JP3628836B2 - Sn or Sn alloy plated copper alloy material - Google Patents

Sn or Sn alloy plated copper alloy material Download PDF

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JP3628836B2
JP3628836B2 JP09309697A JP9309697A JP3628836B2 JP 3628836 B2 JP3628836 B2 JP 3628836B2 JP 09309697 A JP09309697 A JP 09309697A JP 9309697 A JP9309697 A JP 9309697A JP 3628836 B2 JP3628836 B2 JP 3628836B2
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alloy
plating
layer
thickness
plating layer
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JPH10265992A (en
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康弘 真谷
誠昭 磯野
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Kobe Steel Ltd
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Kobe Steel Ltd
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【0001】
【発明の属する技術分野】
本発明は、Sn又はSn合金めっきを施した銅合金材に関わり、特に端子・コネクター等の電気電子部品用に適する銅合金材に関わる。
【0002】
【従来の技術】
Sn又はSn合金めっき銅合金は、自動車用端子をはじめ、民生機器用端子・コネクターの接触部品として用いられている。Snめっきを施す目的は、耐食性、はんだ付け性の向上、接触抵抗(電気抵抗)の低減などであり、Znを含まない銅合金には銅合金に直接Sn又はSn合金めっきが行われ、Znを含有する銅合金には、はんだ付け性を低下させるZn原子のSn層への拡散を防止するために、銅合金の上にまずCu下地めっき層を設け、その上にSn又はSn合金めっきが行われる。
【0003】
一方、最近の自動車の電装化のさらなる進展に伴い、端子を集合させて形成する自動車用集合端子の多ピン化が進んでいる。そして、集合端子材にもその要求特性をよく満足するためSn又はSn合金めっき銅合金が多用されているが、多ピン化の進展に伴い集合端子を嵌合させて組み立てるときの挿入力が大きいことが問題となってきた。挿入力が大きいと自動車を組み立てる際の作業性の低下を招き、生産性が低下するためである。従って、組立時の挿入力及びそのばらつきが小さいSn又はSn合金めっき端子材に対する要求が大きくなってきた。
【0004】
【発明が解決しようとする課題】
端子の挿入力を低下させる手段として、端子を嵌合する際の摩擦係数を低下させることが考えられ、本発明者らの知見によれば、これはSn又はSn合金めっき層の厚さを薄くすることによって達成できる。なお、従来のSn又はSn合金めっき層の厚さは、例えば特開平2−170995号公報、特開平3−197692号公報、特開平4−235292号公報、特開平4−329891号公報等にもみられるように、0.8μmを超えていた。
しかし、Sn又はSn合金めっき層の厚さが薄くなると、銅合金母材又はCu下地めっき層のCu原子がSn又はSn合金めっき層中へ拡散して形成されるCu−Sn金属間化合物が、比較的短時間のうちにめっき表面層にまで到達し、その結果、端子接点部の電気伝導度の経時的低下及び接触抵抗の上昇という問題が、Sn又はSn合金めっき層が厚い場合に比べて短時間のうちに起こるという不具合がある。
【0005】
本発明は、このような問題点に鑑みてなされたもので、端子嵌合時の挿入力を低下させることが可能で、かつ、端子接点部の接触抵抗を長時間にわたり低い値に維持できるなど電気的特性に優れたSn又はSn合金めっき銅合金材を提供することを目的とする。
【0006】
【課題を解決するための手段】
本発明に係るSn又はSn合金めっき銅合金材は、銅合金とSn又はSn合金めっきとの間に厚さ0.10〜1.0μmのCo又はCo合金めっき層を有し、かつSn又はSn合金めっきの厚さが0.10〜0.80μmであり、かつ同材の間の摩擦係数が0.30以下であることを特徴とする。
なお、本発明では、めっき層の厚さは蛍光X線膜厚計によって測定した値とする。
【0007】
以下、上記Sn又はSn合金めっき銅合金材を構成するめっき層等について、より具体的に説明する。
(Co又はCo合金下地めっき層)
銅合金とSn又はSn合金めっきの間にCo又はCo合金下地めっき層を形成するのは、母材の銅合金のCu原子やZn原子のSnめっき層中への拡散に対してCo又はCo合金下地めっき層が障壁として作用することと、下地のCo又はCo合金めっき層中のCo原子のSn又はSn合金めっき層中への拡散速度が非常に小さいことから、Sn又はSn合金めっき層中におけるCu−Sn又はSn−Co金属間化合物の成長を著しく抑制できるからである。
Co又はCo合金下地めっき層のこのような作用効果により、厚さ0.8μmを超えていた従来のSnめっきの厚さを、0.10〜0.80μmに低減することが可能となった。これにより、銅合金材表面の摩擦係数を低くでき、しかも同時にSnめっき表面層の接触抵抗を長時間にわたって低く維持できるようになった。
【0008】
Co又はCo合金下地めっき層の厚さが1.0μmより厚いと、その曲げ加工性が悪いことから、Sn又はSn合金めっき層表面にクラックが発生して曲げ加工性が低下し、一方、Co又はCo合金下地めっき層の厚さが0.1μmより薄いと、そのめっき層による拡散防止効果が減少して母材の銅合金のCu及びZn原子がSn又はSn合金めっき層中に拡散するため、Co又はCo合金下地めっきの適正厚さは0.10〜1.0μmである。さらに望ましいCo又はCo合金めっき層の厚さとは0.1〜0.5μmである。また、本発明において、このめっき層のCo合金としては、Co−Ni、Co−Pd、Co−Ag、Co−Auなどを用いると曲げ加工性の改善に効果がある。
【0009】
なお、この銅合金を自動車用端子として使用した場合など、エンジンルーム等の使用環境では100℃を越えるため、Sn又はSn合金めっき層中のSn(及び下記Pb、Zn、Ni等)がCo又はCo合金めっき層に拡散して、Sn−Co(又はCo合金)合金層が発生することがあるが、このような拡散層が発生した銅合金材も本発明の銅合金材に含まれる。この場合、本発明ではこの拡散層を上記Co又はCo合金めっき層の一部とみなし、拡散層の厚さ+Co又はCo合金めっき層の厚さが0.1〜1.0μmの範囲内にあればよいこととする。むろん、この範囲内にある限り拡散層の有無に関わらずCo又はCo合金めっき層についての前記作用効果は失われない。
また、本発明におけるCo又はCo合金めっき層は、いわゆるめっき以外に蒸着などの方法を用いて形成した層でもよく、上記の厚さ範囲を満たす薄層である限り被覆手段に特に制限はないものとする。
【0010】
(Sn又はSn合金めっき層)
Sn又はSn合金めっき層は薄い方が摩擦係数が低くなり、それによって端子の挿入力も低減できるが、Sn又はSn合金めっき層の厚さが0.10μmより薄いと、Co又はCo合金下地めっき層のCo原子がSn又はSn合金めっき表面に拡散して接触抵抗がかえって増加し、一方、Sn又はSn合金めっき層の厚さが0.80μmより厚くなると摩擦係数が0.30を超え、現状の低挿入力端子の基準挿入力を満たさないため、Snめっきの厚さは0.10〜0.80μmとする。さらに望ましいSn又はSn合金めっき層の厚さとしては0.3〜0.8μmである。また、このめっき層のSn合金としては、Zn、Ni、Pb、Ag、In、Biのうち1種又は2種以上を合計で0.05〜40wt%含む合金が挙げられる。
なお、本発明におけるSn又はSn合金めっき層は、電気めっき、リフローめっき、無電解めっき、溶融めっきのいずれで形成したものでもよい。
【0011】
(銅合金)
本発明は、黄銅、りん青銅、CDA195をはじめ、端子、コネクター、リードフレームなどに用いられている銅合金の全てに適用可能であるが、Co又は/及びSnを成分として含有する銅合金についてCo、Snの2層めっきを行った材料については、回収したスクラップを原料として再利用しやすく、特にCoとSnの双方を含有するCDA195のような銅合金については、回収したスクラップをそのまま原料として溶解することが可能となるために有利である。
【0012】
【実施例】
銅合金母材として、C2600(Cu−30Zn)、CDA195(Cu―1.55wt%Fe―0.85wt%Co―0.55wt%Sn―0.1wt%P)の0.25mmt板材を用い、Co下地めっき及びSnめっきを種々の厚さで施し、これを供試材(実施例及び比較例)とした。Co下地めっきのめっき条件を表1に、Snめっきのめっき条件を表2に示す。そのほか、上記の銅合金母材に銅下地めっき及びSnめっきを施した銅合金材(従来例)を用意した。
【0013】
【表1】

Figure 0003628836
【0014】
【表2】
Figure 0003628836
【0015】
このようにして得た各2層めっき銅合金材のそれぞれについて、下記の要領でSnめっき厚さ、Coめっき厚さを測定し、また、摩擦係数の測定、曲げ加工性評価及び接触抵抗の測定試験を行った。
(めっき層厚の測定方法)
めっき直後に蛍光X線膜厚計によって測定した。
(Snめっき材の摩擦係数測定法)
図1の模式図に示すような摩擦係数測定治具を用いて測定した。すなわち、上記の2層めっき銅合金材を曲率半径1.5mmとなるようプレス成形してメス側試料1を一対作製し、次にメス側試料1でオス側試料2の板を300gf(N)の荷重3をかけて挟みこみ、オス側試料2を50mm/minで引っ張り、そのとき必要な引張力Fをロードセル4で測定し、μ=F/N(N=300gf)より摩擦係数(μ)を測定した。
【0016】
(接触抵抗測定方法)
2層めっき後、25℃、相対湿度70%で90日放置した上記の2層めっき銅合金材の接触抵抗を4端子法により測定した。荷重100gf、設定電圧20mV、設定電流は10mAとした。
(曲げ加工性)
Snめっき直後の2層めっき銅合金材を用いて、W曲げ試験で評価した。幅10mmの試験片(JISZ2204の4号試験片)をJISH3110に規定するW曲げ試験方法に準拠し、曲げ半径0.5mm、線圧100kgf/mmで曲げた後、曲げ部を実体顕微鏡(×40)で観察し、表面の割れの有無を観察した。
【0017】
表3に銅合金母材としてC2600を用いたときの結果、表4にCDA195を用いたときの結果を示す。
【0018】
【表3】
Figure 0003628836
【0019】
【表4】
Figure 0003628836
【0020】
表3及び表4に示すように、Snめっき厚さが0.10〜0.80μmであり、かつ、Coめっき厚さが0.10〜1.0μmの範囲内の実施例No.1〜5及びNo.11〜15は、摩擦係数が0.30以下であり、曲げ加工性、接触抵抗は従来と同等であった。
一方、Snめっき厚さが0.8μmより厚い比較例No.6及びNo.16は、摩擦係数が0.3を超え、基準値を満たさない。
【0021】
Coめっき厚さが1.0μmより厚い比較例No.7及びNo.17は、Snめっき表面にクラックが発生し、曲げ加工性が低下した。
Coめっき厚さが0.1μmより薄い比較例No.8及びNo.18は、接触抵抗が増加した。これは、Coめっき層による拡散防止効果が低く、母材のCu(No.8、No.18)及びZn原子(No.8)が表面に拡散したためである。
Snめっき厚さが0.1μmより薄い比較例No.9及びNo.19は、接触抵抗が増加した。これは、Coめっき層のCo原子がSnめっき層表面に拡散してきたためである。
従来例のNo.10及びNo.20はSnめっき厚が厚く、摩擦係数が0.3を超え、基準値を満たさない。
【0022】
【発明の効果】
本発明によって、低摩擦係数のめっき表面を持ち、かつ電気的特性に優れ、特に端子・コネクターの接触部品として適する電気・電子部品用Sn又はSn合金めっき銅合金材を提供することができる。
【図面の簡単な説明】
【図1】実施例の摩擦係数測定法を説明する模式図である。
【符号の説明】
1 メス側試料
2 オス側試料[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a copper alloy material plated with Sn or Sn alloy, and more particularly to a copper alloy material suitable for electric and electronic parts such as terminals and connectors.
[0002]
[Prior art]
Sn or Sn alloy-plated copper alloy is used as a contact part for terminals and connectors for consumer equipment, including automobile terminals. The purpose of applying Sn plating is to improve corrosion resistance, solderability, reduce contact resistance (electrical resistance), etc. For copper alloys not containing Zn, Sn or Sn alloy plating is performed directly on the copper alloy, and Zn is added. In order to prevent the diffusion of Zn atoms to the Sn layer, which lowers the solderability, the copper alloy contained is first provided with a Cu undercoat layer on the copper alloy, and then Sn or Sn alloy plating is performed thereon. Is called.
[0003]
On the other hand, with the recent further progress in the electrical mounting of automobiles, the number of automobile collective terminals formed by assembling terminals is increasing. In addition, Sn or Sn alloy-plated copper alloy is often used for the aggregate terminal material in order to fully satisfy the required characteristics, but the insertion force when fitting and assembling the aggregate terminal is increased as the number of pins increases. Has become a problem. This is because when the insertion force is large, workability when assembling the automobile is lowered, and productivity is lowered. Therefore, the demand for Sn or Sn alloy plating terminal material with small insertion force and its variation at the time of assembly has increased.
[0004]
[Problems to be solved by the invention]
As means for reducing the insertion force of the terminal, it is conceivable to reduce the coefficient of friction when the terminal is fitted, and according to the knowledge of the present inventors, this reduces the thickness of the Sn or Sn alloy plating layer. Can be achieved. Note that the thickness of the conventional Sn or Sn alloy plating layer can be found in, for example, JP-A-2-170995, JP-A-3-197692, JP-A-4-235292, and JP-A-4-329891. As above, it was over 0.8 μm.
However, when the thickness of the Sn or Sn alloy plating layer is reduced, the Cu-Sn intermetallic compound formed by the diffusion of Cu atoms in the copper alloy base material or the Cu base plating layer into the Sn or Sn alloy plating layer, It reaches the plating surface layer within a relatively short time, and as a result, the problems of a decrease in electrical conductivity of the terminal contact portion and an increase in contact resistance are compared with the case where the Sn or Sn alloy plating layer is thick. There is a defect that occurs in a short time.
[0005]
The present invention has been made in view of such problems, and can reduce the insertion force at the time of terminal fitting, and can maintain the contact resistance of the terminal contact portion at a low value for a long time. It aims at providing Sn or Sn alloy plating copper alloy material excellent in an electrical property.
[0006]
[Means for Solving the Problems]
The Sn or Sn alloy plating copper alloy material according to the present invention has a Co or Co alloy plating layer having a thickness of 0.10 to 1.0 μm between the copper alloy and the Sn or Sn alloy plating, and Sn or Sn. The thickness of the alloy plating is 0.10 to 0.80 μm, and the friction coefficient between the same materials is 0.30 or less.
In the present invention, the thickness of the plating layer is a value measured by a fluorescent X-ray film thickness meter.
[0007]
Hereinafter, the plating layer etc. which comprise the said Sn or Sn alloy plating copper alloy material are demonstrated more concretely.
(Co or Co alloy base plating layer)
The Co or Co alloy base plating layer is formed between the copper alloy and the Sn or Sn alloy plating because the Co or Co alloy with respect to the diffusion of Cu atoms or Zn atoms of the base copper alloy into the Sn plating layer. In the Sn or Sn alloy plating layer, the underlying plating layer acts as a barrier and the diffusion rate of Co atoms in the underlying Co or Co alloy plating layer into the Sn or Sn alloy plating layer is very small. This is because the growth of the Cu—Sn or Sn—Co intermetallic compound can be remarkably suppressed.
Due to such an effect of the Co or Co alloy base plating layer, the thickness of the conventional Sn plating, which has exceeded the thickness of 0.8 μm, can be reduced to 0.10 to 0.80 μm. As a result, the friction coefficient on the surface of the copper alloy material can be lowered, and at the same time, the contact resistance of the Sn plating surface layer can be kept low for a long time.
[0008]
If the thickness of the Co or Co alloy underplating layer is greater than 1.0 μm, the bending workability is poor, so cracks are generated on the Sn or Sn alloy plating layer surface and the bending workability is reduced. Alternatively, if the thickness of the Co alloy base plating layer is less than 0.1 μm, the diffusion preventing effect of the plating layer is reduced and Cu and Zn atoms of the base copper alloy diffuse into the Sn or Sn alloy plating layer. The appropriate thickness of Co or Co alloy base plating is 0.10 to 1.0 μm. A more desirable thickness of the Co or Co alloy plating layer is 0.1 to 0.5 μm. In the present invention, if Co—Ni, Co—Pd, Co—Ag, Co—Au or the like is used as the Co alloy of the plating layer, it is effective in improving the bending workability.
[0009]
In addition, when this copper alloy is used as an automobile terminal or the like, it exceeds 100 ° C. in the use environment such as an engine room. Therefore, Sn (and Pb, Zn, Ni, etc.) in the Sn or Sn alloy plating layer is Co or A Sn—Co (or Co alloy) alloy layer may be generated by diffusing into the Co alloy plating layer. The copper alloy material in which such a diffusion layer is generated is also included in the copper alloy material of the present invention. In this case, in the present invention, the diffusion layer is regarded as a part of the Co or Co alloy plating layer, and the thickness of the diffusion layer + the thickness of the Co or Co alloy plating layer is within the range of 0.1 to 1.0 μm. I will do it. Of course, as long as it is within this range, the above-described effects of the Co or Co alloy plating layer are not lost regardless of the presence or absence of the diffusion layer.
Further, the Co or Co alloy plating layer in the present invention may be a layer formed by a method such as vapor deposition other than so-called plating, and there is no particular limitation on the coating means as long as it is a thin layer satisfying the above thickness range. And
[0010]
(Sn or Sn alloy plating layer)
The thinner the Sn or Sn alloy plating layer, the lower the coefficient of friction, thereby reducing the terminal insertion force. However, if the Sn or Sn alloy plating layer is thinner than 0.10 μm, the Co or Co alloy undercoat layer Co atoms diffused on the Sn or Sn alloy plating surface and the contact resistance increased. On the other hand, when the Sn or Sn alloy plating layer was thicker than 0.80 μm, the friction coefficient exceeded 0.30, In order not to satisfy the standard insertion force of the low insertion force terminal, the Sn plating thickness is set to 0.10 to 0.80 μm. A more desirable Sn or Sn alloy plating layer thickness is 0.3 to 0.8 μm. Examples of the Sn alloy of the plating layer include an alloy containing 0.05 to 40 wt% in total of one or more of Zn, Ni, Pb, Ag, In, and Bi.
Note that the Sn or Sn alloy plating layer in the present invention may be formed by any of electroplating, reflow plating, electroless plating, and hot dipping.
[0011]
(Copper alloy)
The present invention can be applied to all copper alloys used for terminals, connectors, lead frames and the like, including brass, phosphor bronze, CDA195, etc., but for copper alloys containing Co or / and Sn as a component, Co For the Sn-plated material, it is easy to reuse the recovered scrap as a raw material. Especially for a copper alloy such as CDA195 containing both Co and Sn, the recovered scrap is directly dissolved as a raw material. It is advantageous to be able to do so.
[0012]
【Example】
As a copper alloy base material, a 0.25 mmt plate material of C2600 (Cu-30Zn), CDA195 (Cu-1.55 wt% Fe-0.85 wt% Co-0.55 wt% Sn-0.1 wt% P) is used. Base plating and Sn plating were performed in various thicknesses, and this was used as test materials (Examples and Comparative Examples). Table 1 shows the plating conditions for the Co base plating, and Table 2 shows the plating conditions for the Sn plating. In addition, a copper alloy material (conventional example) in which the copper alloy base material was subjected to copper base plating and Sn plating was prepared.
[0013]
[Table 1]
Figure 0003628836
[0014]
[Table 2]
Figure 0003628836
[0015]
For each of the two-layer plated copper alloy materials thus obtained, the Sn plating thickness and the Co plating thickness are measured in the following manner, and the friction coefficient, bending workability evaluation, and contact resistance measurement are measured. A test was conducted.
(Measurement method of plating layer thickness)
Immediately after plating, it was measured with a fluorescent X-ray film thickness meter.
(Method for measuring coefficient of friction of Sn plating material)
It measured using the friction coefficient measuring jig as shown to the schematic diagram of FIG. That is, the two-layer plated copper alloy material is press-molded to have a curvature radius of 1.5 mm to produce a pair of female-side samples 1, and then a plate of male-side sample 2 is 300 gf (N) with female-side sample 1 Then, the male side sample 2 was pulled at 50 mm / min, and the necessary tensile force F was measured with the load cell 4, and the friction coefficient (μ) from μ = F / N (N = 300 gf) Was measured.
[0016]
(Contact resistance measurement method)
After the two-layer plating, the contact resistance of the two-layer plated copper alloy material left for 90 days at 25 ° C. and 70% relative humidity was measured by a four-terminal method. The load was 100 gf, the set voltage was 20 mV, and the set current was 10 mA.
(Bending workability)
Evaluation was performed by a W-bending test using a two-layer plated copper alloy material immediately after Sn plating. A test piece having a width of 10 mm (No. 4 test piece of JISZ2204) was bent at a bending radius of 0.5 mm and a linear pressure of 100 kgf / mm in accordance with the W bending test method specified in JIS 3110. ) And the presence or absence of cracks on the surface was observed.
[0017]
Table 3 shows the results when C2600 was used as the copper alloy base material, and Table 4 shows the results when CDA195 was used.
[0018]
[Table 3]
Figure 0003628836
[0019]
[Table 4]
Figure 0003628836
[0020]
As shown in Tables 3 and 4, Example Nos. In which Sn plating thickness is 0.10 to 0.80 μm and Co plating thickness is in the range of 0.10 to 1.0 μm. 1-5 and no. Nos. 11 to 15 had a friction coefficient of 0.30 or less, and the bending workability and the contact resistance were the same as the conventional ones.
On the other hand, the comparative example No. whose Sn plating thickness is thicker than 0.8 μm. 6 and no. No. 16 has a friction coefficient exceeding 0.3 and does not satisfy the reference value.
[0021]
Comparative example No. Co plating thickness thicker than 1.0 μm 7 and no. In No. 17, cracks occurred on the Sn plating surface, and the bending workability deteriorated.
In Comparative Example No. Co plating thickness less than 0.1 μm 8 and no. 18, contact resistance increased. This is because the effect of preventing diffusion by the Co plating layer is low, and the base materials Cu (No. 8, No. 18) and Zn atoms (No. 8) diffused to the surface.
Comparative Example No. Sn plating thickness less than 0.1 μm 9 and no. 19, the contact resistance increased. This is because Co atoms in the Co plating layer have diffused on the surface of the Sn plating layer.
No. of the conventional example. 10 and no. No. 20 has a thick Sn plating thickness, a friction coefficient exceeds 0.3, and does not satisfy the standard value.
[0022]
【The invention's effect】
According to the present invention, it is possible to provide a Sn or Sn alloy-plated copper alloy material for electrical / electronic parts that has a plating surface with a low friction coefficient and is excellent in electrical characteristics, and is particularly suitable as a contact part for terminals and connectors.
[Brief description of the drawings]
FIG. 1 is a schematic diagram for explaining a friction coefficient measurement method according to an embodiment.
[Explanation of symbols]
1 Female sample 2 Male sample

Claims (1)

銅合金とSn又はSn合金めっきとの間に厚さ0.10〜1.0μmのCo又はCo合金めっき層を有し、かつSn又はSn合金めっきの厚さが0.10〜0.80μmであり、かつ同材の間の摩擦係数が0.30以下であることを特徴とするSn又はSn合金めっき銅合金材。A Co or Co alloy plating layer having a thickness of 0.10 to 1.0 μm is provided between the copper alloy and Sn or Sn alloy plating, and the thickness of the Sn or Sn alloy plating is 0.10 to 0.80 μm. A Sn or Sn alloy-plated copper alloy material having a friction coefficient between the same materials of 0.30 or less.
JP09309697A 1997-03-26 1997-03-26 Sn or Sn alloy plated copper alloy material Expired - Lifetime JP3628836B2 (en)

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Publication number Priority date Publication date Assignee Title
JP3286560B2 (en) * 1997-04-28 2002-05-27 株式会社オートネットワーク技術研究所 Mating connection terminal
JP6011129B2 (en) * 2012-08-07 2016-10-19 三菱マテリアル株式会社 Copper alloy terminal material excellent in insertion / removability and manufacturing method thereof

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