JP2726434B2 - Sn or Sn alloy coating material - Google Patents

Sn or Sn alloy coating material

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Publication number
JP2726434B2
JP2726434B2 JP63138654A JP13865488A JP2726434B2 JP 2726434 B2 JP2726434 B2 JP 2726434B2 JP 63138654 A JP63138654 A JP 63138654A JP 13865488 A JP13865488 A JP 13865488A JP 2726434 B2 JP2726434 B2 JP 2726434B2
Authority
JP
Japan
Prior art keywords
alloy
plating
thickness
coating layer
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP63138654A
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Japanese (ja)
Other versions
JPH01306574A (en
Inventor
晃 松田
Original Assignee
古河電気工業株式会社
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Priority to JP63138654A priority Critical patent/JP2726434B2/en
Publication of JPH01306574A publication Critical patent/JPH01306574A/en
Application granted granted Critical
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Expired - Lifetime legal-status Critical Current

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Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明はCuまたはCu合金を基材とし、中間層としてN
i、Coまたはこれらを含む合金およびAgまたはAg合金の
被覆層を有し最外層にSn、Sn合金の被覆層を設けた電子
部品、機器用のSnまたはSn合金被覆材料に関する。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is based on Cu or Cu alloy,
The present invention relates to a Sn or Sn alloy coating material for electronic components and equipment, which has a coating layer of i, Co or an alloy containing them, and a coating layer of Ag or an Ag alloy and has an outermost layer provided with a coating layer of Sn or a Sn alloy.
〔従来の技術とその課題〕 CuまたはCu合金基材上にSnまたはSn合金を被覆した複
合導体は基体の特性に加えてSnなどの優れた半田付性と
耐食性を有し、また電気接続特性にも優れているため、
コネクター、端子などの接点、リードフレーム、リード
線等の部品リード部、基板回路や配線ケーブル導体のな
どの電子、電機部品として使用されている。
[Conventional technology and its problems] Composite conductors coated with Sn or Sn alloy on Cu or Cu alloy substrate have excellent solderability and corrosion resistance such as Sn in addition to the characteristics of the substrate, and electrical connection characteristics Is also excellent,
It is used as electronic and electric parts such as connectors, terminals and other contact parts, lead parts such as lead frames and lead wires, board circuits and wiring cable conductors.
これらの材料は通常CuまたはCu合金基材上に直接、電
気めっきや溶融めっき、クラッド等によりSnまたはSn合
金を被覆したものや、中間層としてCu、Ni層等を設けた
後nまたはSn合金を被覆した材料が使用されている。
These materials are usually coated directly on a Cu or Cu alloy substrate with Sn or Sn alloy by electroplating, hot-dip plating, cladding, etc., or after providing a Cu, Ni layer etc. as an intermediate layer, n or Sn alloy Is used.
上記の材料が電子、電機部品が使用される場合、使用
中に外部または自己の発熱により、材料の温度が100℃
程度に上昇するのが一般的であるが、最近の軽薄短小化
等により自己発熱の増大、熱の放散がし難いこと、他の
発熱部への近接化等の事情により120℃以上の温度にお
いて使用されることが進められている。
When the above materials are used for electronic and electric parts, the temperature of the materials is 100 ℃ due to external or self-generated heat during use.
In general, the temperature rises to about 120 ° C or more due to circumstances such as the increase in self-heating, the difficulty in dissipating heat, and the proximity to other heat-generating parts, etc. It is being used.
しかしこの使用温度においては従来のCuを中間層とし
たSnまたはSn合金被覆材料においてはCuとSnの拡散のた
め表面にCuが到達し酸化を起すことおよび純Sn層または
純半田層が拡散により失われて合金層となり外観が損な
われる他、接触抵抗が増加するなど特性が劣化する。ま
たNiを中間層としたものも120℃以上の温度においてはN
i−Snの拡散層を生成し接触抵抗が増加するなどの問題
があった。
However, at this operating temperature, in conventional Sn or Sn alloy coating materials using Cu as an intermediate layer, Cu reaches the surface due to the diffusion of Cu and Sn and causes oxidation, and the pure Sn layer or pure solder layer is diffused. The alloy layer is lost and becomes an alloy layer, the appearance is impaired, and the characteristics are deteriorated such as an increase in contact resistance. In the case where the intermediate layer is made of Ni, N
There was a problem that an i-Sn diffusion layer was formed and contact resistance increased.
〔発明が解決しようとする課題〕[Problems to be solved by the invention]
本発明は上記の問題について検討の結果、高温におけ
る使用に拘わらず、表面の酸化変色がなく接触抵抗の増
加が少なく、長期間にわたり、外観および接触特性が良
好なSnまたはSnの合金被覆材料を開発したものである。
As a result of studying the above problems, the present invention provides a Sn or Sn alloy coating material having good appearance and contact characteristics over a long period of time, with little increase in contact resistance without oxidative discoloration of the surface, regardless of use at high temperatures. It was developed.
〔課題を解決するための手段および作用〕[Means and actions for solving the problem]
本発明は、CuまたはCu合金基材表面にNi、Coまたはこ
れらを含む合金の第1被覆層を設けその表面にAgまたは
Ag合金の第2被覆層を設け、さらにその表面にSnまたは
Sn合金の被覆層を設けてなるSnまたはSn合金被覆材料で
あり、前記第1被覆層の厚さを0.05〜1.0μm、前記第
2被覆層の厚さを0.005〜0.5μmとしたものである。
The present invention provides a first coating layer of Ni, Co or an alloy containing these on a Cu or Cu alloy substrate surface, and on the surface thereof, Ag or
A second coating layer of an Ag alloy is provided, and Sn or Sn is further provided on the surface thereof.
Sn or a Sn alloy coating material provided with a Sn alloy coating layer, wherein the thickness of the first coating layer is 0.05 to 1.0 μm and the thickness of the second coating layer is 0.005 to 0.5 μm. .
すなわち本発明は、CuまたはCu合金からなる基材表面
にNi、Coまたはこれらを含む合金の第1被覆層を設け
て、基材のCuまたはCu合金が最外層のSnまたはSn合金被
覆層に拡散するのを防止、さらに第2層のAgまたはAg合
金の被覆層を設けて第1被覆層の金属または合金が最外
層のSnまたはSn合金層に拡散するのを防止し、高温下に
おいても最外層のSnまたはSn合金被覆層が長期にわたり
拡散合金化されず、表面の酸化変色を防止し、かつ接触
抵抗の増加を減少せしめたものである。
That is, the present invention provides a first coating layer of Ni, Co or an alloy containing these on the surface of a substrate made of Cu or Cu alloy, and the Cu or Cu alloy of the substrate is coated on the outermost Sn or Sn alloy coating layer. It prevents diffusion and further provides a second layer of Ag or an Ag alloy coating layer to prevent the metal or alloy of the first coating layer from diffusing into the outermost Sn or Sn alloy layer. The outermost Sn or Sn alloy coating layer is not subjected to diffusion alloying for a long period of time, preventing oxidative discoloration of the surface and reducing an increase in contact resistance.
本発明においてCuまたはCu合金基材とは、純銅、黄
銅、青銅の他、丹銅、りん青銅、キュプロニッケル、各
種リードフレーム用銅合金などであり、またSnまたはSn
合金とは、Snの他、通常の半田合金が使用できる。上記
の被覆層の被覆方法は電気めっき、無電解めっき、蒸
着、PVD、CVD等が適用できる。そしてNi、Coまたはこれ
らを含む合金の第1被覆層の厚さが0.05〜1.0μmであ
ることが必要であり、0.05μmより薄いと拡散防止効果
が少なく、これより厚くなると加工性が低下する。また
AgまたはAg合金被覆層の厚さが0.05〜0.5μmであるこ
とが必要であり、これより薄いと拡散防止効果が充分で
なく、0.5μmを越えると経済上好ましくない。さらに
最外層のSnまたはSn合金被覆層の厚さは従来から通常用
いられている材料のものであり0.5〜10μmの範囲が適
当である。
In the present invention, the Cu or Cu alloy base material, other than pure copper, brass, bronze, copper bronze, phosphor bronze, cupronickel, copper alloys for various lead frames, and the like, and Sn or Sn
As the alloy, a normal solder alloy other than Sn can be used. As the coating method of the above-mentioned coating layer, electroplating, electroless plating, vapor deposition, PVD, CVD and the like can be applied. It is necessary that the thickness of the first coating layer of Ni, Co or an alloy containing them is 0.05 to 1.0 μm, and if the thickness is less than 0.05 μm, the effect of preventing diffusion is small, and if the thickness is more than this, workability is reduced. . Also
It is necessary that the thickness of the Ag or Ag alloy coating layer be 0.05 to 0.5 μm. If the thickness is less than this, the diffusion preventing effect is not sufficient, and if it exceeds 0.5 μm, it is economically undesirable. Further, the thickness of the outermost Sn or Sn alloy coating layer is a thickness of a conventionally used material, and is suitably in the range of 0.5 to 10 μm.
また第1被覆層としては、Ni、Coの他Ni−Cu、Ni−C
r、Ni−Zn、Ni−P、Ni−Cu−P、Co−P、Ni−Co、Ni
−Feなどの合金が適用でき、第2被覆層してはAgの他Ag
−In、Ag−Sn、Ag−Zn、Ag−Niなどの合金が適用でき
る。
In addition, as the first coating layer, other than Ni and Co, Ni-Cu, Ni-C
r, Ni-Zn, Ni-P, Ni-Cu-P, Co-P, Ni-Co, Ni
-Alloys such as -Fe can be applied, and Ag as well as Ag is used as the second coating layer.
Alloys such as -In, Ag-Sn, Ag-Zn, and Ag-Ni can be applied.
本発明は上記したように、第1被覆層がCuまたはCu合
金基材と最外層のSnまたはSn合金被覆層の拡散を防止
し、さらに第2被覆層が、第1被覆層と最外層のSnまた
はSn合金被覆層の拡散を防止して最外層のSnまたはSn合
金被覆層表面の酸化変色をなくし、かつ接触抵抗の増加
を防止し、従って接触特性の劣化を著しく低減するもの
である。
According to the present invention, as described above, the first coating layer prevents the diffusion of the Cu or Cu alloy base material and the outermost Sn or Sn alloy coating layer, and the second coating layer further comprises the first coating layer and the outermost layer. The purpose of the present invention is to prevent the Sn or Sn alloy coating layer from diffusing to eliminate the oxidative discoloration of the surface of the outermost Sn or Sn alloy coating layer and to prevent an increase in contact resistance, and thus to significantly reduce the deterioration of contact characteristics.
〔実施例〕〔Example〕
以下に本発明の一実施例について説明する。 Hereinafter, an embodiment of the present invention will be described.
実施例1 板厚0.3mmの7/3黄銅条を、電解脱脂、酸洗、水洗後、
スルファミン酸浴を用いてめっき厚さ0.05、0.2、0.5、
1.0μmのNiめっきを施し、さらにこの表面に青化浴を
用いて、めっき厚さが0.005、0.05、0.2、0.5μmのAg
めっきを施し、さらにこの表面に硫酸浴を用いて厚さ1.
0μmの光沢Snめっきを行なってSnめっき被覆材料を作
製した。
Example 1 A 0.3 mm thick 7/3 brass strip was subjected to electrolytic degreasing, pickling, and water washing.
Using a sulfamic acid bath, plating thickness 0.05, 0.2, 0.5,
Apply 1.0μm Ni plating, and further use a bluing bath on this surface to make the plating thickness 0.005, 0.05, 0.2, 0.5μm Ag
Plating is applied, and the thickness of this surface is increased to 1.
A bright Sn plating of 0 μm was performed to produce a Sn plating coating material.
比較例1 Niめっき厚を1.2μmとし、Agめっきをしなかったこ
と以外は実施例1と同様にしてSnめっき被覆材料を作製
した。
Comparative Example 1 An Sn plating coating material was produced in the same manner as in Example 1 except that the Ni plating thickness was 1.2 μm and that Ag plating was not performed.
比較例2 Niめっきを施さず、Agめっき厚を0.2μmとした以外
は実施例1と同様にしてSnめっき被覆材料を作製した。
Comparative Example 2 An Sn plating coating material was produced in the same manner as in Example 1 except that the Ni plating was not applied and the Ag plating thickness was changed to 0.2 μm.
比較例3 Niめっき厚を0.03μm、Agめっき厚を0.2μmとした
以外は実施例1と同様にしてSnめっき被覆材料を作製し
た。
Comparative Example 3 An Sn plating coating material was produced in the same manner as in Example 1, except that the Ni plating thickness was 0.03 μm and the Ag plating thickness was 0.2 μm.
比較例4 Niめっき厚を0.5μm、Agめっき厚を0.001μmとした
以外は実施例1と同様にしてSnめっき被覆材料を作製し
た。
Comparative Example 4 An Sn plating coating material was produced in the same manner as in Example 1 except that the Ni plating thickness was 0.5 μm and the Ag plating thickness was 0.001 μm.
比較例5 NiおよびAgめっき施さず、Cuを青化浴にて0.6μmの
厚さにめっきする以外は実施例1と同様にしてSnめっき
被覆材料を作製した。
Comparative Example 5 An Sn plating coating material was produced in the same manner as in Example 1 except that Ni and Ag plating were not performed and Cu was plated to a thickness of 0.6 μm in a bluing bath.
比較例6 Niめっきのめっき厚さが2.0μmである以外は実施例
1と同様にしてSnめっき被覆材料を作製した。
Comparative Example 6 An Sn plating coating material was produced in the same manner as in Example 1 except that the plating thickness of the Ni plating was 2.0 μm.
実施例2 板厚0.2mmのりん青銅条を電解脱脂、酸洗、水洗し、
ワット浴を用いNiを0.5μmめっきし、その表面にAg−I
nめっきを青化浴にて0.2μm施し、その表面にフェノー
ルスルフォン酸浴を用いて半田めっきを1.2μmの厚さ
に施してSn合金被覆材料を作製した。
Example 2 A phosphor bronze strip having a thickness of 0.2 mm was electrolytically degreased, pickled, and washed with water.
Using a Watt bath, Ni was plated 0.5 μm, and the surface was Ag-I
The n-plating was applied in a bluing bath at 0.2 μm, and the surface thereof was subjected to solder plating using a phenolsulfonic acid bath to a thickness of 1.2 μm to produce a Sn alloy coating material.
実施例3 Niの代りに塩化物−ふっ化物浴を用いてSn−Ni合金め
っきを0.5μm施した以外は実施例2と同様にしてSn合
金被覆材料を作製した。
Example 3 A Sn alloy-coated material was produced in the same manner as in Example 2, except that 0.5 μm of Sn—Ni alloy plating was applied using a chloride-fluoride bath instead of Ni.
上記の実施例および比較例において作製した各試料に
ついて、150℃のエアーバス内に4週間大気加熱した後
の外観、接触抵抗、純Sn層の厚さおよび0.2Rの90°曲げ
試験を行なった。この結果を第1表に示す。
Each sample prepared in the above Examples and Comparative Examples was subjected to a 90 ° bending test of appearance, contact resistance, pure Sn layer thickness, and 0.2R after heating in air in a 150 ° C. air bath for 4 weeks. . Table 1 shows the results.
第1表から明らかなように本発明の実施例1〜3の被
覆材料はいずれも外観における表面の変色がなく良好で
接触抵抗が小さく、また残存Sn厚さも多いことが判る。
これに対し比較例1〜5のものは、いずれも外観表面の
変色が多くまた接触抵抗も多く、残存Sn厚さも非常に少
ないことが判る。
As is clear from Table 1, all of the coating materials of Examples 1 to 3 of the present invention have good appearance without discoloration of the surface in appearance, have low contact resistance, and have a large residual Sn thickness.
On the other hand, in each of Comparative Examples 1 to 5, it can be seen that the discoloration of the appearance surface is large, the contact resistance is large, and the residual Sn thickness is very small.
比較例6は90°曲げ割れにおいてあまり良好でなかっ
た。
Comparative Example 6 was not so good in 90 ° bending cracks.
〔効果〕〔effect〕
以上に説明したように本発明によれば、高温の使用に
おいても表面変色が少なく、かつ接触特性の劣化の極め
て少ない。SnまたはSn合金被覆材料が得られるもので工
業上顕著な効果を奏するものである。
As described above, according to the present invention, the surface discoloration is small even at a high temperature, and the contact characteristics are extremely deteriorated. It is a material that can obtain a Sn or Sn alloy coating material and has industrially remarkable effects.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 H01L 23/50 H01R 13/03 A H01R 13/03 H05K 1/09 C H05K 1/09 H01G 1/14 F ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification number Agency reference number FI Technical display location H01L 23/50 H01R 13/03 A H01R 13/03 H05K 1/09 C H05K 1/09 H01G 1 / 14 F

Claims (1)

    (57)【特許請求の範囲】(57) [Claims]
  1. 【請求項1】CuまたはCu合金基材表面にNi、Coまたはこ
    れらを含む合金の第1被覆層を設け、その表面にAgまた
    はAg合金の第2被覆層を設け、さらにその表面にSnまた
    はSn合金の被覆層を設けてなるSnまたはSn合金被覆材料
    であって、前記第1被覆層の厚さが0.05〜1.0μm、前
    記第2被覆層の厚さが0.005〜0.5μmである、Snまたは
    Sn合金被覆材料。
    1. A first coating layer of Ni, Co or an alloy containing them is provided on the surface of a Cu or Cu alloy substrate, a second coating layer of Ag or an Ag alloy is provided on the surface, and Sn or Sn is further provided on the surface. Sn or a Sn alloy coating material provided with a Sn alloy coating layer, wherein the thickness of the first coating layer is 0.05 to 1.0 μm and the thickness of the second coating layer is 0.005 to 0.5 μm. Or
    Sn alloy coating material.
JP63138654A 1988-06-06 1988-06-06 Sn or Sn alloy coating material Expired - Lifetime JP2726434B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP63138654A JP2726434B2 (en) 1988-06-06 1988-06-06 Sn or Sn alloy coating material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63138654A JP2726434B2 (en) 1988-06-06 1988-06-06 Sn or Sn alloy coating material

Publications (2)

Publication Number Publication Date
JPH01306574A JPH01306574A (en) 1989-12-11
JP2726434B2 true JP2726434B2 (en) 1998-03-11

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JP2726434B2 (en)

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