄銅、洋白、ベリリウム銅、コルソン合金などの銅系材料、鉄、ステンレス鋼などの鉄系材料、銅被覆鉄材やニッケル被覆鉄材などの複合材料、各種のニッケル合金やアルミニウム合金などの金属材料が適宜用いられる。 In the present invention, the conductive substrate 1 includes copper, phosphor bronze, brass, white, beryllium copper, Corson alloy and other copper-based materials, iron, Iron-based materials such as stainless steel, composite materials such as copper-coated iron materials and nickel-coated iron materials, and metal materials such as various nickel alloys and aluminum alloys are appropriately used.

前記導電性基体１に用いられる各種金属材料のうち、特に銅、銅合金などの銅系材料は導電性と機械的強度のバランスに優れ好適である。前記導電性基体が銅系材料以外の場合は、その表面に銅または銅合金を被覆しておくと耐食性および下地めっき層との密着性が向上する。 Of the various metal materials used for the conductive substrate 1, copper-based materials such as copper and copper alloys are particularly suitable because of their excellent balance between conductivity and mechanical strength. When the conductive substrate is other than a copper-based material, corrosion resistance and adhesion to the underlying plating layer are improved by covering the surface with copper or a copper alloy.

前記導電性基体１上に設ける下地層２は、基体１の成分が最外層６に熱拡散するのを防止するバリア機能を有するＮｉ、Ｃｏ、Ｆｅなどの金属、これらを主成分とするＮｉ−Ｐ系、Ｎｉ−Ｓｎ系、Ｃｏ−Ｐ系、Ｎｉ−Ｃｏ系、Ｎｉ−Ｃｏ−Ｐ系、Ｎｉ−Ｃｕ系、Ｎｉ−Ｃｒ系、Ｎｉ−Ｚｎ系、Ｎｉ−Ｆｅ系などの合金が好適に用いられる。これら金属および合金は、めっき処理性が良好で、価格的にも問題がない。中でも、ＮｉおよびＮｉ合金はバリア機能が高温環境下にあっても衰えないため推奨される。 The base layer 2 provided on the conductive substrate 1 is made of a metal such as Ni, Co, Fe or the like having a barrier function for preventing the components of the substrate 1 from thermally diffusing into the outermost layer 6, and Ni— having these as a main component. P, Ni—Sn, Co—P, Ni—Co, Ni—Co—P, Ni—Cu, Ni—Cr, Ni—Zn, Ni—Fe, and other alloys are preferred. Used. These metals and alloys have good plating processability and no problem in price. Among these, Ni and Ni alloys are recommended because the barrier function does not deteriorate even in a high temperature environment.

前記下地層２に用いるＮｉなどの金属（合金）は、融点が１０００℃以上と高く、接続コネクタの使用環境温度は２００℃以下と低いため、下地層はそれ自身熱拡散を起こし難いうえ、そのバリア機能が有効に発現される。下地層２には、導電性基体１の材質によっては導電性基体１と銅系層３との（銅系層３が存在しない場合には導電性基体１と中間層４との）密着性を高める機能もある。 Since the metal (alloy) such as Ni used for the underlayer 2 has a high melting point of 1000 ° C. or higher and the operating environment temperature of the connector is as low as 200 ° C. or less, the underlayer itself hardly causes thermal diffusion. The barrier function is effectively expressed. Depending on the material of the conductive substrate 1, the base layer 2 may have adhesion between the conductive substrate 1 and the copper-based layer 3 (the conductive substrate 1 and the intermediate layer 4 when the copper-based layer 3 is not present). There is also a function to enhance.

下地層２の厚みは、０．０５μｍ未満ではそのバリア機能が十分に発揮されなくなり、３μｍを超えるとめっき歪みが大きくなって基体１から剥離し易くなる。従って０．０５〜３μｍが望ましい。下地層の厚みの上限は端子加工性を考慮すると１．５μｍ、さらには０．５μｍが望ましい。 When the thickness of the underlayer 2 is less than 0.05 μm, the barrier function is not fully exhibited, and when it exceeds 3 μm, the plating distortion increases and the base layer 1 is easily peeled off. Therefore, 0.05 to 3 μm is desirable. The upper limit of the thickness of the underlayer is preferably 1.5 μm, more preferably 0.5 μm, considering the terminal processability.

前記めっき積層体８のＣｕ層（内、外）には、Ｃｕの他、Ｃｕ−Ｓｎ系などの銅合金が適用できる。銅合金のＣｕ濃度は５０質量％以上が望ましい。 In addition to Cu, a Cu alloy such as Cu—Sn can be applied to the Cu layer (inside and outside) of the plated laminate 8. The Cu concentration of the copper alloy is desirably 50% by mass or more.

前記めっき積層体８のＳｎ層４’がＳｎでＣｕ層（内、外）３’、５’がＣｕの場合のＳｎ層４’とＣｕ層（内＋外）の体積比（Ｓｎ層／Ｃｕ層）が１．９以上のめっき積層体に所定の熱処理を施すことにより、基体１上に下地層２、その上に銅系層３、その上にＣｕ−Ｓｎ金属間化合物層（中間層）４、その上に錫系層５、その上にＣｕ−Ｓｎ金属間化合物層（最外層）６が形成された請求項１に記載した発明のめっき材料７が得られる。めっき積層体８のＣｕ層（内）３’を薄くするか、設けないことにより前記銅系層３の存在しない請求項２に記載した発明のめっき材料７が得られる。
めっき積層体８のＳｎ層４’の厚みは０．０３８〜４．０μｍが望ましく、その上限は３．０μｍであることがさらに望ましい。 When the Sn layer 4 'of the plating laminate 8 is Sn and the Cu layer (inner / outer) 3', and 5 'is Cu, the volume ratio of the Sn layer 4' and the Cu layer (inner + outer) (Sn layer / Cu Layer) is subjected to a predetermined heat treatment, whereby a base layer 2 is formed on the substrate 1, a copper-based layer 3 is formed thereon, and a Cu—Sn intermetallic compound layer (intermediate layer) is formed thereon. 4. A plating material 7 according to the invention described in claim 1 in which a tin-based layer 5 is formed thereon and a Cu—Sn intermetallic compound layer (outermost layer) 6 is formed thereon. By thinning or not providing the Cu layer (inner) 3 ′ of the plated laminate 8, the plating material 7 according to the invention described in claim 2 in which the copper-based layer 3 does not exist can be obtained.
The thickness of the Sn layer 4 ′ of the plated laminate 8 is preferably 0.038 to 4.0 μm, and the upper limit is more preferably 3.0 μm.

前記めっき積層体８のＮｉ層２’、Ｃｕ層（内、外）３’、５’およびＳｎ層４’はＰＶＤ法などによっても形成できるが、湿式めっき法が簡便かつ低コストで望ましい。 The Ni layer 2 ′, Cu layers (inside and outside) 3 ′, 5 ′ and Sn layer 4 ′ of the plated laminate 8 can be formed by a PVD method or the like, but a wet plating method is preferable because it is simple and low cost.

本発明において、最外層のＣｕ−Ｓｎ金属間化合物層６としてはＣｕ_６Ｓｎ_５、Ｃｕ_３Ｓｎ、Ｃｕ_４Ｓｎなどが挙げられる。Ｃｕ_６Ｓｎ_５はＣｕの１体積に対しＳｎの１．９０体積が反応して生成される。Ｃｕ_３ＳｎはＣｕの１体積に対しＳｎの０．７６体積が反応して生成される。Ｃｕ_４ＳｎはＣｕの１体積に対しＳｎの０．５７体積が反応して生成される。 In the present invention, examples of the outermost Cu—Sn intermetallic compound layer 6 include Cu ₆ Sn ₅ , Cu ₃ Sn, and Cu ₄ Sn. Cu ₆ Sn ₅ is produced by reacting 1.90 volumes of Sn with 1 volume of Cu. Cu ₃ Sn is produced by reacting 0.76 volume of Sn with 1 volume of Cu. Cu ₄ Sn is produced by reacting 0.57 volume of Sn with 1 volume of Cu.

従って、Ｓｎ層４’とＣｕ層（内＋外）の体積比（Ｓｎ層／Ｃｕ層）が、例えば１．９０を超えるめっき積層体８を長時間熱処理するとＣｕ_６Ｓｎ_５が主体の中間層４或いは最外層６が形成される。
熱処理時間が短いときは、めっき積層体８のＣｕ層（内、外）３’、５’のＳｎ層４’から離れた箇所にはＣｕ_３Ｓｎ或いはＣｕ_４Ｓｎが主体のＣｕ−Ｓｎ金属間化合物が形成される。このようなめっき材料（請求項５に記載した発明）によってもフレッティング現象が起き難い端子などが得られる。 Accordingly, when the plating laminate 8 having a volume ratio (Sn layer / Cu layer) of the Sn layer 4 ′ and the Cu layer (inside + outside) exceeds 1.90, for example, when the heat treatment is performed for a long time, the intermediate layer mainly composed of Cu ₆ Sn ₅ 4 or the outermost layer 6 is formed.
When the heat treatment time is short, Cu ₃ Sn or Cu ₄ Sn mainly composed of Cu ₃ Sn or Cu ₄ Sn is disposed at a position away from the Cu layer (inside and outside) 3 ′ and 5 ′ of the plated laminate 8. A compound is formed. Even with such a plating material (the invention described in claim 5), it is possible to obtain a terminal or the like that hardly causes fretting phenomenon.

本発明において、最外層のＣｕ−Ｓｎ金属間化合物層６をＣｕ_６Ｓｎ_５層とＣｕ_３Ｓｎ層の２層で構成する場合（請求項５に記載した発明）の各層の厚みは特に規定しないが、Ｃｕ_６Ｓｎ_５は０．０１〜５．０μｍ、Ｃｕ_３Ｓｎは０．００８〜４．０μｍが望ましい。中間層（Ｃｕ−Ｓｎ金属間化合物層）についても同様である。 In the present invention, the thickness of each layer in the case where the outermost Cu—Sn intermetallic compound layer 6 is composed of two layers of a Cu ₆ Sn ₅ layer and a Cu ₃ Sn layer (the invention described in claim 5) is not particularly defined. However, Cu ₆ Sn ₅ is desirably 0.01 to 5.0 μm, and Cu ₃ Sn is desirably 0.008 to 4.0 μm. The same applies to the intermediate layer (Cu—Sn intermetallic compound layer).

前記めっき積層体８のＳｎ層４’の体積比が大きく、かつ熱処理を高温側または長時間側に設定して施す場合は、めっき積層体８のＳｎ層４’を形成していたＳｎまたはＳｎ合金が、中間層４または最外層６にＳｎ相またはＳｎ合金相（９）が分散することがある。この場合もフレッティング現象が起き難い端子などが得られる点、めっき積層体８の設計およびその熱処理が容易に行える点については他の実施形態と変わるところはない。 When the volume ratio of the Sn layer 4 ′ of the plating laminate 8 is large and the heat treatment is performed on the high temperature side or the long time side, the Sn or Sn forming the Sn layer 4 ′ of the plating laminate 8 is formed. In the alloy, the Sn phase or the Sn alloy phase (9) may be dispersed in the intermediate layer 4 or the outermost layer 6. In this case as well, there is no difference from the other embodiments in that a terminal that is less likely to cause fretting phenomenon can be obtained, and that the plated laminate 8 can be easily designed and heat-treated.

本発明において、Ｓｎ相またはＳｎ合金相（９）が分散した中間層４または最外層６のＣｕ−Ｓｎ金属間化合物は、通常Ｃｕ_６Ｓｎ_５化合物が主体となる。 In the present invention, the Cu—Sn intermetallic compound of the intermediate layer 4 or the outermost layer 6 in which the Sn phase or the Sn alloy phase (9) is dispersed is usually mainly a Cu ₆ Sn ₅ compound.

本発明において、最外層６のＣｕ−Ｓｎ金属間化合物（Ｃｕ_６Ｓｎ_５）によるフレッティング現象の防止効果はＳｎ相またはＳｎ合金相（９）の有無に関係なく良好に得られる。 In the present invention, the effect of preventing the fretting phenomenon by the Cu—Sn intermetallic compound (Cu ₆ Sn ₅ ) in the outermost layer 6 can be obtained satisfactorily regardless of the presence or absence of the Sn phase or the Sn alloy phase (9).

本発明において、めっき材料７の各層間（導電性基体と下地層間を含む）に、隣接する層より薄い異種材料のめっき層を介在させてもよい。まためっき材料７の形状は、条、丸線、角線など任意である。 In the present invention, a plating layer made of a different material thinner than the adjacent layers may be interposed between the layers of the plating material 7 (including the conductive substrate and the base layer). Moreover, the shape of the plating material 7 is arbitrary, such as a strip, a round line, and a square line.

［実施例１］
厚み０．２５ｍｍの銅合金（黄銅）条に脱脂および酸洗をこの順に施し、次いで前記銅合金条にＮｉ、Ｃｕ、Ｓｎ、Ｃｕをこの順に層状に電気めっきしてめっき積層体を作製し、次いでこのめっき積層体８に熱処理をリフロー処理法により施して図１（イ）に示す構成のめっき材料７を製造した。熱処理条件は、リフロー炉内の温度を７４０℃、サンプルの実体温度を２８５℃とした。めっき積層体８のＮｉ層２’の厚みは０．４μｍとし、Ｃｕ層（内）３’、Ｓｎ層４’、Ｃｕ層（外）５’の厚み（体積）は種々に変化させた。Ｓｎ層４’とＣｕ層（内＋外）の厚み（体積）比（Ｓｎ層／Ｃｕ層）は１．９５〜２．２０の範囲で種々に変化させた。
各金属のめっき条件を表１に示す。 [Example 1]
Degreasing and pickling are performed in this order on a copper alloy strip (brass) having a thickness of 0.25 mm, and then Ni, Cu, Sn, and Cu are electroplated in this order on the copper alloy strip in order to produce a plated laminate. Next, the plating laminate 8 was subjected to a heat treatment by a reflow processing method to produce a plating material 7 having the structure shown in FIG. The heat treatment conditions were such that the temperature in the reflow furnace was 740 ° C. and the actual temperature of the sample was 285 ° C. The thickness of the Ni layer 2 ′ of the plated laminate 8 was 0.4 μm, and the thickness (volume) of the Cu layer (inner) 3 ′, Sn layer 4 ′, and Cu layer (outer) 5 ′ was variously changed. The thickness (volume) ratio (Sn layer / Cu layer) of the Sn layer 4 ′ and the Cu layer (inside + outside) was variously changed in the range of 1.95 to 2.20.
Table 1 shows the plating conditions for each metal.

得られた各々のめっき材料について、下記の微摺動試験を摺動往復回数１０００回まで行い、接触抵抗値の変化を連続的に測定した。 About each obtained plating material, the following fine sliding test was done to the frequency | count of sliding reciprocation 1000 times, and the change of the contact resistance value was measured continuously.

前記微摺動試験は次のようにして行った。
即ち、図３に示すように各２枚のめっき材料１１、１２を用意し、各々脱脂洗浄後に、めっき材料１１に設けた曲率半径１．０５ｍｍの半球状張出部（凸部外面が最外層面）１１ａに、めっき材料１２の最外層面１２ａを、接触圧力３Ｎで接触させ、この状態で両者を、温度２０℃、湿度６５％の環境下で、摺動距離３０μｍで往復摺動させ、両めっき材料１１、１２間に開放電圧２０ｍＶを負荷して定電流５ｍＡを流し、摺動中の電圧降下を４端子法により測定して電気抵抗の変化を1秒ごとに求めた。往復運動の周波数は約３．３Ｈｚで行った。微摺動試験前の接触抵抗値と微摺動試験中の最大接触抵抗値を表２に示す。 The fine sliding test was performed as follows.
That is, as shown in FIG. 3, two plating materials 11 and 12 are prepared, and after each degreasing and cleaning, a hemispherical overhanging portion (the outer surface of the convex portion is the outermost surface) having a radius of curvature of 1.05 mm provided on the plating material 11 The outermost layer surface 12a of the plating material 12 is brought into contact with the layer surface 11a at a contact pressure of 3N, and in this state, both are reciprocated at a sliding distance of 30 μm in an environment of a temperature of 20 ° C. and a humidity of 65%. An open-circuit voltage of 20 mV was applied between the plating materials 11 and 12, a constant current of 5 mA was applied, and the voltage drop during sliding was measured by the four-terminal method to determine the change in electrical resistance every second. The frequency of reciprocating motion was about 3.3 Hz. Table 2 shows the contact resistance value before the fine sliding test and the maximum contact resistance value during the fine sliding test.

各めっき材料７について、（１）最外層６と中間層４のＣｕ−Ｓｎ金属間化合物層の厚み、および錫系層５の厚みをコクール社製のＲ５０溶液を用いたアノード溶解法により測定した。（２）銅系層３および最外層６の表面に残存するＣｕの厚みをコクール社製のＲ５２の溶液を用いたアノード溶解法により測定した。（３）下地層（Ｎｉ層）２の厚みを、蛍光Ｘ線膜厚計を用いて測定した。測定面積はいずれも１ｃｍ^２とした。各厚みの測定結果を表２に併記した。 About each plating material 7, (1) The thickness of the Cu-Sn intermetallic compound layer of the outermost layer 6 and the intermediate | middle layer 4, and the thickness of the tin-type layer 5 were measured by the anodic dissolution method using R50 solution made from a Cocourt company. . (2) The thickness of Cu remaining on the surfaces of the copper-based layer 3 and the outermost layer 6 was measured by an anodic dissolution method using a solution of R52 manufactured by Kocourt. (3) The thickness of the underlayer (Ni layer) 2 was measured using a fluorescent X-ray film thickness meter. The measurement area was 1 cm ² for all. The measurement results for each thickness are also shown in Table 2.

［実施例２］
熱処理をバッチ処理法により施した他は、実施例１と同じ方法により図１（イ）または（ロ）に示す構成のめっき材料７を製造し、実施例１と同じ試験、調査を行った。 [Example 2]
A plating material 7 having the structure shown in FIG. 1 (a) or (b) was manufactured by the same method as in Example 1 except that the heat treatment was performed by a batch processing method, and the same tests and investigations as in Example 1 were performed.

［比較例１］
めっき積層体のＳｎ層とＣｕ層（内＋外）の体積比（Ｓｎ層／Ｃｕ層）を１．９０とした他は、実施例１または２と同じ方法によりめっき材料を製造し、実施例１と同じ試験、調査を行った。 [Comparative Example 1]
A plating material was produced by the same method as in Example 1 or 2, except that the volume ratio (Sn layer / Cu layer) of the Sn layer and the Cu layer (inside + outside) of the plating laminate was 1.90. The same test and investigation as in No. 1 were conducted.

［比較例２］
めっき積層体のＳｎ層とＣｕ層（内＋外）の体積比（Ｓｎ層／Ｃｕ層）を１．８０とした他は、実施例１または２と同じ方法によりめっき材料を製造し、実施例１と同じ試験、調査を行った。 [Comparative Example 2]
A plating material was produced by the same method as in Example 1 or 2, except that the volume ratio (Sn layer / Cu layer) of the Sn layer and the Cu layer (inside + outside) of the plating laminate was 1.80. The same test and investigation as in No. 1 were conducted.

［比較例３］
銅合金基体上にＮｉ下地層とＳｎ最外層をこの順に電気めっきしためっき材料について実施例１と同じ試験、調査を行った。Ｓｎの厚みは２通りに変えた。 [Comparative Example 3]
The same test and investigation as in Example 1 were performed on a plating material obtained by electroplating a Ni underlayer and an Sn outermost layer in this order on a copper alloy substrate. The thickness of Sn was changed in two ways.

実施例１、２および比較例１〜３の調査結果を表２に示す。なお、表２における熱処理条件は、サンプルの実体温度を記載している。 The investigation results of Examples 1 and 2 and Comparative Examples 1 to 3 are shown in Table 2. In addition, the heat treatment conditions in Table 2 describe the actual temperature of the sample.

表２から明らかなように、本発明例のめっき材料７（実施例１、２）は、いずれも微摺動試験中の最大接触抵抗値が低かった。これは本発明例のめっき材料７は、最外層６が硬質のＣｕ−Ｓｎ金属間化合物からなるためフレッティング現象が起き難く、しかも最外層６の下に錫系層５および中間層４が存在してＮｉなどの下地成分の熱拡散が防止され、さらに下地層２により基体１の成分の熱拡散が防止されて、最外層６が汚染されずその機能が良好に保持されたためである。 As is apparent from Table 2, the plating materials 7 of Examples of the present invention (Examples 1 and 2) all had a low maximum contact resistance value during the fine sliding test. This is because the plating material 7 of the present invention has an outermost layer 6 made of a hard Cu—Sn intermetallic compound, so that the fretting phenomenon hardly occurs, and the tin-based layer 5 and the intermediate layer 4 exist below the outermost layer 6. This is because the thermal diffusion of the base component such as Ni is prevented, and further, the thermal diffusion of the component of the substrate 1 is prevented by the base layer 2, and the outermost layer 6 is not contaminated and its function is well maintained.

これに対し、比較例１は銅系層も錫系層も存在しないため製造が困難であった。また比較例２は前記体積比が１．８０のため最外層表面にＣｕ層が残存し、また比較例３は最外層がＳｎ層のためフレッティング現象が起きて、いずれも接触抵抗が大幅に増加した。 In contrast, Comparative Example 1 was difficult to manufacture because neither a copper-based layer nor a tin-based layer was present. In Comparative Example 2, the volume ratio is 1.80, so that the Cu layer remains on the outermost layer surface. In Comparative Example 3, the outermost layer is a Sn layer, and thus fretting phenomenon occurs. Increased.

前記微摺動試験で接触抵抗が１０ｍΩを超えると自動車用端子への使用が困難とされているが、本発明のめっき材料７（実施例１、２）はいずれも１０ｍΩを大幅に下回っており自動車用端子として十分使用できるものである。 When the contact resistance exceeds 10 mΩ in the fine sliding test, it is considered difficult to use for automobile terminals, but the plating materials 7 (Examples 1 and 2) of the present invention are significantly below 10 mΩ. It can be used as a car terminal.

［実施例３］
下地層２をＮｉ層（０．２μｍ）とＮｉ−Ｃｏ−Ｐ系合金層（０．２μｍ）の２層に設けた他は、実施例１のＮｏ．１と同じ方法によりめっき材料を作製し、実施例１と同じ方法により微摺動試験を行った。その結果、接触抵抗は初期値が１．７ｍΩ、微摺動試験中の最大値が３．２ｍΩといずれも極めて低い値を示した。これは基体１の成分の拡散が熱処理時および使用中において、より確実に防止されたためである。 [Example 3]
Example No. 1 in Example 1 except that the underlayer 2 was provided in two layers, a Ni layer (0.2 μm) and a Ni—Co—P alloy layer (0.2 μm). A plating material was produced by the same method as in Example 1, and a fine sliding test was conducted by the same method as in Example 1. As a result, the initial value of the contact resistance was 1.7 mΩ, and the maximum value during the micro-sliding test was 3.2 mΩ, both showing extremely low values. This is because the diffusion of the components of the substrate 1 is more reliably prevented during the heat treatment and during use.

［実施例４］
めっき積層体８の熱処理時間を短くした（熱処理時間：１２ｈ）他は、実施例２のＮｏ．４と同じ方法によりめっき材料７を作製し、実施例１と同じ方法により微摺動試験を行った。このめっき材料７は、中間層４の下側（基体側）がＣｕ_３Ｓｎ化合物を主体とし、上側がＣｕ_６Ｓｎ_５化合物を主体とし、最外層６の下側（基体側）がＣｕ_６Ｓｎ_５化合物を主体とし、上側がＣｕ_３Ｓｎ化合物を主体とするめっき材料であったが、接触抵抗は、初期値が２．１ｍΩ、微摺動試験中の最大値が４．６ｍΩであり、中間層４および最外層６の全体がＣｕ_６Ｓｎ_５化合物を主体とするめっき材料（実施例２のＮｏ．４）と同等の低い接触抵抗値を示した。 [Example 4]
Other than shortening the heat treatment time of the plated laminate 8 (heat treatment time: 12 h) A plating material 7 was produced by the same method as in Example 4, and a fine sliding test was conducted by the same method as in Example 1. In this plating material 7, the lower side (base side) of the intermediate layer 4 is mainly composed of Cu ₃ Sn compound, the upper side is mainly composed of Cu ₆ Sn ₅ compound, and the lower side (base side) of the outermost layer 6 is Cu ₆ Sn. _Although the plating material was mainly composed of ₅ compounds and the upper side was mainly composed of Cu ₃ Sn compound, the contact resistance had an initial value of 2.1 mΩ and a maximum value of 4.6 mΩ in the micro-sliding test. The entire layer 4 and outermost layer 6 exhibited a low contact resistance value equivalent to the plating material (No. 4 in Example 2) mainly composed of Cu ₆ Sn ₅ compound.

［実施例５］
実施例１のＮｏ．３のめっき積層体８を用い、リフロー処理を実施例１Ｎｏ．３の場合より高めの温度（リフロー炉内の温度：７７０℃）で施した他は、実施例１と同じ方法によりめっき材料７を製造した。
得られためっき材料７は、構成が図１（イ）に示したものとほぼ同じであるが、錫系層５の厚みが減少し、最外層６および中間層４はＣｕ_６Ｓｎ_５を主体とするＣｕ−Ｓｎ金属間化合物にＳｎ相またはＳｎ合金相９が分散し、図１（イ）と図１（ハ）の中間の構成を有するものであった。
このめっき材料７について実施例１と同じ摺動試験を行い、接触抵抗値の変化を連続的に測定した。その結果は、接触抵抗は初期値が１．８ｍΩ、最大値が３．６ｍΩであり、実施例１のＮｏ．３の結果と同等であった。 [Example 5]
No. of Example 1 No. 3 plating laminate 8 and reflow treatment in Example 1 No. The plating material 7 was manufactured by the same method as Example 1 except having performed at the temperature higher than the case of 3 (temperature in a reflow furnace: 770 degreeC).
The obtained plating material 7 has substantially the same structure as that shown in FIG. 1A, but the thickness of the tin-based layer 5 is reduced, and the outermost layer 6 and the intermediate layer 4 are mainly composed of Cu ₆ Sn ₅ . The Sn phase or the Sn alloy phase 9 was dispersed in the Cu—Sn intermetallic compound to have an intermediate structure between FIG. 1 (A) and FIG. 1 (C).
This plating material 7 was subjected to the same sliding test as in Example 1, and the change in the contact resistance value was continuously measured. As a result, the contact resistance had an initial value of 1.8 mΩ and a maximum value of 3.6 mΩ. It was equivalent to the result of 3.

［実施例６］
実施例２のＮｏ．６の積層体を用い、熱処理を実施例２Ｎｏ．６の場合より高めの温度（サンプルの実体温度：１８０℃）で施した他は、実施例１と同じ方法によりめっき材料を製造した。
得られためっき材料は、構成が図１（ロ）に示したものとほぼ同じであるが、錫系層５の厚みが減少し、最外層６および中間層４はＣｕ_６Ｓｎ_５を主体とするＣｕ−Ｓｎ金属間化合物にＳｎ相またはＳｎ合金相９が分散し、図１（ロ）と図１（ハ）の中間の構成を有するものであった。
このめっき材料７について実施例１と同じ摺動試験を行い、接触抵抗値の変化を連続的に測定した。その結果、接触抵抗は初期値が１．８ｍΩ、最大値が３．８ｍΩであり、実施例１のＮｏ．３の結果と同等であった。 [Example 6]
No. 2 in Example 2. No. 6 was used for heat treatment in Example 2 No. A plating material was produced by the same method as in Example 1 except that it was performed at a temperature higher than the case of 6 (substance temperature of the sample: 180 ° C.).
The obtained plating material has substantially the same structure as that shown in FIG. 1B, but the thickness of the tin-based layer 5 is reduced, and the outermost layer 6 and the intermediate layer 4 are mainly composed of Cu ₆ Sn _5. The Sn phase or the Sn alloy phase 9 was dispersed in the Cu—Sn intermetallic compound to be formed, and had an intermediate configuration between FIG. 1 (B) and FIG. 1 (C).
This plating material 7 was subjected to the same sliding test as in Example 1, and the change in the contact resistance value was continuously measured. As a result, the contact resistance had an initial value of 1.8 mΩ and a maximum value of 3.8 mΩ. It was equivalent to the result of 3.

［実施例７］
厚み０．２５ｍｍの銅合金（黄銅）条に脱脂および酸洗をこの順に施し、次いで前記銅合金条にＮｉ、Ｃｕ、Ｓｎ、Ｃｕをこの順に層状に表１に示す条件で電気めっきしてめっき積層体８を作製し、次いでこのめっき積層体８に熱処理をリフロー処理法により実施例５と同じ条件で施してめっき材料７を製造し、実施例１と同じ試験、調査を行った。ここでは、めっき積層体８のＮｉ層２’の厚みは０．４μｍとし、Ｃｕ層（内）３’とＣｕ層（外）５’の厚み（体積）比（内／外）は３．０とし、Ｓｎ層４’とＣｕ層（内＋外）の厚み（体積）比（Ｓｎ層／Ｃｕ層）は２．６０とした。なお、Ｓｎ層４’の厚みは１．０μｍとした。 [Example 7]
A copper alloy strip (brass) having a thickness of 0.25 mm is subjected to degreasing and pickling in this order, and then the copper alloy strip is electroplated with Ni, Cu, Sn, and Cu in this order in the order of layers as shown in Table 1. The laminated body 8 was produced, and then the plated laminated body 8 was subjected to a heat treatment by the reflow treatment method under the same conditions as in Example 5 to produce a plating material 7. The same tests and investigations as in Example 1 were performed. Here, the thickness of the Ni layer 2 ′ of the plated laminate 8 is 0.4 μm, and the thickness (volume) ratio (inner / outer) of the Cu layer (inner) 3 ′ and the Cu layer (outer) 5 ′ is 3.0. The thickness (volume) ratio (Sn layer / Cu layer) of the Sn layer 4 ′ and the Cu layer (inside + outside) was 2.60. The thickness of the Sn layer 4 ′ was 1.0 μm.

得られためっき材料７は、構成が図１（ハ）に示すような、下地層２上に銅系層３が、その上に最外層６が形成されたものであり、最外層６はＣｕ_６Ｓｎ_５を主体とするＣｕ−Ｓｎ金属間化合物にＳｎ相またはＳｎ合金相９が分散したものであった。
このめっき材料７について実施例１と同じ摺動試験を行い、接触抵抗値の変化を連続的に測定した。その結果、接触抵抗は初期値が１．８ｍΩ、最大値が３．９ｍΩであり、実施例１のＮｏ．３の結果と同等であった。 The obtained plating material 7 has a structure as shown in FIG. 1 (c), in which the copper-based layer 3 is formed on the base layer 2, and the outermost layer 6 is formed thereon. The outermost layer 6 is made of Cu. _The Sn phase or Sn alloy phase 9 was dispersed in a Cu—Sn intermetallic compound mainly composed of ₆ Sn ₅ .
This plating material 7 was subjected to the same sliding test as in Example 1, and the change in the contact resistance value was continuously measured. As a result, the contact resistance had an initial value of 1.8 mΩ and a maximum value of 3.9 mΩ. It was equivalent to the result of 3.

［実施例８］
実施例７において、Ｃｕ層（内）３’とＣｕ層（外）５’の厚み（体積）比（内／外）を１．０とし、Ｓｎ層とＣｕ層（内＋外）の厚み（体積）比（Ｓｎ層／Ｃｕ層）を２．６０とした他は、実施例７と同じ方法によりめっき材料７を製造し、実施例７と同じ試験、調査を行った。 [Example 8]
In Example 7, the thickness (volume) ratio (inner / outer) of the Cu layer (inner) 3 ′ and the Cu layer (outer) 5 ′ is 1.0, and the thickness of the Sn layer and Cu layer (inner + outer) ( A plating material 7 was produced by the same method as in Example 7 except that the volume ratio (Sn layer / Cu layer) was 2.60, and the same tests and investigations as in Example 7 were performed.

得られためっき材料７は、構成が図１（ニ）に示すような、下地層２上に最外層６が形成されたものであり、最外層６はＣｕ_６Ｓｎ_５を主体とするＣｕ−Ｓｎ金属間化合物にＳｎ相またはＳｎ合金相９が分散したものであった。このめっき材料は、接触抵抗が初期値１．９ｍΩ、最大値４．０ｍΩであり実施例１のＮｏ．３の結果と同等であった。 The resulting plated material 7 is configuration as shown in FIG. 1 (d), which outermost layer 6 is formed on the underlying layer 2, the outermost layer 6 is mainly composed of Cu ₆ Sn ₅ Cu- The Sn phase or the Sn alloy phase 9 was dispersed in the Sn intermetallic compound. This plating material had an initial value of 1.9 mΩ and a maximum value of 4.0 mΩ as the contact resistance. It was equivalent to the result of 3.

実施例５〜８の試験結果から、中間層４および最外層６、または最外層６のＣｕ−Ｓｎ金属間化合物にＳｎ相またはＳｎ合金相９が分散しためっき材料７においても低い接触抵抗値が得られることがわかる。このめっき材料７は中間層４或いは最外層６にＳｎ相およびＳｎ合金相９が分散されたものであり、実施例１〜４と同様、めっき積層体８の設計および熱処理が容易に行え、生産性に優れる。 From the test results of Examples 5 to 8, the contact resistance value is low even in the plating material 7 in which the Sn phase or the Sn alloy phase 9 is dispersed in the intermediate layer 4 and the outermost layer 6 or the Cu—Sn intermetallic compound of the outermost layer 6. It turns out that it is obtained. This plating material 7 is obtained by dispersing the Sn phase and the Sn alloy phase 9 in the intermediate layer 4 or the outermost layer 6. As in Examples 1 to 4, the plating laminate 8 can be easily designed and heat-treated. Excellent in properties.

実施例１〜８で得られためっき材料７を用いて嵌合型コネクタ端子を製造し、自動車のエンジンルーム内で実用に供したところ、いずれも長期に渡り良好な挿抜性が安定して得られることが確認された。 When the fitting type connector terminal is manufactured using the plating material 7 obtained in Examples 1 to 8 and put into practical use in the engine room of an automobile, good insertion / extraction properties can be stably obtained over a long period of time. It was confirmed that

（イ）〜（ニ）は本発明のめっき材料の実施形態の一例を示す斜視説明図である。(A)-(d) is a perspective explanatory drawing which shows an example of embodiment of the plating material of this invention. 本発明のめっき材料の製造に用いるめっき積層体の実施形態を示す斜視説明図である。It is a perspective explanatory view showing an embodiment of a plating layered product used for manufacture of a plating material of the present invention. 微摺動試験方法の斜視説明図である。It is a perspective explanatory view of a fine sliding test method.

符号の説明Explanation of symbols

１導電性基体
２Ｎｉなどからなる下地層
３ＣｕまたはＣｕ合金からなる銅系層
４Ｃｕ−Ｓｎ金属間化合物からなる中間層
５ＳｎまたはＳｎ合金からなる錫系層
６Ｃｕ−Ｓｎ金属間化合物からなる最外層
７めっき材料
２’ Ｎｉ層
３’ Ｃｕ層（内）
４’ Ｓｎ層
５’ Ｃｕ層（外）
８めっき積層体
９Ｓｎ相またはＳｎ合金相
１１めっき材料
１１ａめっき材料に設けた半球状張出部
１２めっき材料
１２ａめっき材料の最外層面 DESCRIPTION OF SYMBOLS 1 Conductive substrate 2 Base layer made of Ni or the like 3 Copper-based layer made of Cu or Cu alloy 4 Intermediate layer made of Cu-Sn intermetallic compound 5 Tin-based layer made of Sn or Sn alloy 6 From Cu-Sn intermetallic compound Outermost layer 7 plating material 2 ′ Ni layer 3 ′ Cu layer (inner)
4 'Sn layer 5' Cu layer (outside)
8 Plating laminate 9 Sn phase or Sn alloy phase 11 Plating material 11a Hemispherical overhang 12 provided on plating material Plating material 12a Outermost layer surface of plating material

Claims

導電性基体上にニッケル、ニッケル合金、コバルト、コバルト合金、鉄、鉄合金のいずれか１種からなる下地層、その上に銅または銅合金からなる銅系層、その上にＣｕ−Ｓｎ金属間化合物からなる中間層、その上に錫または錫合金からなる錫系層、その上にＣｕ−Ｓｎ金属間化合物からなる最外層が設けられていることを特徴とするめっき材料。 A base layer made of any one of nickel, nickel alloy, cobalt, cobalt alloy, iron, and iron alloy on a conductive substrate, a copper-based layer made of copper or a copper alloy thereon, and a Cu-Sn metal space between them A plating material comprising: an intermediate layer made of a compound; a tin-based layer made of tin or a tin alloy; and an outermost layer made of a Cu—Sn intermetallic compound.

導電性基体上にニッケル、ニッケル合金、コバルト、コバルト合金、鉄、鉄合金のいずれか１種からなる下地層、その上にＣｕ−Ｓｎ金属間化合物からなる中間層、その上に錫または錫合金からなる錫系層、その上にＣｕ−Ｓｎ金属間化合物からなる最外層が設けられていることを特徴とするめっき材料。 An underlayer made of nickel, nickel alloy, cobalt, cobalt alloy, iron or iron alloy on a conductive substrate, an intermediate layer made of Cu-Sn intermetallic compound thereon, and tin or a tin alloy thereon A plating material, comprising: a tin-based layer comprising: an outermost layer comprising a Cu—Sn intermetallic compound;

前記中間層および最外層のＣｕ−Ｓｎ金属間化合物がＣｕ_３Ｓｎ化合物を主体とすることを特徴とする請求項１または２に記載のめっき材料。 Plating material according to claim 1 or 2, wherein the intermediate layer and the outermost layer of the Cu-Sn intermetallic compound is characterized by mainly comprising Cu 3 _Sn compound.

前記中間層および最外層のＣｕ−Ｓｎ金属間化合物がＣｕ_６Ｓｎ_５化合物を主体とすることを特徴とする請求項１または２に記載のめっき材料。 The plating material according to claim 1, wherein the Cu—Sn intermetallic compound of the intermediate layer and the outermost layer is mainly composed of a Cu ₆ Sn ₅ compound.

前記中間層が上下２層からなり、下側（基体側）の中間層がＣｕ_３Ｓｎ化合物を主体とし、上側の中間層がＣｕ_６Ｓｎ_５化合物を主体とし、前記最外層が上下２層からなり、下側（基体側）の最外層がＣｕ_６Ｓｎ_５化合物を主体とし、上側の最外層がＣｕ_３Ｓｎ化合物を主体とすることを特徴とする請求項１または２に記載のめっき材料。 The intermediate layer is composed of two upper and lower layers, the lower (substrate side) intermediate layer is mainly composed of Cu ₃ Sn compound, the upper intermediate layer is mainly composed of Cu ₆ Sn ₅ compound, and the outermost layer is composed of upper and lower layers. The plating material according to claim 1, wherein the outermost layer on the lower side (substrate side) is mainly composed of a Cu ₆ Sn ₅ compound, and the uppermost outermost layer is mainly composed of a Cu ₃ Sn compound.

前記Ｃｕ_６Ｓｎ_５化合物にＳｎ相またはＳｎ合金相が分散していることを特徴とする請求項４または５に記載のめっき材料。 The plating material according to claim 4 or 5, wherein an Sn phase or an Sn alloy phase is dispersed in the Cu ₆ Sn ₅ compound.

導電性基体上にニッケル、ニッケル合金、コバルト、コバルト合金、鉄、鉄合金のいずれか１種からなる下地層、その上に銅または銅合金からなる銅系層、その上にＣｕ−Ｓｎ金属間化合物からなる最外層が設けられており、前記最外層のＣｕ−Ｓｎ金属間化合物がＣｕ_６Ｓｎ_５化合物を主体とし、前記Ｃｕ_６Ｓｎ_５化合物にＳｎ相またはＳｎ合金相が分散していることを特徴とするめっき材料。 A base layer made of any one of nickel, nickel alloy, cobalt, cobalt alloy, iron, and iron alloy on a conductive substrate, a copper-based layer made of copper or a copper alloy thereon, and a Cu-Sn metal space between them and the outermost layer is provided made of a compound, the Cu-Sn intermetallic compound of said outermost layer is composed mainly of _Cu 6 Sn ₅ compound, Sn phase or Sn alloy phase in the _Cu 6 Sn ₅ compound is dispersed Plating material characterized by

導電性基体上にニッケル、ニッケル合金、コバルト、コバルト合金、鉄、鉄合金のいずれか１種からなる下地層、その上にＣｕ−Ｓｎ金属間化合物からなる最外層が設けられており、前記最外層のＣｕ−Ｓｎ金属間化合物がＣｕ_６Ｓｎ_５化合物を主体とし、前記Ｃｕ_６Ｓｎ_５化合物にＳｎ相またはＳｎ合金相が分散していることを特徴とするめっき材料。 A base layer made of any one of nickel, nickel alloy, cobalt, cobalt alloy, iron, and iron alloy is provided on the conductive substrate, and an outermost layer made of Cu-Sn intermetallic compound is provided on the base layer. plating material Cu-Sn intermetallic compound layer is mainly composed of _Cu 6 Sn ₅ compound, Sn phase or Sn alloy phase in the _Cu 6 Sn ₅ compound, characterized in that the dispersed.

前記導電性基体上に、下地層が少なくとも２層設けられていることを特徴とする請求項１乃至８のいずれかに記載のめっき材料。 The plating material according to claim 1, wherein at least two underlayers are provided on the conductive substrate.

電気電子部品の少なくとも摺動部が請求項１乃至９のいずれかに記載のめっき材料からなることを特徴とする電気電子部品。 An electrical / electronic component, wherein at least a sliding portion of the electrical / electronic component is made of the plating material according to claim 1.

嵌合型コネクタまたは接触子に用いられることを特徴とする請求項１０に記載の電気電子部品。 The electric / electronic component according to claim 10, wherein the electric / electronic component is used for a fitting-type connector or a contact.