JPWO2018074256A1 - Conductive strip - Google Patents

Conductive strip Download PDF

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JPWO2018074256A1
JPWO2018074256A1 JP2018546247A JP2018546247A JPWO2018074256A1 JP WO2018074256 A1 JPWO2018074256 A1 JP WO2018074256A1 JP 2018546247 A JP2018546247 A JP 2018546247A JP 2018546247 A JP2018546247 A JP 2018546247A JP WO2018074256 A1 JPWO2018074256 A1 JP WO2018074256A1
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alloy
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conductive strip
oxide
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JP7060514B2 (en
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秀一 北河
秀一 北河
昭頼 橘
昭頼 橘
良和 奥野
良和 奥野
恵人 藤井
恵人 藤井
達也 中津川
達也 中津川
紳悟 川田
紳悟 川田
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THE FURUKAW ELECTRIC CO., LTD.
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/02—Single bars, rods, wires, or strips
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/025—Composite material having copper as the basic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Laminated Bodies (AREA)

Abstract

【課題】高温環境下で低接触抵抗を維持して耐熱性に優れ、かつ、低挿入性に優れる導電性条材を提供する。【解決手段】ＣｕまたはＣｕ合金からなる導電性基材の上に、ＮｉまたはＮｉ合金からなる層、Ｃｕを主成分とする層、ＣｕおよびＳｎからなる合金層をこの順に有する導電性条材であって、前記ＮｉまたはＮｉ合金からなる層の厚さが０．１〜２．０μｍ、前記Ｃｕを主成分とする層の厚さが０．０１〜０．１μｍ、前記ＣｕおよびＳｎからなる合金層の厚さが０．１〜２．０μｍであって、表面粗さＲａが０．０５〜１．０μｍであり、表面に形成される酸化物膜中にＣｕの酸化物およびＳｎの酸化物が含まれ、酸化物膜の厚さが５０ｎｍ以下であり、Ｓｎの酸化物の割合（％）が９０％以上であり、かつ、この導電性条材を温度１４０℃で１２０時間の条件で大気中において加熱した後の接触抵抗が、Ａｇプローブを介した荷重１Ｎの条件下で１０ｍΩ以下である、導電性条材。【選択図】図１Disclosed is a conductive strip material that maintains a low contact resistance in a high temperature environment, is excellent in heat resistance, and is excellent in low insertion property. A conductive strip having a layer made of Ni or a Ni alloy, a layer containing Cu as a main component, and an alloy layer made of Cu and Sn in this order on a conductive substrate made of Cu or a Cu alloy. The thickness of the layer made of Ni or Ni alloy is 0.1 to 2.0 μm, the thickness of the layer mainly composed of Cu is 0.01 to 0.1 μm, and the alloy is made of Cu and Sn. The layer thickness is 0.1 to 2.0 μm, the surface roughness Ra is 0.05 to 1.0 μm, and an oxide of Cu and an oxide of Sn are formed in the oxide film formed on the surface The oxide film has a thickness of 50 nm or less, the Sn oxide ratio (%) is 90% or more, and the conductive strip is air-conditioned at a temperature of 140 ° C. for 120 hours. The contact resistance after heating inside is a strip with a load of 1 N through the Ag probe. It is 10mΩ or less under a conductive strip member. [Selection] Figure 1

Description

本発明は、車載部品、電気電子部品、リードフレーム、リレー、スイッチ、ソケット等に好適な導電性条材に関する。   The present invention relates to a conductive strip suitable for in-vehicle components, electrical / electronic components, lead frames, relays, switches, sockets, and the like.

電気接点材には、従来から電気伝導性に優れた銅（Ｃｕ）または銅合金が利用されてきたが、近年は接点特性の向上が進み、銅または銅合金をそのまま用いるケースは減少している。このような従来の材料に代わって銅または銅合金上に各種表面処理した材料が製造・利用されている。特に電気接点材として、電気接点部に銅または銅合金上にスズ（Ｓｎ）またはＳｎ合金がめっきされた部材が汎用されている。   Conventionally, copper (Cu) or a copper alloy having excellent electrical conductivity has been used as an electrical contact material. However, in recent years, contact characteristics have been improved, and the number of cases using copper or a copper alloy as it is is decreasing. . Instead of such conventional materials, various surface-treated materials on copper or copper alloys are manufactured and used. In particular, as an electrical contact material, a member in which tin (Sn) or Sn alloy is plated on copper or a copper alloy on an electrical contact portion is widely used.

このめっき材料は、導電性基材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と耐食性とはんだ付け性を備えた高性能導電体として知られており、電気・電子機器に用いられる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、銅などの導電性基材の合金成分が前記めっき層に拡散するのを防止するため、導電性基材上にバリア機能を有するニッケル（Ｎｉ）、コバルト（Ｃｏ）などが下地めっきされる。   This plating material is known as a high-performance conductor with excellent conductivity and strength of conductive substrates and excellent electrical connectivity, corrosion resistance and solderability of plating layers. Widely used for various terminals and connectors used. This plating material is usually nickel (Ni), cobalt (Co), etc. having a barrier function on the conductive substrate in order to prevent the alloy component of the conductive substrate such as copper from diffusing into the plating layer. Is undercoated.

このめっき材料を端子として用いた場合、例えば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めっき層のＳｎが易酸化性のため、Ｓｎめっき層の表面に酸化皮膜が形成される。この酸化皮膜は脆いため端子接続時に破れて、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。   When this plating material is used as a terminal, for example, in a high temperature environment such as in an automobile engine room, Sn of the Sn plating layer on the surface of the terminal is easily oxidizable, so that an oxide film is formed on the surface of the Sn plating layer. . Since this oxide film is fragile, it is broken at the time of terminal connection, and the underlying unoxidized Sn plating layer is exposed to provide good electrical connectivity.

しかし、近年の電気接点材の使用環境として、高温環境下において使用されるケースが多くなっている。例えば自動車のエンジンルーム内でのセンサー用接点材料などは、１００℃〜２００℃等の高温環境下で使用される可能性が高まっている。このため、従来の民生機器で想定された使用温度よりも高温における接点特性等の信頼性が求められている。特に接点特性の信頼性を左右する原因として、高温下では、導電性基材成分の拡散および表面酸化により最表層での接触抵抗を増大させてしまうことが問題となっている。   However, in recent years, there are many cases where electrical contact materials are used in high temperature environments. For example, a sensor contact material in an engine room of an automobile is likely to be used in a high temperature environment such as 100 ° C. to 200 ° C. For this reason, reliability such as contact characteristics at a temperature higher than the operating temperature assumed in conventional consumer devices is required. In particular, as a cause that affects the reliability of the contact characteristics, there is a problem that the contact resistance in the outermost layer is increased due to diffusion and surface oxidation of the conductive base material component at high temperatures.

また、車両の組み立て性向上のため、挿入力を下げる試みとして、硬いＣｕと軟らかいＳｎとの合金層を拡散させる方式がとられている。しかし、表面に存在するＣｕの酸化により接触抵抗が悪化することが問題とされてきた。そのため、この導電性基材成分の拡散抑制および酸化防止について種々検討がなされてきた。   Further, in order to improve the assemblability of the vehicle, a method of diffusing an alloy layer of hard Cu and soft Sn is used as an attempt to reduce the insertion force. However, it has been a problem that contact resistance deteriorates due to oxidation of Cu existing on the surface. Therefore, various studies have been made on diffusion suppression and oxidation prevention of the conductive base material component.

特許文献１では、所定の銅合金（Ｃｕ−Ｎｉ−Ｓｎ−Ｐ合金）よりなる母材上に形成された拡散バリア層としてのＮｉまたはＮｉ合金層（以下、単にＮｉ層という。）、拡散バリア層の上層として拡散バリア層状に形成された中間層としてのＣｕ−Ｓｎ合金層、最表層としてのＳｎまたはＳｎ合金層（以下、単にＳｎ層という。）（これら３つの層は、導電性の表面皮覆層である。）を各々所定の層厚で有することにより長期の接触信頼性を維持している。
このように、特許文献１では、接続用端子の長期にわたる接触信頼性を維持する方法として、Ｃｕ−Ｓｎ合金中間層を拡散バリア層として用いている。Ｃｕ−Ｓｎ合金中間層の種類は規定されているが、表面に形成される酸化物膜（Ｃｕ２Ｏ膜）の規定及びその制御については記載されていない。特許文献１では、Ｓｎ層／Ｃｕ−Ｓｎ層／Ｎｉ層の構成及びそれらの厚さを規定しているが、酸化物の内、Ｃｕ２Ｏ膜が表面近傍に存在しないことを規定している。In Patent Document 1, Ni or a Ni alloy layer (hereinafter simply referred to as a Ni layer) as a diffusion barrier layer formed on a base material made of a predetermined copper alloy (Cu—Ni—Sn—P alloy), a diffusion barrier. Cu—Sn alloy layer as an intermediate layer formed as a diffusion barrier layer as an upper layer of the layer, Sn or Sn alloy layer as an outermost layer (hereinafter simply referred to as Sn layer) (these three layers are conductive surfaces) Long-term contact reliability is maintained by having a predetermined layer thickness.
As described above, in Patent Document 1, the Cu—Sn alloy intermediate layer is used as the diffusion barrier layer as a method of maintaining the contact reliability over a long period of the connection terminal. The type of the Cu-Sn alloy intermediate layer is specified, for defining and controlling the oxide film formed on the surface (Cu 2 O layer) is not described. In Patent Document 1, the structure of Sn layer / Cu—Sn layer / Ni layer and the thickness thereof are specified, but it is specified that the Cu 2 O film does not exist in the vicinity of the surface among the oxides. .

特開２０１５−１５１５７０JP2015-151570

近年、例えば車載部品においては、環境温度の高温化や電気駆動車の普及による電流量増加により、これまで以上に材料に高温下での良好な電気接続性（以下、単に耐熱性という。）が求められている。その他の用途においても、環境温度の高温化や、部品の小型化や高出力化に伴う回路電流密度の増加が見られており、やはり耐熱性の向上が求められている。   In recent years, for example, in in-vehicle parts, due to the increase in the amount of current due to the increase in the environmental temperature and the spread of electric driving vehicles, the material has better electrical connectivity at higher temperatures (hereinafter simply referred to as heat resistance) than ever before. It has been demanded. In other applications as well, an increase in circuit current density has been observed as the environmental temperature is increased, and the size and output of parts are reduced, so that improvement in heat resistance is also required.

前記特許文献１に記載された従来の技術では、近年の高温耐久性の要求の高まりに対応するには不十分である。つまり、高温環境下で形成される拡散層の形状により、母材のＣｕ合金が、Ｎｉ層、Ｃｕ−Ｓｎ合金層を介して、Ｓｎ層に拡散し、Ｓｎ層と反応してＳｎ層厚が減少する。さらには、もしＳｎ層がなくなってしまうと最表層に母材のＣｕ合金が露出し、さらには酸化銅（Ｃｕ２Ｏ膜）を形成し接触抵抗が上昇するという問題がある。The conventional technique described in Patent Document 1 is insufficient to cope with the recent increase in demand for high temperature durability. That is, depending on the shape of the diffusion layer formed in a high temperature environment, the base Cu alloy diffuses into the Sn layer via the Ni layer and the Cu—Sn alloy layer, reacts with the Sn layer, and the Sn layer thickness increases. Decrease. Furthermore, if the Sn layer disappears, the base Cu alloy is exposed in the outermost layer, and further, copper oxide (Cu 2 O film) is formed and the contact resistance increases.

上記の事情に鑑み、本発明の課題は、高温環境下で低接触抵抗を維持して耐熱性に優れ、かつ、低挿入性に優れる導電性条材を提供することである。   In view of the above circumstances, an object of the present invention is to provide a conductive strip material that maintains a low contact resistance under a high temperature environment, has excellent heat resistance, and is excellent in low insertion property.

本発明者らは、車載部品、電気電子部品、リードフレーム、リレー、スイッチ、ソケット等に好適なＳｎめっき材について鋭意研究を行い、ＣｕまたはＣｕ合金からなる導電性基材の上に、ＮｉまたはＮｉ合金からなる層、Ｃｕを主成分とする層、ＣｕおよびＳｎからなる合金層をこの順に有する導電性条材であって、これら３つの層厚を各々所定の範囲に規定し、表面粗さＲａが所定の範囲であり、表面に形成される酸化物膜中にＣｕの酸化物およびＳｎの酸化物が含まれ、その厚さが所定の範囲であり、Ｓｎの酸化物が所定の割合以上であって、この導電性条材を温度１４０℃で１２０時間の条件で大気中において加熱した後の接触抵抗が、Ａｇプローブを介した荷重１Ｎの条件下で所定の範囲以下である導電性条材であることで、課題を解決することを見出した。   The present inventors have earnestly studied Sn plating materials suitable for in-vehicle parts, electrical and electronic parts, lead frames, relays, switches, sockets, etc., and on a conductive substrate made of Cu or Cu alloy, Ni or A conductive strip having a Ni alloy layer, a Cu-based layer, and an Cu and Sn alloy layer in this order, each of which has a predetermined thickness and a surface roughness. Ra is in a predetermined range, the oxide film formed on the surface includes Cu oxide and Sn oxide, the thickness is in a predetermined range, and Sn oxide is a predetermined ratio or more The contact resistance after heating the conductive strip in the atmosphere at a temperature of 140 ° C. for 120 hours is below a predetermined range under a load of 1 N through the Ag probe. It is a problem by being a material It was found to be solved.

本発明によれば、下記の手段が提供される。
（１）ＣｕまたはＣｕ合金からなる導電性基材の上に、ＮｉまたはＮｉ合金からなる層、Ｃｕを主成分とする層、ＣｕおよびＳｎからなる合金層をこの順に有する導電性条材であって、
前記ＮｉまたはＮｉ合金からなる層の厚さが０．１〜２．０μｍ、前記Ｃｕを主成分とする層の厚さが０．０１〜０．１μｍ、前記ＣｕおよびＳｎからなる合金層の厚さが０．１〜２．０μｍであって、
表面粗さＲａが０．０５〜１．０μｍであり、表面に形成される酸化物膜中にＣｕの酸化物およびＳｎの酸化物が含まれ、酸化物膜の厚さが５０ｎｍ以下であり、Ｓｎの酸化物の割合（％）が９０％以上であり、かつ、この導電性条材を温度１４０℃で１２０時間の条件で大気中において加熱した後の接触抵抗が、Ａｇプローブを介した荷重１Ｎの条件下で１０ｍΩ以下であることを特徴とする導電性条材。
（２）前記ＮｉまたはＮｉ合金からなる層の厚さが０．２〜１．０μｍ、前記Ｃｕを主成分とする層の厚さが０．０１〜０．０５μｍ、前記ＣｕおよびＳｎからなる合金層の厚さが０．４〜１．５μｍである（１）項に記載の導電性条材。
（３）前記表面に形成される酸化物膜中に銅の酸化物がＣｕＯまたはＣｕ２Ｏからなり、Ｓｎの酸化物がＳｎＯまたはＳｎＯ２からなる（１）又は（２）項に記載の導電性条材。
（４）前記導電性条材の表面の動摩擦係数が、０．３０以下である（１）〜（３）のいずれか１項に記載の導電性条材。According to the present invention, the following means are provided.
(1) A conductive strip having a layer made of Ni or Ni alloy, a layer containing Cu as a main component, and an alloy layer made of Cu and Sn in this order on a conductive substrate made of Cu or Cu alloy. And
The thickness of the layer made of Ni or Ni alloy is 0.1 to 2.0 μm, the thickness of the layer mainly composed of Cu is 0.01 to 0.1 μm, the thickness of the alloy layer made of Cu and Sn Is 0.1 to 2.0 μm,
The surface roughness Ra is 0.05 to 1.0 μm, the oxide film formed on the surface contains Cu oxide and Sn oxide, and the thickness of the oxide film is 50 nm or less, The ratio of Sn oxide (%) is 90% or more, and the contact resistance after heating the conductive strip in the atmosphere at a temperature of 140 ° C. for 120 hours is the load through the Ag probe. A conductive strip characterized by being 10 mΩ or less under the condition of 1N.
(2) The thickness of the Ni or Ni alloy layer is 0.2 to 1.0 μm, the thickness of the Cu-based layer is 0.01 to 0.05 μm, and the Cu and Sn alloy The conductive strip according to item (1), wherein the layer has a thickness of 0.4 to 1.5 μm.
(3) Conductivity according to (1) or (2), wherein a copper oxide is formed of CuO or Cu 2 O and an oxide of Sn is formed of SnO or SnO 2 in the oxide film formed on the surface. Sex strip material.
(4) The conductive strip according to any one of (1) to (3), wherein the surface of the conductive strip has a dynamic friction coefficient of 0.30 or less.

本発明の導電性条材によれば、表面でのＣｕ系酸化物の成長による接触抵抗の増加を防ぐことができる。また、接点部分の摺動やフレッティング等で表面がワイピングされ、新生面が露出した後に再形成される酸化物膜でもＳｎの酸化物の割合（％）が９０％以上である（Ｃｕ系酸化物の割合が１０％を超えない）ため、実使用上、高温長時間保持後においても、接触抵抗の上昇を抑えることによって耐熱性に優れる。また、本発明の導電性条材は、挿入力が小さくて、低挿入性に優れる。
ここで、「ワイピング」とは、接点部が摺動することにより、表面の汚れや酸化物膜が取り除かれ、新生面が生じる現象をいう。
本発明の上記及び他の特徴及び利点は、適宜添付の図面を参照して、下記の記載からより明らかになるであろう。According to the conductive strip of the present invention, an increase in contact resistance due to the growth of Cu-based oxide on the surface can be prevented. Further, even in the oxide film that is re-formed after the surface is wiped by sliding or fretting of the contact portion and the new surface is exposed, the Sn oxide ratio (%) is 90% or more (Cu-based oxide) Therefore, even after holding at high temperature for a long time, the heat resistance is excellent by suppressing the increase in contact resistance. Further, the conductive strip of the present invention has a low insertion force and is excellent in low insertion property.
Here, “wiping” refers to a phenomenon in which a dirt or oxide film on the surface is removed and a new surface is generated when the contact portion slides.
The above and other features and advantages of the present invention will become more apparent from the following description, with reference where appropriate to the accompanying drawings.

図１（ａ）は、本発明の導電性条材の一実施形態（表面に、ＳｎまたはＳｎ合金層が存在しない場合）の側面断面図であり、図１（ｂ）は、図１（ａ）を紙面の上方から見た場合の平面図である。Fig.1 (a) is side surface sectional drawing of one Embodiment (when Sn or Sn alloy layer does not exist in the surface) of the electroconductive strip | belt material of this invention, FIG.1 (b) is FIG. ) Is a plan view when viewed from above the sheet. 図２（ａ）は、本発明の導電性条材の別の実施形態（表面に、ＳｎまたはＳｎ合金層が海島状に存在する場合）の側面断面図であり、図２（ｂ）は、図２（ａ）を紙面の上方から見た場合の平面図である。FIG. 2A is a side cross-sectional view of another embodiment of the conductive strip of the present invention (when Sn or Sn alloy layer is present on the surface in the form of sea islands), and FIG. It is a top view at the time of seeing Fig.2 (a) from the upper direction of a paper surface.

本発明の導電性条材の好ましい一実施形態について、詳細に説明する。図１（ａ）および１（ｂ）に示すように、本発明の導電性条材（１０）は、ＣｕまたはＣｕ合金からなる導電性基材（１）上に、ＮｉまたはＮｉ合金からなる層（２）、Ｃｕを主成分とする層（３）、ＣｕおよびＳｎからなる合金層（例えば、Ｃｕ３Ｓｎ層、Ｃｕ６Ｓｎ５層などのＣｕ−Ｓｎ合金層）（４）が、この順で形成された構成である。A preferred embodiment of the conductive strip of the present invention will be described in detail. As shown in FIGS. 1 (a) and 1 (b), the conductive strip (10) of the present invention is a layer made of Ni or Ni alloy on a conductive substrate (1) made of Cu or Cu alloy. (2), a layer mainly composed of Cu (3), an alloy layer composed of Cu and Sn (for example, Cu—Sn alloy layers such as Cu 3 Sn layer and Cu 6 Sn 5 layer) (4) in this order. It is the structure formed by.

導電性基材（１）の母材は、通常、導電性材料に用いられているＣｕまたはＣｕ合金からなる導電性基材を、特に制限なく用いることができる。
導電性基材（１）の形状には特に制限は無く、例えば板、条、箔、線などがある。以下では実施形態として板材、条材について説明するが、その形状はこれらに限定されるものではない。ＣｕまたはＣｕ合金の種類は特に限定されるものではなく、使用する用途の強度、導電率等の要求に応じて、適宜選択すれば良い。
導電性基材（１）に用いることができる銅合金の一例として、ＣＤＡ（Ｃｏｐｐｅｒ Ｄｅｖｅｌｏｐｍｅｎｔ Ａｓｓｏｃｉａｔｉｏｎ）掲載合金である「Ｃ１４４１０（Ｃｕ−０．１５Ｓｎ、古河電気工業（株）製、商品名：ＥＦＴＥＣ３）」、「Ｃ１９４００（Ｃｕ−Ｆｅ系合金材料、Ｃｕ−２．３Ｆｅ−０．０３Ｐ−０．１５Ｚｎ）」、「Ｃ１８０４５（Ｃｕ−０．３Ｃｒ−０．２５Ｓｎ−０．５Ｚｎ、古河電気工業（株）製、商品名：ＥＦＴＥＣ６４Ｔ）」、「Ｃ６４７７０（コルソン系合金（Ｃｕ−Ｎｉ−Ｓｉ系合金）材料、古河電気工業（株）製、商品名：ＥＦＴＥＣ−９７）」、「Ｃ６４７７５（コルソン系合金材料、古河電気工業（株）製、商品名：ＥＦＴＥＣ−８２０）」等を用いることができる。（なお、前記銅合金の各元素の前の数字の単位は銅合金中の質量％を示す。）また、ＴＰＣ（タフピッチ銅）やＯＦＣ（無酸素銅）、りん青銅、黄銅（例えば、７０質量％Ｃｕ−３０質量％Ｚｎ。７／３黄銅と略記する。）等も用いることができる。導電性や放熱性を向上させるという観点からは、導電率が１０％ＩＡＣＳ以上の銅合金の条材とすることが好ましい。なお、銅合金を導電性基材（１）として取り扱う時での本発明の「基材成分」とは、基金属である銅のことを示すものとする。導電性基材（１）の厚さには特に制限はないが、通常、０．０５〜２．００ｍｍであり、好ましくは、０．１〜１．２ｍｍである。As the base material of the conductive substrate (1), a conductive substrate made of Cu or a Cu alloy, which is usually used for a conductive material, can be used without any particular limitation.
There is no restriction | limiting in particular in the shape of an electroconductive base material (1), For example, there exist a board, a strip, foil, a line | wire, etc. Below, although a board | plate material and a strip are demonstrated as embodiment, the shape is not limited to these. The kind of Cu or Cu alloy is not particularly limited, and may be appropriately selected according to the demands for strength, conductivity and the like of the intended use.
As an example of a copper alloy that can be used for the conductive substrate (1), CDA (Copper Development Association) listed alloy “C14410 (Cu-0.15Sn, Furukawa Electric Co., Ltd., trade name: EFTEC3)” "C19400 (Cu-Fe alloy material, Cu-2.3Fe-0.03P-0.15Zn)", "C18045 (Cu-0.3Cr-0.25Sn-0.5Zn, Furukawa Electric Co., Ltd. , Product name: EFTEC64T), “C64770 (Corson alloy (Cu—Ni—Si alloy) material, Furukawa Electric Co., Ltd., product name: EFTEC-97)”, “C64775 (Corson alloy) Materials, manufactured by Furukawa Electric Co., Ltd., trade name: EFTEC-820) "and the like can be used. (The unit of the number before each element of the copper alloy indicates mass% in the copper alloy.) Also, TPC (tough pitch copper), OFC (oxygen-free copper), phosphor bronze, brass (for example, 70 mass) % Cu-30 mass% Zn, abbreviated as 7/3 brass), etc. can also be used. From the viewpoint of improving electrical conductivity and heat dissipation, it is preferable to use a copper alloy strip having an electrical conductivity of 10% IACS or higher. In addition, when handling a copper alloy as an electroconductive base material (1), the "base material component" of this invention shall show the copper which is a base metal. Although there is no restriction | limiting in particular in the thickness of an electroconductive base material (1), Usually, it is 0.05-2.00 mm, Preferably, it is 0.1-1.2 mm.

ＮｉまたはＮｉ合金からなる層（２）は、例えばＮｉが用いられ、導電性基材（１）からＣｕおよびＳｎからなる合金層（４）である表面層への基材成分Ｃｕの拡散を抑制する拡散バリア層として作用する。ＮｉまたはＮｉ合金からなる層（２）の厚さは０．１〜２．０μｍであり、０．２〜１．０μｍが好ましい。薄すぎると基材成分Ｃｕの拡散抑制効果が小さくなり、導電性条材（１０）の耐熱性が低下する。また厚すぎると曲げ加工性が低下し、曲げ部の割れが生じる恐れがある。またＮｉまたはＮｉ合金からなる層（２）はＮｉ合金で形成されていても良く、例えばＮｉ−Ｐ、Ｎｉ−Ｃｕ、Ｎｉ−Ｃｒ、Ｎｉ−Ｓｎ、Ｎｉ−Ｚｎ、Ｎｉ−Ｆｅ等を用いることができる。   The layer (2) made of Ni or Ni alloy is made of, for example, Ni and suppresses diffusion of the base material component Cu from the conductive base material (1) to the surface layer which is an alloy layer (4) made of Cu and Sn. Acts as a diffusion barrier layer. The thickness of the layer (2) made of Ni or Ni alloy is 0.1 to 2.0 μm, preferably 0.2 to 1.0 μm. When it is too thin, the diffusion suppressing effect of the base material component Cu is reduced, and the heat resistance of the conductive strip (10) is lowered. On the other hand, if the thickness is too thick, the bending workability is lowered, and there is a risk that the bent portion will be cracked. Further, the layer (2) made of Ni or Ni alloy may be made of Ni alloy, for example, Ni—P, Ni—Cu, Ni—Cr, Ni—Sn, Ni—Zn, Ni—Fe or the like is used. Can do.

Ｃｕを主成分とする層（３）とＣｕおよびＳｎからなる合金層（４）は、ＮｉまたはＮｉ合金からなる層（２）上に、Ｃｕを主成分とする層（３）、およびＳｎまたはＳｎ合金からなる層である表面層（５）を順に形成した後にリフロー処理することで、Ｃｕを主成分とする層（３）とＳｎまたはＳｎ合金からなる層（５）とが反応することで得られる。   The layer (3) mainly composed of Cu and the alloy layer (4) composed of Cu and Sn are formed on the layer (2) composed of Ni or Ni alloy, the layer (3) composed mainly of Cu, and Sn or By forming the surface layer (5), which is a layer made of Sn alloy, in order and then performing a reflow treatment, the layer (3) containing Cu as a main component and the layer (5) made of Sn or Sn alloy react. can get.

Ｃｕを主成分とする層（３）とは、Ｃｕが５０質量％以上で構成されていることを意味する。さらには７５質量％以上で構成されていることが好ましい。例えば、Ｃｕ、Ｃｕ−Ｎｉ、Ｃｕ−Ｓｎからなる。Ｃｕを主成分とする層（３）の厚さは０．０１〜０．１μｍであり、０．０１〜０．０５μｍであることが好ましい。薄すぎると拡散バリア層としての効果が小さくなり、導電性条材（１０）の耐熱性が低下する。また厚すぎると加熱劣化後のめっき表面でのＣｕ濃度が上昇し、Ｃｕ酸化物の濃度が増加する恐れがある。   The layer (3) containing Cu as a main component means that Cu is composed of 50% by mass or more. Further, it is preferably composed of 75% by mass or more. For example, it consists of Cu, Cu-Ni, Cu-Sn. The thickness of the layer (3) containing Cu as a main component is 0.01 to 0.1 μm, and preferably 0.01 to 0.05 μm. If it is too thin, the effect as a diffusion barrier layer is reduced, and the heat resistance of the conductive strip (10) is lowered. On the other hand, if it is too thick, the Cu concentration on the plating surface after heat deterioration may increase, and the concentration of Cu oxide may increase.

また、ＣｕおよびＳｎからなる合金層（４）は、主にＣｕ３ＳｎやＣｕ６Ｓｎ５などからなる。主にＣｕ３ＳｎやＣｕ６Ｓｎ５からなるとは、Ｃｕ３ＳｎやＣｕ６Ｓｎ５が５０質量％以上で構成されていることを意味する。表面層（５）であるＳｎまたはＳｎ合金からなる層が、リフロー処理によってＣｕを主成分とする層（３）と反応した後には、ＣｕおよびＳｎからなる合金層（４）が、基材成分の拡散を防止する拡散バリア層として作用する。ＣｕおよびＳｎからなる合金層（４）の厚さは０．１〜２．０μｍであり、０．４〜１．５μｍであることが好ましい。さらには０．３５〜０．７μｍであることが好ましい。薄すぎると拡散バリア層としての効果が小さくなり、導電性条材（１０）の耐熱性が低下する。また厚すぎると曲げ加工性が低下し、曲げ部の割れが生じる恐れがある。
また、ＳｎまたはＳｎ合金からなる層（５）が残存する場合、海島状に存在することが好ましい。（図２（ａ）および２（ｂ）参照。）The alloy layer (4) made of Cu and Sn is mainly made of Cu 3 Sn, Cu 6 Sn 5 or the like. Consisting mainly of Cu 3 Sn or Cu 6 Sn 5 means that Cu 3 Sn or Cu 6 Sn 5 is composed of 50% by mass or more. After the surface layer (5) made of Sn or Sn alloy reacts with the layer (3) containing Cu as a main component by the reflow treatment, the alloy layer (4) made of Cu and Sn becomes the base material component. Acts as a diffusion barrier layer to prevent the diffusion of The thickness of the alloy layer (4) made of Cu and Sn is 0.1 to 2.0 μm, and preferably 0.4 to 1.5 μm. Furthermore, it is preferable that it is 0.35-0.7 micrometer. If it is too thin, the effect as a diffusion barrier layer is reduced, and the heat resistance of the conductive strip (10) is lowered. On the other hand, if the thickness is too thick, the bending workability is lowered, and there is a risk that the bent portion will be cracked.
Further, when the layer (5) made of Sn or Sn alloy remains, it is preferably present in a sea island shape. (See FIGS. 2 (a) and 2 (b).)

本発明の導電性条材（１０）において、ＳｎまたはＳｎ合金からなる層（表面層）（５）は、ＣｕまたはＣｕ合金からなる導電性基材（１）の上に、ＮｉまたはＮｉ合金からなる層（２）、Ｃｕを主成分とする層（３）およびＳｎまたはＳｎ合金からなる層（表面層）（５）を順に形成した後にリフロー処理した際、ＣｕおよびＳｎからなる合金層（４）の形成に使われることにより、図１（ａ）および１（ｂ）に示すように、全てＣｕおよびＳｎからなる合金層（４）の形成に使われ、消失してしまってもよい。また、図２（ａ）および２（ｂ）に示すように、ＳｎまたはＳｎ合金からなる層（表面層）（５）の一部が使われず、海島状に残存しても良い。残存したＳｎまたはＳｎ合金からなる層（表面層）（５）の厚さは、０〜０．１μｍであることが好ましく、０〜０．０５μｍであることがより好ましい。厚すぎると動摩擦係数が高くなるため、摺動部材として不適である。   In the conductive strip (10) of the present invention, the layer (surface layer) (5) made of Sn or Sn alloy is made of Ni or Ni alloy on the conductive substrate (1) made of Cu or Cu alloy. When the layer (2), the layer (3) containing Cu as a main component, and the layer (surface layer) (5) made of Sn or Sn alloy are sequentially formed and then subjected to reflow treatment, an alloy layer (4 1), it may be used to form an alloy layer (4) made of Cu and Sn and disappear as shown in FIGS. 1 (a) and 1 (b). Further, as shown in FIGS. 2 (a) and 2 (b), a part of the layer (surface layer) (5) made of Sn or Sn alloy may not be used and may remain in the shape of a sea island. The thickness of the remaining layer (surface layer) (5) made of Sn or Sn alloy is preferably 0 to 0.1 μm, and more preferably 0 to 0.05 μm. If it is too thick, the coefficient of dynamic friction becomes high, so it is not suitable as a sliding member.

次に、本実施形態の導電性条材（１０）の製造方法について説明する。本実施形態の導電性条材（１０）は通常、ＣｕまたはＣｕ合金からなる導電性基材（１）上にＮｉまたはＮｉ合金めっき→ＣｕまたはＣｕ合金めっき（Ｃｕを主成分とする層を形成する。）→ＳｎまたはＳｎ合金めっきを順に行い、その後、リフロー処理を行なうことで製造される。本実施形態の製造方法においては、ＣｕまたはＣｕ合金めっきのめっき条件が重要であり、浴温を３０〜６０℃、電流密度を６〜３０Ａ／ｄｍ２に調整する。各工程の前後に、脱脂、酸洗、水洗、乾燥処理を適宜行ってもよい。本発明の製造方法は、従来と同程度の工程数でありながら、それぞれのめっき工程条件、特にＣｕまたはＣｕ合金めっきのめっき条件を適切に調整することで、材料特性の向上を実現した。Next, the manufacturing method of the electroconductive strip (10) of this embodiment is demonstrated. The conductive strip (10) of the present embodiment is usually formed of Ni or Ni alloy plating → Cu or Cu alloy plating (a layer containing Cu as a main component) on a conductive substrate (1) made of Cu or Cu alloy. It is manufactured by performing Sn or Sn alloy plating in order, and then performing a reflow process. In the manufacturing method of this embodiment, the plating conditions for Cu or Cu alloy plating are important, and the bath temperature is adjusted to 30 to 60 ° C., and the current density is adjusted to 6 to 30 A / dm 2 . Before and after each step, degreasing, pickling, washing with water, and drying treatment may be appropriately performed. Although the manufacturing method of the present invention has the same number of steps as the conventional method, the material characteristics can be improved by appropriately adjusting the respective plating process conditions, particularly the plating conditions of Cu or Cu alloy plating.

＜ＮｉまたはＮｉ合金からなる層（２）を形成するＮｉまたはＮｉ合金めっき＞
ＮｉまたはＮｉ合金は、一般的な方法でめっきすれば良い。めっき浴としては、例えばスルファミン浴やワット浴、硫酸浴等を使用できる。めっき条件は、浴温２０〜６０℃、電流密度１〜２０Ａ／ｄｍ２でめっきすればよい。<Ni or Ni alloy plating forming the layer (2) made of Ni or Ni alloy>
Ni or Ni alloy may be plated by a general method. As the plating bath, for example, a sulfamine bath, a watt bath, a sulfuric acid bath, or the like can be used. The plating conditions may be plating at a bath temperature of 20 to 60 ° C. and a current density of 1 to 20 A / dm 2 .

＜Ｃｕを主成分とする層（３）を形成するためのＣｕまたはＣｕ合金めっき＞
ＣｕまたはＣｕ合金は、次のような方法でめっきすれば良い。具体的には、浴温を３０〜６０℃程度、電流密度を６〜３０Ａ／ｄｍ２程度の範囲で制御する。撹拌強度は例えば、撹拌速度を３００〜１０００ｒｐｍの範囲に調整すればよい。めっき浴としては、例えば硫酸浴やシアン浴を使用できる。<Cu or Cu alloy plating for forming the layer (3) containing Cu as a main component>
Cu or Cu alloy may be plated by the following method. Specifically, the bath temperature is controlled in the range of about 30 to 60 ° C., and the current density is controlled in the range of about 6 to 30 A / dm 2 . What is necessary is just to adjust the stirring intensity | strength to the range of 300-1000 rpm, for example. For example, a sulfuric acid bath or a cyan bath can be used as the plating bath.

＜ＣｕおよびＳｎからなる合金層（４）を形成するためのＳｎまたはＳｎ合金めっき＞
ＳｎまたはＳｎ合金は、一般的な方法でめっきすれば良い。めっき浴としては、例えば硫酸浴等を使用できる。めっき条件は、浴温１０〜４０℃、電流密度１〜３０Ａ／ｄｍ２でめっきすればよい。<Sn or Sn alloy plating for forming an alloy layer (4) made of Cu and Sn>
The Sn or Sn alloy may be plated by a general method. As the plating bath, for example, a sulfuric acid bath can be used. The plating conditions may be plating at a bath temperature of 10 to 40 ° C. and a current density of 1 to 30 A / dm 2 .

＜リフロー処理＞
上記３つの層を形成した後のリフロー処理は、一般的な方法で実施できる。例えば４００〜８００℃に設定した炉内に材料を通過させ、５〜２０秒間加熱した後、冷却すればよい。リフロー処理により、ＣｕまたはＣｕ合金めっきとＳｎまたはＳｎ合金めっきが反応し、ＣｕおよびＳｎからなる合金層（４）が形成される。<Reflow processing>
The reflow process after forming the three layers can be performed by a general method. For example, the material may be passed through a furnace set to 400 to 800 ° C., heated for 5 to 20 seconds, and then cooled. By the reflow treatment, Cu or Cu alloy plating and Sn or Sn alloy plating react to form an alloy layer (4) made of Cu and Sn.

したがって、リフロー処理によりＣｕまたはＣｕ合金めっきとＳｎまたはＳｎ合金めっきを、ＳｎまたはＳｎ合金めっきが無くなるまで反応させてＣｕおよびＳｎからなる合金層（４）を形成した場合は、図１（ａ）および１（ｂ）のようにＮｉまたはＮｉ合金めっき層（２）の上に、Ｃｕを主成分とする層（３）、さらにその上にＣｕおよびＳｎからなる合金層（４）が形成される。   Therefore, when an alloy layer (4) made of Cu and Sn is formed by reacting Cu or Cu alloy plating and Sn or Sn alloy plating until the Sn or Sn alloy plating disappears by reflow treatment, FIG. And 1 (b), a layer (3) mainly composed of Cu is formed on the Ni or Ni alloy plating layer (2), and an alloy layer (4) composed of Cu and Sn is formed thereon. .

またリフロー処理によりＣｕを主成分とする層（３）とＳｎまたはＳｎ合金からなる層（表面層）（５）を、ＳｎまたはＳｎ合金からなる層（表面層）（５）が海島状のようなまだらに一部残るように反応させてＣｕおよびＳｎからなる合金層（４）を形成した場合は、図２（ａ）および２（ｂ）のように表面の酸化物膜（１１）が形成される表面層としてＳｎまたはＳｎ合金からなる層（５）が一部残る。
なお、ＳｎまたはＳｎ合金からなる層（５）が厚い場合は残るが、海島状のようなまだらになる。ただし、ＳｎまたはＳｎ合金からなる層（５）が厚すぎると、摩擦係数が下がらないため、残る場合は上記海島状になる。In addition, the layer (3) composed mainly of Cu and the layer (surface layer) (5) made of Sn or Sn alloy by reflow treatment, and the layer (surface layer) (5) made of Sn or Sn alloy seems to have a sea island shape. When the alloy layer (4) made of Cu and Sn is formed by reacting so as to remain partly, the oxide film (11) on the surface is formed as shown in FIGS. 2 (a) and 2 (b). As a surface layer, a part of the layer (5) made of Sn or Sn alloy remains.
In addition, although it remains when the layer (5) made of Sn or Sn alloy is thick, it becomes mottled like a sea island. However, if the layer (5) made of Sn or Sn alloy is too thick, the friction coefficient does not decrease.

ここで、導電性条材（１０）は、表面粗さ（算術平均粗さ）Ｒａが０．０５〜１．０μｍである。さらには０．０５〜０．７μｍが好ましい。表面粗さＲａは、ＪＩＳ Ｂ ０６０１：２００１に従って測定し、求めることができる。表面粗さＲａが上記範囲にあることで、表面層と化合物層の接する面積が小さくなり、母材からの元素拡散を抑えることができ、ひいては表面のＣｕ酸化物量を減らすことが可能になる。   Here, the conductive strip (10) has a surface roughness (arithmetic mean roughness) Ra of 0.05 to 1.0 μm. Furthermore, 0.05-0.7 micrometer is preferable. The surface roughness Ra can be measured and determined according to JIS B 0601: 2001. When the surface roughness Ra is in the above range, the contact area between the surface layer and the compound layer is reduced, element diffusion from the base material can be suppressed, and the amount of Cu oxide on the surface can be reduced.

また、導電性条材（１０）の表面の酸化物膜（１１）中には、Ｃｕの酸化物がＣｕＯまたはＣｕ２Ｏからなり、Ｓｎの酸化物がＳｎＯまたはＳｎＯ２からなる。本発明の導電性条材（１０）においては、酸化物膜の厚さが５０ｎｍ以下である。さらには４〜３０ｍｍが好ましい。また、Ｓｎの酸化物の割合（％）が、９０％以上である。さらには９４〜９６％が好ましい。酸化物膜の厚さとＳｎの酸化物の割合は、以下のようにして求めることができる。
まず、導電性条材（１０）を、塩化カリウムを含む導電性液体に浸漬し、既定の面積（ここでは１ｃｍ２）、一定電流（ここでは１０ｍＡ）を流すカソード還元法によって表面を還元させ、その時の還元電位および電流値から酸化物膜の厚さを計算にて求める。
また、酸化物組成に関しては、ＸＰＳ（Ｘ線光電子分光法）を用いて、表面の酸化物膜を同定し、Ｓｎ酸化物の割合（％）を求める。
さらに、本発明の導電性条材（１０）を温度１４０℃で１２０時間の条件で大気中において加熱した後の接触抵抗が、Ａｇプローブを介した荷重１Ｎの条件下で１０ｍΩ以下である。In the oxide film (11) on the surface of the conductive strip (10), the Cu oxide is made of CuO or Cu 2 O, and the Sn oxide is made of SnO or SnO 2 . In the conductive strip (10) of the present invention, the thickness of the oxide film is 50 nm or less. Furthermore, 4-30 mm is preferable. Further, the ratio (%) of the oxide of Sn is 90% or more. Furthermore, 94 to 96% is preferable. The thickness of the oxide film and the ratio of Sn oxide can be determined as follows.
First, the conductive strip (10) is immersed in a conductive liquid containing potassium chloride, and the surface is reduced by a cathode reduction method in which a predetermined area (here 1 cm 2 ) and a constant current (here 10 mA) are passed, The thickness of the oxide film is obtained by calculation from the reduction potential and current value at that time.
Regarding the oxide composition, the surface oxide film is identified using XPS (X-ray photoelectron spectroscopy), and the ratio (%) of the Sn oxide is obtained.
Further, the contact resistance after heating the conductive strip (10) of the present invention in the atmosphere at a temperature of 140 ° C. for 120 hours is 10 mΩ or less under a load of 1 N through the Ag probe.

導電性条材（１０）の表面の動摩擦係数が、０．３０以下であることが好ましい。さらに好ましくは０．０５以上０．２５以下である。この動摩擦係数が大きすぎると、端子やスイッチに加工した際に、摩耗が大きくなり、接点としての寿命が短くなる可能性や、挿入力が上昇し部品の組み立て性が悪化するといった問題が生じる可能性がある。なお、動摩擦係数は、表面に存在する軟らかいＳｎの存在量に依存し、ＳｎまたはＳｎ合金からなる層（表面層）の厚さを極力薄くすることで低下させることができる。   The dynamic friction coefficient of the surface of the conductive strip (10) is preferably 0.30 or less. More preferably, it is 0.05 or more and 0.25 or less. If the coefficient of dynamic friction is too large, there is a possibility that wear will increase when the terminal or switch is processed, and the service life as a contact may be shortened, or the insertion force may increase and the assembly of parts may deteriorate. There is sex. The dynamic friction coefficient depends on the amount of soft Sn present on the surface, and can be lowered by making the thickness of the layer (surface layer) made of Sn or Sn alloy as thin as possible.

（導電性基材（１０）の用途）
本実施形態の導電性基材（１０）は、特に高温下での耐熱性（電気接続性）に優れ、かつ、挿入力が小さいものである。このため本発明の導電性基材（１０）は、小型端子、高圧大電流端子等の車載部品の他、端子、コネクタ、リードフレームなどの電気電子部品に好適である。(Use of conductive substrate (10))
The conductive substrate (10) of this embodiment is excellent in heat resistance (electrical connectivity) particularly at high temperatures and has a small insertion force. For this reason, the electroconductive base material (10) of this invention is suitable for electric and electronic components, such as a terminal, a connector, and a lead frame other than vehicle-mounted components, such as a small terminal and a high voltage | pressure high current terminal.

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

板厚０．２５ｍｍの銅合金基材（商品名：ＥＦＴＥＣ−９７、導電率４０％ＩＡＣＳ）に電解脱脂、酸洗を行った後、Ｎｉめっき、Ｃｕめっき、Ｓｎめっきを順に施し、表２に示したリフロー時の温度の炉中を５〜１０秒間通過させリフロー処理した。各めっき条件を表１に示す。なお、各発明例では、リフロー処理後に、ＣｕめっきとＳｎめっきを反応させて、Ｓｎ層を消失させＣｕ−Ｓｎ合金層に変換した試験例（実施例１〜７）（図１（ａ）および１（ｂ）参照）とＳｎ層が残存した試験例（実施例８〜９）（図２（ａ）および２（ｂ）参照）がある。比較例では、発明例と同様に、Ｓｎ層が消失した試験例（比較例１〜５、８および９）（図１（ａ）および１（ｂ）参照）と、Ｓｎ層が残存した試験例（比較例６〜７）（図２（ａ）および２（ｂ）参照）とがある。また、比較例４、７では、リフロー処理後にＣｕ層が消失していた。
このような条件で、後述の表２に示す通り、本発明の範囲に入る例として、層厚構成の異なる発明例１〜９の導電性条材（１０）を作成した。
また比較例として、本発明の規定から外れている導電性条材も作製した（比較例１〜９）。After performing electrolytic degreasing and pickling on a copper alloy substrate (trade name: EFTEC-97, conductivity 40% IACS) having a plate thickness of 0.25 mm, Ni plating, Cu plating, and Sn plating were sequentially performed. Reflow treatment was performed by passing through the furnace at the indicated reflow temperature for 5 to 10 seconds. Each plating condition is shown in Table 1. In each example of the invention, after reflow treatment, Cu plating and Sn plating were reacted to eliminate Sn layer and convert to Cu—Sn alloy layer (Examples 1 to 7) (FIGS. 1A and 1B). 1 (b)) and test examples (Examples 8 to 9) in which the Sn layer remained (see FIGS. 2 (a) and 2 (b)). In the comparative example, similar to the inventive example, the test examples in which the Sn layer disappeared (Comparative Examples 1 to 5, 8 and 9) (see FIGS. 1A and 1B) and the test example in which the Sn layer remained (Comparative Examples 6 to 7) (see FIGS. 2A and 2B). In Comparative Examples 4 and 7, the Cu layer disappeared after the reflow treatment.
Under such conditions, as shown in Table 2 to be described later, conductive strips (10) of Invention Examples 1 to 9 having different layer thickness configurations were prepared as examples falling within the scope of the present invention.
In addition, as a comparative example, conductive strips that were not within the scope of the present invention were also produced (Comparative Examples 1 to 9).

Figure 2018074256
Figure 2018074256

［カソード電解脱脂］
脱脂液：ＮａＯＨ ６０ｇ／リットル
脱脂条件：２．５Ａ／ｄｍ２、温度６０℃、脱脂時間６０秒[Cathode electrolytic degreasing]
Degreasing solution: NaOH 60 g / liter Degreasing conditions: 2.5 A / dm 2 , temperature 60 ° C., degreasing time 60 seconds

［酸洗］
酸洗液：１０％硫酸
酸洗条件：３０秒、浸漬、室温[Pickling]
Pickling solution: 10% sulfuric acid pickling conditions: 30 seconds, immersion, room temperature

このようにして製造した供試材について、下記の試験により特性の評価を実施した。   The specimens thus manufactured were evaluated for characteristics by the following test.

（導電性条材の層厚測定）
ＪＩＳ Ｈ ８５０１の１０に記載された定電流溶解法により、導電性条材の各層の平均層厚を測定した。(Measurement of layer thickness of conductive strip)
The average layer thickness of each layer of the conductive strip was measured by the constant current melting method described in 10 of JIS H8501.

（表面粗さＲａ）
導電性条材（１０）の表面粗さＲａは、ＪＩＳ Ｂ ０６０１：２００１に従って測定し、求めた。(Surface roughness Ra)
The surface roughness Ra of the conductive strip (10) was measured and determined according to JIS B 0601: 2001.

（組織観察−酸化物膜の厚さとＳｎの酸化物の割合）
塩化カリウムを含む導電性液体に浸漬し、既定の面積（ここでは１ｃｍ２）、一定電流（ここでは１０ｍＡ）を流すカソード還元法によって表面を還元させ、その時の還元電位および電流値から酸化物膜の厚さを計算にて求めた。また、酸化物組成に関しては、ＸＰＳ（Ｘ線光電子分光法）を用いて、表面の酸化物膜を同定し、Ｓｎ酸化物の割合（％）を求めた。(Structure observation-oxide film thickness and Sn oxide ratio)
The surface is reduced by a cathode reduction method in which the surface is immersed in a conductive liquid containing potassium chloride and a predetermined area (here 1 cm 2 ) and a constant current (here 10 mA) is passed, and the oxide film is obtained from the reduction potential and current value at that time. The thickness of was calculated. Further, regarding the oxide composition, the surface oxide film was identified by using XPS (X-ray photoelectron spectroscopy), and the ratio (%) of the Sn oxide was obtained.

（高温下での耐熱性）
高温下での耐熱性として、１４０℃、１２０時間の条件で大気中において加熱後の接触抵抗は、定電流測定法（４端子法）にて測定した抵抗値から算出し、Ａｇプローブを介した荷重１Ｎの条件下で１０ｍΩ以下であることを優れている（○）と判断とした。一方、この接触抵抗が１０ｍΩよりも大きかった場合を劣る（×）と判断した。(Heat resistance at high temperature)
As the heat resistance at high temperature, the contact resistance after heating in the atmosphere at 140 ° C. for 120 hours was calculated from the resistance value measured by the constant current measurement method (4-terminal method), and passed through an Ag probe. It was judged as being excellent (◯) that it was 10 mΩ or less under the condition of a load of 1 N. On the other hand, the case where this contact resistance was larger than 10 mΩ was judged to be inferior (×).

（動摩擦係数）
動摩擦係数は、バウデン試験機を用いて、押し付け荷重３Ｎ、プローブはＳｎめっきとし、０．５Ｒ張出として測定した。動摩擦係数が０．３０以下である試験例を○（良）、動摩擦係数が０．３０より大きい場合の試験例を×（劣）と評価した。
ここで、この動摩擦係数が０．３０以下であるとは、挿入力が低いことを意味する。(Dynamic friction coefficient)
The dynamic friction coefficient was measured using a Bowden testing machine with a pressing load of 3N, a probe with Sn plating, and a 0.5R overhang. A test example having a dynamic friction coefficient of 0.30 or less was evaluated as ◯ (good), and a test example in which the dynamic friction coefficient was greater than 0.30 was evaluated as x (inferior).
Here, this dynamic friction coefficient being 0.30 or less means that the insertion force is low.

Figure 2018074256
Figure 2018074256

表２に、作製した導電性条材（１０）の各層のめっき厚（層厚）、表面粗さＲａ（μｍ）、リフロー時の炉温（℃）、酸化物膜の厚さ（ｎｍ）及びＳｎ酸化物の割合（％）、並びに前記特性の評価結果をまとめて示した。
ここで表２中、「リフロー後の層厚（μｍ）」と記載した欄には、各層の層厚（μｍ）を示した。この内、「Ｎｉ」と記載した欄はＮｉまたはＮｉ合金からなる層（２）の厚さを示し、「Ｃｕ」と記載した欄はＣｕを主成分とする層（３）の厚さを示し、「ＣｕＳｎ」と記載した欄はＣｕおよびＳｎからなる合金層（４）の厚さを示し、「Ｓｎ」と記載した欄は表面に海島状に残存したＳｎまたはＳｎ合金からなる層（５）の厚さを、それぞれ示す。
実施例８〜９は、ＳｎまたはＳｎ合金からなる層が海島状に存在しており、その存在比が、全表面に対する面積比で２５％未満であった。一方、比較例６〜７は、これを満たさずに大きかった。Table 2 shows the plating thickness (layer thickness), surface roughness Ra (μm), furnace temperature during reflow (° C.), oxide film thickness (nm) and the thickness of each layer of the conductive strip (10) thus prepared. The ratio (%) of Sn oxide and the evaluation results of the above characteristics are shown together.
Here, in Table 2, the column of “layer thickness after reflow (μm)” indicates the layer thickness (μm) of each layer. Among these, the column described as “Ni” indicates the thickness of the layer (2) made of Ni or Ni alloy, and the column described as “Cu” indicates the thickness of the layer (3) mainly composed of Cu. The column marked “CuSn” indicates the thickness of the alloy layer (4) made of Cu and Sn, and the column marked “Sn” is the layer made of Sn or Sn alloy (5) remaining on the surface in the form of sea islands. The thickness of each is shown.
In Examples 8 to 9, a layer made of Sn or an Sn alloy was present in the shape of a sea island, and the abundance ratio was less than 25% in terms of the area ratio relative to the entire surface. On the other hand, Comparative Examples 6-7 were large without satisfying this.

表２において、本発明の条件を満たす、発明例１〜９はいずれも高温下での耐熱性、低挿入性（所定の低い動摩擦係数）の両方に優れていた。
これに対し、比較例１は、Ｓｎ酸化物の割合が低すぎたため、高温下での耐熱性が劣った。比較例２では、Ｃｕ系酸化物の割合が多く、高温下での耐熱性が劣るとともに、接触抵抗が悪化してしまった。比較例４では、Ｃｕ下地が残存せずめっき密着性が劣る結果（上記表には示していない。）となった。比較例５では、Ｃｕ下地が厚すぎ、Ｃｕ系酸化物の割合が大きく、接触抵抗が悪化してしまった。比較例６では残存するＳｎ層が厚く、高温下での耐熱性が劣るとともに、動摩擦係数が高くなりすぎた。比較例７ではＳｎ層が厚いとともにＣｕ下地が残存せず、動摩擦係数が高くなるとともに密着性が悪化（上記表には示していない。）した。比較例８では表面粗さ（Ｒａ、μｍ）が粗く、高温下での耐熱性が劣るとともに、形成される銅系酸化物の割合が高くなって接触抵抗が悪化してしまった。比較例９は、Ｎｉ皮膜が存在せず、また、酸化物膜厚が厚かったため、高温下での耐熱性と動摩擦係数が両方とも劣った。
以上から、本発明の条件を満たす導電性条材が優れた特性を示すことが確認された。In Table 2, Invention Examples 1 to 9, which satisfy the conditions of the present invention, were all excellent in both heat resistance at a high temperature and low insertion property (predetermined low dynamic friction coefficient).
In contrast, Comparative Example 1 was inferior in heat resistance at high temperatures because the Sn oxide ratio was too low. In Comparative Example 2, the ratio of the Cu-based oxide was large, the heat resistance at high temperature was inferior, and the contact resistance was deteriorated. In Comparative Example 4, no Cu base remained and the plating adhesion was inferior (not shown in the above table). In Comparative Example 5, the Cu base was too thick, the ratio of the Cu-based oxide was large, and the contact resistance was deteriorated. In Comparative Example 6, the remaining Sn layer was thick, the heat resistance at high temperature was inferior, and the dynamic friction coefficient was too high. In Comparative Example 7, the Sn layer was thick and the Cu base did not remain, the dynamic friction coefficient increased, and the adhesion deteriorated (not shown in the above table). In Comparative Example 8, the surface roughness (Ra, μm) was rough, the heat resistance at high temperature was inferior, and the proportion of the copper-based oxide formed was high, resulting in poor contact resistance. In Comparative Example 9, since the Ni film was not present and the oxide film thickness was large, both the heat resistance at high temperature and the dynamic friction coefficient were inferior.
From the above, it was confirmed that the conductive strip satisfying the conditions of the present invention exhibits excellent characteristics.

本発明をその実施態様とともに説明したが、我々は特に指定しない限り我々の発明を説明のどの細部においても限定しようとするものではなく、添付の請求の範囲に示した発明の精神と範囲に反することなく幅広く解釈されるべきであると考える。   While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

本願は、２０１６年１０月１７日に日本国で特許出願された特願２０１６−２０３６２９に基づく優先権を主張するものであり、これはここに参照してその内容を本明細書の記載の一部として取り込む。   This application claims the priority based on Japanese Patent Application No. 2006-203629 for which it applied for a patent in Japan on October 17, 2016, and this is referred to here for the contents of this specification. Capture as part.

１ ＣｕまたはＣｕ合金からなる導電性基材
２ ＮｉまたはＮｉ合金からなる層
３ Ｃｕを主成分とする層
４ ＣｕおよびＳｎからなる合金層
５ ＳｎまたはＳｎ合金からなる層（表面層）
１０ 導電性条材
１１ 表面の酸化物膜

DESCRIPTION OF SYMBOLS 1 Conductive base material which consists of Cu or Cu alloy 2 Layer which consists of Ni or Ni alloy 3 Layer which has Cu as a main component 4 Alloy layer which consists of Cu and Sn 5 Layer which consists of Sn or Sn alloy (surface layer)
10 conductive strip 11 oxide film on the surface

Claims (4)

ＣｕまたはＣｕ合金からなる導電性基材の上に、ＮｉまたはＮｉ合金からなる層、Ｃｕを主成分とする層、ＣｕおよびＳｎからなる合金層をこの順に有する導電性条材であって、
前記ＮｉまたはＮｉ合金からなる層の厚さが０．１〜２．０μｍ、前記Ｃｕを主成分とする層の厚さが０．０１〜０．１μｍ、前記ＣｕおよびＳｎからなる合金層の厚さが０．１〜２．０μｍであって、
表面粗さＲａが０．０５〜１．０μｍであり、表面に形成される酸化物膜中にＣｕの酸化物およびＳｎの酸化物が含まれ、酸化物膜の厚さが５０ｎｍ以下であり、Ｓｎの酸化物の割合（％）が９０％以上であり、かつ、この導電性条材を温度１４０℃で１２０時間の条件で大気中において加熱した後の接触抵抗が、Ａｇプローブを介した荷重１Ｎの条件下で１０ｍΩ以下であることを特徴とする導電性条材。On a conductive base material made of Cu or Cu alloy, a conductive strip having a layer made of Ni or Ni alloy, a layer mainly composed of Cu, and an alloy layer made of Cu and Sn in this order,
The thickness of the layer made of Ni or Ni alloy is 0.1 to 2.0 μm, the thickness of the layer mainly composed of Cu is 0.01 to 0.1 μm, the thickness of the alloy layer made of Cu and Sn Is 0.1 to 2.0 μm,
The surface roughness Ra is 0.05 to 1.0 μm, the oxide film formed on the surface contains Cu oxide and Sn oxide, and the thickness of the oxide film is 50 nm or less, The ratio of Sn oxide (%) is 90% or more, and the contact resistance after heating the conductive strip in the atmosphere at a temperature of 140 ° C. for 120 hours is the load through the Ag probe. A conductive strip characterized by being 10 mΩ or less under the condition of 1N. 前記ＮｉまたはＮｉ合金からなる層の厚さが０．２〜１．０μｍ、前記Ｃｕを主成分とする層の厚さが０．０１〜０．０５μｍ、前記ＣｕおよびＳｎからなる合金層の厚さが０．４〜１．５μｍである請求項１に記載の導電性条材。   The thickness of the layer made of Ni or Ni alloy is 0.2 to 1.0 μm, the thickness of the layer mainly composed of Cu is 0.01 to 0.05 μm, and the thickness of the alloy layer made of Cu and Sn The conductive strip according to claim 1, having a thickness of 0.4 to 1.5 μm. 前記表面に形成される酸化物膜中に銅の酸化物がＣｕＯまたはＣｕ２Ｏからなり、Ｓｎの酸化物がＳｎＯまたはＳｎＯ２からなる請求項１または２に記載の導電性条材。3. The conductive strip according to claim 1, wherein a copper oxide is made of CuO or Cu 2 O, and an Sn oxide is made of SnO or SnO 2 in the oxide film formed on the surface. 前記導電性条材の表面の動摩擦係数が、０．３０以下である請求項１〜３のいずれか１項に記載の導電性条材。

The conductive strip according to any one of claims 1 to 3, wherein the surface of the conductive strip has a dynamic friction coefficient of 0.30 or less.

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