JP4397245B2 - Tin-plated copper alloy material for electric and electronic parts and method for producing the same - Google Patents

Tin-plated copper alloy material for electric and electronic parts and method for producing the same Download PDF

Info

Publication number
JP4397245B2
JP4397245B2 JP2004034282A JP2004034282A JP4397245B2 JP 4397245 B2 JP4397245 B2 JP 4397245B2 JP 2004034282 A JP2004034282 A JP 2004034282A JP 2004034282 A JP2004034282 A JP 2004034282A JP 4397245 B2 JP4397245 B2 JP 4397245B2
Authority
JP
Japan
Prior art keywords
layer
copper alloy
plating layer
tin
base material
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 - Fee Related
Application number
JP2004034282A
Other languages
Japanese (ja)
Other versions
JP2005226097A (en
Inventor
利久 原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kobe Steel Ltd
Original Assignee
Kobe Steel Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kobe Steel Ltd filed Critical Kobe Steel Ltd
Priority to JP2004034282A priority Critical patent/JP4397245B2/en
Publication of JP2005226097A publication Critical patent/JP2005226097A/en
Application granted granted Critical
Publication of JP4397245B2 publication Critical patent/JP4397245B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Landscapes

  • Electroplating Methods And Accessories (AREA)

Description

本発明は、主として自動車・民生用の端子、コネクタ、ジャンクションブロック、回路基板等の電気・電子部品に用いられる錫めっき銅合金材であり、特にオス、メス端子からなる嵌合型端子として用いたとき、嵌合時の挿入力が低く、高温で使用される場合においても優れた電気的信頼性が保持でき、耐食性にも優れる錫めっき銅合金材に関する。   The present invention is a tin-plated copper alloy material mainly used for electric / electronic parts such as automobile / consumer terminals, connectors, junction blocks, circuit boards, etc., and particularly used as a fitting type terminal composed of male and female terminals. In particular, the present invention relates to a tin-plated copper alloy material that has a low insertion force at the time of fitting, can maintain excellent electrical reliability even when used at high temperatures, and has excellent corrosion resistance.

自動車等の電線の接続に用いられるコネクタには、銅合金に錫めっきを施したオス端子とメス端子の組み合せからなる嵌合型端子が使用されている。嵌合型端子が複数個集合したコネクタを多極端子コネクタという。
自動車の電装化が進むなかで、このようなコネクタの極数、すなわち、一つのコネクタの中の端子の数は増加している。端子数が増加すると挿入力が大きくなり、実装に道具が必要になったり、人が挿入する場合でも大きな力を必要とするようになり、その組み立て作業の効率を低下させる原因になる。このため、極数が増加しても、挿入力が従来よりも大きくならないように、低挿入力の端子が要求されている。
A connector used for connecting an electric wire of an automobile or the like uses a fitting type terminal composed of a combination of a male terminal and a female terminal obtained by tin-plating a copper alloy. A connector in which a plurality of fitting type terminals are gathered is called a multipolar terminal connector.
The number of poles of such a connector, that is, the number of terminals in one connector, is increasing as automobiles are becoming more electrical. When the number of terminals increases, the insertion force increases, and a tool is required for mounting, or a large force is required even when a person inserts, which causes a reduction in the efficiency of the assembly work. For this reason, even if the number of poles increases, a terminal with a low insertion force is required so that the insertion force does not become larger than before.

錫めっき端子は、Snめっきを薄くすることにより挿入力が低下する。しかし、自動車室内の省スペース化の要求からコネクターの設置個所は室内からエンジンルーム内への移行が進展し、エンジンルームでの雰囲気温度は最大150℃程度に到達する。そのため、Snめっきを薄くすると銅又は銅合金母材からCu及び合金元素が拡散し、あるいはNi等の下地めっきが拡散してSnめっき表層に酸化物を形成し、端子の接触抵抗が増加する問題が顕在化する。接触抵抗が増加すると、電子制御機器の誤作動が懸念される。従って、現実にはSnめっき厚さを薄くし、かつ電気的信頼性を維持することは大変困難である。
また、排ガスとして亜硫酸ガスが発生する工業地帯等において長時間運転又は放置する場合、その亜硫酸ガスにより表面めっき層が腐食し、さらに腐食が銅合金母材にまで達して嵌合型端子としての信頼性が失われる。
The tin plating terminal has a reduced insertion force by thinning the Sn plating. However, due to the demand for space saving in the automobile interior, the connector installation location has been shifted from the interior to the engine compartment, and the ambient temperature in the engine compartment reaches about 150 ° C. at the maximum. Therefore, when Sn plating is thinned, Cu and alloy elements diffuse from the copper or copper alloy base material, or the base plating such as Ni diffuses to form an oxide on the surface of the Sn plating, thereby increasing the contact resistance of the terminal. Becomes apparent. When the contact resistance increases, there is a concern about malfunction of the electronic control device. Therefore, in reality, it is very difficult to reduce the Sn plating thickness and maintain the electrical reliability.
In addition, when operating or leaving for a long time in an industrial area where sulfurous acid gas is generated as exhaust gas, the surface plating layer corrodes due to the sulfurous acid gas, and further, the corrosion reaches the copper alloy base material, which is reliable as a mating type terminal. Sex is lost.

下記特許文献1〜3に、従来の錫めっき銅合金材が記載されている。下記特許文献4〜9に、ニッケルと錫と亜鉛を含む従来の端子・コネクタ用銅合金材が記載されている。
特許文献1には、Cu−Ni−Zn系の洋白素材上に、Niめっき層、Sn及びCuの金属間化合物層、Snめっき層を順次形成した錫めっき銅合金材が記載されている。この錫めっき銅合金材はリードフレーム用であり、嵌合型端子用としての特性は検討されていない。
特許文献2には、銅又は銅合金基材上に、25〜40%のニッケルを含む銅のバリア層(厚さ0.2〜2.5μm)と、その上にSn又はSn合金被覆層を有する錫めっき銅合金材が記載されている。これは嵌合型端子用であるが、コネクタの挿入力についてはまったく検討されていない。
特許文献3には、Snめっき厚が薄く、低挿入力の端子用錫めっき銅合金材が記載されている。
The following patent documents 1 to 3 describe conventional tin-plated copper alloy materials. Patent Documents 4 to 9 listed below describe conventional copper alloy materials for terminals and connectors containing nickel, tin, and zinc.
Patent Document 1 describes a tin-plated copper alloy material in which a Ni plating layer, an Sn and Cu intermetallic compound layer, and an Sn plating layer are sequentially formed on a Cu-Ni-Zn-based white material. This tin-plated copper alloy material is used for lead frames, and its characteristics for fitting type terminals have not been studied.
In Patent Document 2, a copper barrier layer (thickness 0.2 to 2.5 μm) containing nickel of 25 to 40% on a copper or copper alloy base material, and a Sn or Sn alloy coating layer thereon. A tin-plated copper alloy material is described. This is for a mating type terminal, but the insertion force of the connector has not been studied at all.
Patent Document 3 describes a tin-plated copper alloy material for terminals having a thin Sn plating thickness and a low insertion force.

特開平6−196349号公報JP-A-6-196349 特表2001−526734号公報JP 2001-526734 A 特開平10−46363号公報JP 10-46363 A 特開昭61−127842号公報JP-A 61-127842 特開平3−226536号公報JP-A-3-226536 特開2000−80427号公報JP 2000-80427 A 特開平3−10035号公報Japanese Patent Laid-Open No. 3-10035 特開平11−335756号公報JP-A-11-335756 特開平10−46363号公報JP 10-46363 A

ところで、高温放置後の電気的信頼性や耐食性について、使用環境は年々厳しくなっており、銅合金単独で特性を保持するのは難しく、錫めっき銅合金材が実用化されているが、さらに160℃という高温環境での電気的信頼性が要求され、同時に低挿入力が要求されるようになると、従来の錫めっき銅合金材では、対応が難しくなっている。
そこで、本発明者らは、銅合金母材側よりNi層、Cu−Sn合金層及びSn層からなる表面めっき層を形成した錫めっき銅合金材を提案した(特願2002−219155)。この錫めっき銅合金材は、高温雰囲気下で長時間経過後も電気的信頼性が維持でき、同時に低挿入力、亜硫酸ガス耐食性等の特性を満足している。
By the way, with regard to electrical reliability and corrosion resistance after being left at high temperature, the usage environment has become severe year by year, and it is difficult to maintain the characteristics of the copper alloy alone, and tin-plated copper alloy materials have been put to practical use. When electrical reliability in a high temperature environment of ° C. is required and at the same time a low insertion force is required, it is difficult to cope with conventional tin-plated copper alloy materials.
Therefore, the present inventors have proposed a tin-plated copper alloy material in which a surface plating layer composed of a Ni layer, a Cu—Sn alloy layer and a Sn layer is formed from the copper alloy base material side (Japanese Patent Application No. 2002-219155). This tin-plated copper alloy material can maintain electrical reliability even after a long time in a high-temperature atmosphere, and at the same time satisfies characteristics such as low insertion force and sulfurous acid gas corrosion resistance.

しかしながら、錫めっき端子の電気的信頼性、低挿入力及び耐食性等の特性は表面被覆層のみで決まるわけではなく銅合金母材の材質も重要である。例えば、高い導電率であれば端子の発熱を抑えることができるし、本発明者が見い出したところによれば母材硬度が錫めっき銅合金材の表面硬度及び挿入力に影響し、高温放置時の銅合金母材と表面めっき層の界面におけるボイドの発生(めっき層の剥離の原因となる)の程度は銅合金母材の材質によって変化する。
従って、本発明は、Ni層、Cu−Sn合金層及びSn層からなる表面めっき層に最適な銅合金母材を見い出し、高温放置後の電気的信頼性が高く、耐食性に優れ、かつ高温放置後のめっき層の剥離がなく、特に低挿入力の嵌合型端子用として優れた特性を有する、電気・電子部品用錫めっき銅合金材を得ることを目的とする。
However, characteristics such as electrical reliability, low insertion force, and corrosion resistance of the tin-plated terminal are not determined solely by the surface coating layer, but the material of the copper alloy base material is also important. For example, if the electrical conductivity is high, the heat generation of the terminal can be suppressed, and the present inventors have found that the base material hardness affects the surface hardness and insertion force of the tin-plated copper alloy material, The degree of void generation (causing peeling of the plating layer) at the interface between the copper alloy base material and the surface plating layer varies depending on the material of the copper alloy base material.
Therefore, the present invention finds an optimal copper alloy base material for a surface plating layer comprising a Ni layer, a Cu—Sn alloy layer, and a Sn layer, has high electrical reliability after being left at high temperature, excellent corrosion resistance, and left at high temperature. An object of the present invention is to obtain a tin-plated copper alloy material for electric / electronic parts which has no subsequent peeling of the plating layer and has excellent characteristics particularly for a fitting type terminal having a low insertion force.

本発明に係る電気・電子部品用錫めっき銅合金材は、Ni:0.01〜9%、Sn:0.01〜5%、Zn:0.001〜15%、さらに必要に応じてP:0.0001〜0.05%とSi:0.0001〜1%のいずれか一方又は双方を含有し、残部Cuと不純物からなり、導電率20%IACS以上の銅合金母材表面に、Ni層及びCu−Sn合金層からなる表面めっき層がこの順に形成され、あるいはNi層、Cu−Sn合金層及びSn層からなる表面めっき層がこの順に形成されていることを特徴とする。銅合金母材とNi層の間にCuめっき層を形成することもできる。   The tin-plated copper alloy material for electric / electronic parts according to the present invention includes Ni: 0.01 to 9%, Sn: 0.01 to 5%, Zn: 0.001 to 15%, and P: One or both of 0.0001 to 0.05% and Si: 0.0001 to 1%, the balance being Cu and impurities, the Ni layer on the surface of the copper alloy base material having a conductivity of 20% or more IACS And a surface plating layer composed of a Cu—Sn alloy layer is formed in this order, or a surface plating layer composed of a Ni layer, a Cu—Sn alloy layer, and a Sn layer is formed in this order. A Cu plating layer may be formed between the copper alloy base material and the Ni layer.

上記銅合金母材は、さらにMn、Cr、Mg、Be、Al、Ca、Ti、V、Fe、Co、Zr、Nb、Mo、Ag、In、Pb、Hf、Ta、B、S、C、Se、Te、Sbの1種又は2種以上を総量で3%以下含み得る。また、Niの質量(銅合金母材がさらにFe又は/及びTiを含む場合は、Ni、Fe及びTiの合計質量)をaとし、PとSiの合計質量をbとしたとき、両者の質量比a/bが3.5以上であることが望ましい。銅合金母材がPとSiをどちらも含まないときは、当然上記関係を満たす。
上記表面めっき層において、Ni層の厚さが0.1〜1.0μm、Cu−Sn合金層の厚さが0.1〜1.0μm、Sn層の厚さが3.0μm以下、さらにNi層の下地としてのCu層の厚さは0.1〜1.0μmであることが望ましい。
The copper alloy base material further includes Mn, Cr, Mg, Be, Al, Ca, Ti, V, Fe, Co, Zr, Nb, Mo, Ag, In, Pb, Hf, Ta, B, S, C, One or more of Se, Te, and Sb may be included in a total amount of 3% or less. Moreover, when the mass of Ni (when the copper alloy base material further includes Fe or / and Ti, the total mass of Ni, Fe and Ti) is a, and the total mass of P and Si is b, the mass of both It is desirable that the ratio a / b is 3.5 or more. When the copper alloy base material contains neither P nor Si, the above relationship is naturally satisfied.
In the surface plating layer, the Ni layer has a thickness of 0.1 to 1.0 μm, the Cu—Sn alloy layer has a thickness of 0.1 to 1.0 μm, the Sn layer has a thickness of 3.0 μm or less, and Ni The thickness of the Cu layer as the base of the layer is preferably 0.1 to 1.0 μm.

上記錫めっき銅合金材は、前記組成の銅合金母材の表面に、Niめっき層、Cuめっき層及びSnめっき層からなる表面めっき層をこの順に形成した後、100〜600℃で10分以下の加熱処理を行ってCu−Sn合金層を形成し、前記表面めっき層をNi層及びCu−Sn合金層、あるいはさらにSn層からなる表面めっき層とすることにより、製造することができる。ここで、Cuめっき層はCu合金を含み、Snめっき層はSn合金を含む。具体的に、Cuめっき層の銅合金としてCu−1〜50%Sn、Snめっき層のSn合金としてSn−1〜10%Cu、Sn−1〜10%Ag、Sn−1〜10%Biの各合金を挙げることができる。なお、このようなSn合金によるSnめっき層は、ウイスカ発生防止の観点から、それ自体、現在実用化されている。このCu合金又はSn合金に含まれる合金元素は、加熱処理後に形成されるCu−Sn合金層にも含まれることになる。この製造方法において、必要に応じてNiめっき層の下地としてCuめっき層を形成する。このCuめっき層もCu合金を含み、具体的にCu−1〜10%Znを挙げることができる。
加熱処理後の表面めっき層において前記厚さのCu層、Ni層、Cu−Sn合金層及びSn層を得るには、加熱処理前においてNiめっき層の厚さを0.1〜1.0μm、Cuめっき層の厚さを0.05〜0.5μm、Snめっき層の厚さを0.05〜3.5μmの範囲内で形成すればよい。一方、Cuめっき層とSnめっき層を合金化させてCu−Sn合金層を形成する代わりに、直接Cu−Sn合金めっきを行うこともでき、その場合は加熱処理による合金化は不要となる。
The tin-plated copper alloy material is formed with a surface plating layer composed of a Ni plating layer, a Cu plating layer and a Sn plating layer in this order on the surface of the copper alloy base material having the above composition, and then at 100 to 600 ° C. for 10 minutes or less. The Cu—Sn alloy layer is formed by performing the heat treatment, and the surface plating layer can be manufactured by forming a Ni plating layer and a Cu—Sn alloy layer, or a surface plating layer made of a Sn layer. Here, the Cu plating layer includes a Cu alloy, and the Sn plating layer includes a Sn alloy. Specifically, Cu-1 to 50% Sn as the copper alloy of the Cu plating layer, Sn-1 to 10% Cu, Sn-1 to 10% Ag, Sn-1 to 10% Bi as the Sn alloy of the Sn plating layer Each alloy can be mentioned. In addition, the Sn plating layer made of such an Sn alloy is currently put into practical use from the viewpoint of preventing whisker generation. The alloy element contained in this Cu alloy or Sn alloy is also contained in the Cu—Sn alloy layer formed after the heat treatment. In this manufacturing method, a Cu plating layer is formed as a base of the Ni plating layer as necessary. This Cu plating layer also contains a Cu alloy, and specifically Cu-1 to 10% Zn can be mentioned.
In order to obtain the Cu layer, Ni layer, Cu—Sn alloy layer and Sn layer having the above thickness in the surface plating layer after the heat treatment, the thickness of the Ni plating layer is 0.1 to 1.0 μm before the heat treatment, What is necessary is just to form the thickness of Cu plating layer in the range of 0.05-0.5 micrometer, and the thickness of Sn plating layer in the range of 0.05-3.5 micrometer. On the other hand, instead of alloying the Cu plating layer and the Sn plating layer to form the Cu—Sn alloy layer, direct Cu—Sn alloy plating can also be performed. In this case, alloying by heat treatment is unnecessary.

本発明によれば、高温雰囲気下において銅合金素材と被覆層の界面の接合信頼性(めっきの剥離防止)及び電気的信頼性(低接触抵抗)を維持でき、かつ耐食性に優れた電気・電子部品用錫めっき銅合金材を得ることができる。この錫めっき銅合金材は、銅合金母材の硬度が高く、表面硬度Hv90以上(荷重25g)を得ることができるため挿入力が低く、さらに銅合金母材の強度が550N/mm以上と高く、曲げ加工性にも優れていることから、特に低挿入力が求められる嵌合型端子用として優れている。例えば端子幅が1mm以下の小型端子や加工性の厳しいボックス型端子に使用した場合、挿入力が低く、高温で使用される場合においても優れた電気的信頼性が保持できる。そのほか、本発明に係る銅合金母材は応力緩和特性、ばね性などについても優れており、表面めっき層と同じくNi及びSnを含むため、リサイクル性にも優れる。 According to the present invention, it is possible to maintain the bonding reliability (prevention of plating peeling) and electrical reliability (low contact resistance) at the interface between the copper alloy material and the coating layer in a high-temperature atmosphere, and it has excellent corrosion resistance. A tin-plated copper alloy material for parts can be obtained. Since this tin-plated copper alloy material has a high hardness of the copper alloy base material and can obtain a surface hardness of Hv90 or higher (load 25 g), the insertion force is low, and the strength of the copper alloy base material is 550 N / mm 2 or higher. Since it is high and has excellent bending workability, it is particularly excellent for fitting type terminals that require low insertion force. For example, when it is used for a small terminal having a terminal width of 1 mm or less or a box-type terminal with severe workability, the insertion force is low, and excellent electrical reliability can be maintained even when used at a high temperature. In addition, the copper alloy base material according to the present invention is excellent in stress relaxation characteristics, spring properties, and the like, and also contains Ni and Sn as well as the surface plating layer, and is excellent in recyclability.

従来の溶融Snめっき(Hot Air Leveled Tin、Hot Dip)は、層厚が5〜10μmと厚く、耐食性は良いが挿入力が高かった。一方、挿入力を低くするためにSnめっき層を薄くすると、高温放置後の耐食性が低下する問題があった。そこでSnめっき層を薄くし同時に耐食性を確保するため、下地にNiめっき層を形成することを検討したが、Niめっき層の上に直接Snめっきを行うと、高温放置時にSnとNiの合金層が成長し、接触抵抗が高くなる問題があった。
この問題は、Niめっき層とSnめっき層の間にCuめっき層を形成することにより解決された。Cuめっき層とSnめっき層は加熱により合金化してCu−Sn合金層を形成する。銅合金母材表面に、この表面めっき層を形成することにより、高温放置した後でも接触抵抗を低く維持でき、耐食性に優れ、かつ挿入力が低い錫めっき銅合金材が得られる。
以下、本発明に係る表面めっき層について説明する。
Conventional hot Sn plating (Hot Air Leveled Tin, Hot Dip) has a thickness of 5 to 10 μm and good corrosion resistance, but has a high insertion force. On the other hand, if the Sn plating layer is made thin in order to reduce the insertion force, there is a problem that the corrosion resistance after leaving at high temperature is lowered. Therefore, in order to make the Sn plating layer thin and at the same time secure corrosion resistance, it was considered to form a Ni plating layer on the underlayer. However, if Sn plating is directly performed on the Ni plating layer, an alloy layer of Sn and Ni when left at high temperature There has been a problem that the contact resistance becomes high.
This problem was solved by forming a Cu plating layer between the Ni plating layer and the Sn plating layer. The Cu plating layer and the Sn plating layer are alloyed by heating to form a Cu—Sn alloy layer. By forming this surface plating layer on the surface of the copper alloy base material, a tin-plated copper alloy material having excellent corrosion resistance and low insertion force can be obtained even after being left at a high temperature.
Hereinafter, the surface plating layer according to the present invention will be described.

本発明において、銅合金母材表面にNi層を形成するのは、銅合金母材成分が表面へ拡散するのを防止するためである。このNi層厚さが0.1μm未満では、めっき層の欠陥から母材成分の拡散が起こり、高温放置後の亜硫酸ガス耐食性が低下する。一方、1.0μmを超えると成形加工性が低下し、小型の端子の成形が困難となる。従って、Ni層は厚さが0.1〜1.0μm、好ましくは0.1〜0.5μmとする。
Ni層の上に形成されたCu−Sn合金層はη相であり、Ni成分が表面へ拡散するのを防ぐ役割をもつ。このCu−Sn合金層厚さが0.1μm未満では、Ni層からのNiの拡散を抑制できない。一方、1.0μmを超えると、成形加工性が低下し、かつ高温放置後の接触抵抗が増加する。従って、Cu−Sn合金層は0.1〜1.0μmが望ましい。
In the present invention, the Ni layer is formed on the surface of the copper alloy base material in order to prevent the copper alloy base material component from diffusing to the surface. If this Ni layer thickness is less than 0.1 μm, diffusion of the base material component occurs due to defects in the plating layer, and the sulfurous acid gas corrosion resistance after standing at high temperature decreases. On the other hand, when the thickness exceeds 1.0 μm, molding processability is deteriorated and it becomes difficult to mold a small terminal. Therefore, the Ni layer has a thickness of 0.1 to 1.0 μm, preferably 0.1 to 0.5 μm.
The Cu—Sn alloy layer formed on the Ni layer is in the η phase and has a role of preventing the Ni component from diffusing to the surface. When the Cu—Sn alloy layer thickness is less than 0.1 μm, the diffusion of Ni from the Ni layer cannot be suppressed. On the other hand, when it exceeds 1.0 μm, the moldability is lowered and the contact resistance after being left at high temperature is increased. Therefore, the Cu—Sn alloy layer is desirably 0.1 to 1.0 μm.

高温放置後の接触抵抗を低く維持するためには、Cu−Sn合金層のCu含有量は60%以下であることが望ましい。この組成比を得るには、加熱処理前のCuめっき層とSnめっき層の厚さを調整し、加熱処理後に当該組成比を得る。あるいは、この組成比のCu−Sn合金めっき層を直接形成する。Cu−Sn合金層のCu含有量が60%以下であることにより、Sn層がなくても接触抵抗を低く維持することができるが、Sn層があれば(厚く形成されるほど)耐食性が改善され、かつ高温放置後の接触抵抗を低く維持できるため、Sn層は0.1μm以上あることが望ましい。一方、Sn層が厚くなると挿入力が高くなるためSn層は3.0μm以下が望ましい。さらに望ましいのは1.0μm以下である。
銅合金母材とNi層の間に形成するCu層は、銅合金母材中の合金成分(特にZn)が表面めっき層側に拡散するのを抑制して、はんだ付け性の劣化を防止する作用をもつ。このCu層は、0.1μm未満では銅合金母材中の合金成分の拡散を抑制できない。一方、1.0μmを超えると、成形加工性が低下する。従って、この下地Cu層は0.1〜1.0μmが望ましい
In order to keep the contact resistance after being left at a high temperature low, the Cu content of the Cu—Sn alloy layer is desirably 60% or less. In order to obtain this composition ratio, the thicknesses of the Cu plating layer and the Sn plating layer before the heat treatment are adjusted, and the composition ratio is obtained after the heat treatment. Alternatively, a Cu—Sn alloy plating layer having this composition ratio is directly formed. When the Cu content of the Cu-Sn alloy layer is 60% or less, the contact resistance can be kept low even without the Sn layer, but the corrosion resistance improves with the Sn layer (the thicker the layer is formed). In addition, since the contact resistance after being left at high temperature can be kept low, the Sn layer is desirably 0.1 μm or more. On the other hand, when the Sn layer becomes thicker, the insertion force becomes higher. More desirable is 1.0 μm or less.
The Cu layer formed between the copper alloy base material and the Ni layer prevents the alloy components (particularly Zn) in the copper alloy base material from diffusing to the surface plating layer side, thereby preventing deterioration of solderability. Has an effect. If this Cu layer is less than 0.1 μm, diffusion of alloy components in the copper alloy base material cannot be suppressed. On the other hand, when it exceeds 1.0 μm, the moldability is lowered. Therefore, the base Cu layer is preferably 0.1 to 1.0 μm.

一方、錫めっき銅合金材を加熱(高温に長時間放置)すると、銅合金母材中の添加成分がNiめっき層に拡散し銅合金母材とNiめっき層の界面にボイドが発生する。その状態を概念的に示すものが図1である。銅合金母材1とNi層2の間にボイド3が形成されている。ボイドの発生は表面めっき層の剥離の原因となるため、これを抑制することが望ましい。本発明の銅合金母材組成は、このボイドの発生を防止するために最適な組成として選定されたものである。
以下、本発明に係る銅合金母材について説明する。
On the other hand, when the tin-plated copper alloy material is heated (left at high temperature for a long time), the additive component in the copper alloy base material diffuses into the Ni plating layer and voids are generated at the interface between the copper alloy base material and the Ni plating layer. FIG. 1 conceptually shows the state. A void 3 is formed between the copper alloy base material 1 and the Ni layer 2. Since the generation of voids causes peeling of the surface plating layer, it is desirable to suppress this. The copper alloy base material composition of the present invention is selected as an optimal composition in order to prevent the generation of voids.
Hereinafter, the copper alloy base material according to the present invention will be described.

銅合金母材を鋳造する時の脱酸素剤として添加されるSiやPは、加熱によりNi層と反応し、NiSiやNiPなどの金属間化合物を作り、ボイド発生の原因となる。銅合金母材中にNiを添加することにより、このNiが母材中のSiやPを補足して析出物となり、これらがNi層へ拡散するのを防止し、ボイド発生を抑制する。そのため、銅合金母材中のNi含有量は0.01%以上、さらに0.1%以上が望ましい。一方、含有量が9%を超えると導電率が低下する。従って、Ni含有量は0.01〜9%とする。望ましくは0.1〜5.0%である。
高い耐熱信頼性(高温放置後もボイドに起因するめっき剥離がない)を得るためには、Niの質量をaとし、SiとPの合計質量をbとしたとき、a/bを3.5以上とすることが望ましい。より高い耐熱信頼性を確保するには、a/bは4.0以上が望ましい。SiとPの両方とも実質的に含まない場合は、当然a/bはこの関係を満たす。
なお、Fe及びTiもNiと同等の作用を有する。従って、銅合金母材が、Fe又は/及びTiを含む場合、Ni、Fe及びTiの合計質量をaとして計算する。FeとTiの双方を含まない場合、aはNiの質量となる。
Si or P added as an oxygen scavenger when casting a copper alloy base material reacts with the Ni layer by heating to form an intermetallic compound such as Ni 2 Si or NiP, which causes voids. By adding Ni to the copper alloy base material, this Ni supplements Si and P in the base material to become precipitates, which prevent them from diffusing into the Ni layer and suppress the generation of voids. Therefore, the Ni content in the copper alloy base material is preferably 0.01% or more, and more preferably 0.1% or more. On the other hand, if the content exceeds 9%, the electrical conductivity decreases. Therefore, the Ni content is set to 0.01 to 9%. Desirably, it is 0.1 to 5.0%.
In order to obtain high heat resistance reliability (there is no plating peeling due to voids even after standing at high temperature), when the mass of Ni is a and the total mass of Si and P is b, a / b is 3.5. It is desirable to set it above. In order to ensure higher heat resistance reliability, a / b is preferably 4.0 or more. When both Si and P are substantially not included, a / b naturally satisfies this relationship.
Note that Fe and Ti have the same effect as Ni. Accordingly, when the copper alloy base material contains Fe or / and Ti, the total mass of Ni, Fe and Ti is calculated as a. When both Fe and Ti are not included, a is the mass of Ni.

Znは、Niと共に添加することにより、銅合金母材とNi層の界面のボイド発生を抑制でする作用を有する。銅合金母材中のZnの含有は0.001%以上の微量でもこの効果があるが、0.1%以上が望ましい。一方、含有量が15%を超えると応力腐食割れを起こして端子としての信頼性が低下し、導電率が下がる。従って、Zn含有量は0.001〜15%とする。望ましくは0.1〜3%である。
Snは、銅合金母材中に固溶し、銅合金母材と表面めっき層の電位差を少なくして耐食性を改善するとともに、引張り強度やばね特性を向上させる効果がある。Snの含有量は0.01%以上の微量でも効果はあるが、0.05%以上添加することが望ましい。一方、Snは添加量に従って導電率が低下する。従って、Sn含有量は0.05〜5%とする。望ましくは0.1〜3%である。
Mn〜Sbの元素は、不純物として又は添加元素として銅合金中に含まれ得る。これらの元素が微量含まれると、銅合金の結晶粒径を小さくしたり結晶粒界を強化することにより、耐熱性や加工性を向上させる作用を有し、さらに含有量が増えると銅合金の強度を向上させる作用を有するが、含有量が多くなると導電率が低下するため、総量で3%以下に制限する。
Zn, when added together with Ni, has the effect of suppressing void generation at the interface between the copper alloy base material and the Ni layer. The Zn content in the copper alloy base material has this effect even with a trace amount of 0.001% or more, but is preferably 0.1% or more. On the other hand, if the content exceeds 15%, stress corrosion cracking occurs, the reliability as a terminal decreases, and the electrical conductivity decreases. Therefore, the Zn content is 0.001 to 15%. Desirably, it is 0.1 to 3%.
Sn dissolves in the copper alloy base material, reduces the potential difference between the copper alloy base material and the surface plating layer, improves the corrosion resistance, and has the effect of improving the tensile strength and spring characteristics. Even if the Sn content is as small as 0.01% or more, it is effective, but it is desirable to add 0.05% or more. On the other hand, the conductivity of Sn decreases with the addition amount. Therefore, the Sn content is 0.05 to 5%. Desirably, it is 0.1 to 3%.
The elements Mn to Sb can be contained in the copper alloy as impurities or as additive elements. When these elements are contained in a small amount, it has the effect of improving heat resistance and workability by reducing the crystal grain size of the copper alloy or strengthening the crystal grain boundary. Although it has the effect | action which improves an intensity | strength, since electrical conductivity will fall when content increases, it restrict | limits to 3% or less in total.

本発明では、銅合金母材がNi、Sn及びZnを含み、これにより銅合金母材に550N/mm以上の高い引張り強さとHv150以上の高い硬度が得られる。電気回路が多くなり電気配線が小型化すると、小型端子(例えば幅2mm以下)が必要とされるようになり、高い引張強さと優れた曲げ加工性が必要とされるが、本発明の銅合金母材はこれに適している。また、銅合金母材の硬度が高いことにより、本発明の錫めっき銅合金材は表面硬度が高く低挿入力端子に適した材料となる。本発明では表面硬度Hv90(荷重0.098N)以上が達成され、Sn層が多少厚くても摩擦係数0.5以下となり、低挿入力が得られる。
小型端子では流す電流に制限があり発熱するため、導電率はできるだけ高く、20%IACS以上が望ましい。本発明の銅合金母材において、Ni、Sn及びZnの含有量を調整するとともに、Niほかの添加元素を金属間化合物として適宜析出させることにより、20%IACS以上の導電率は容易に達成できる。同様の手法で40%IACS以上を達成することも可能で、その場合、端子に流せる電流規格を上げることもできる。Ni等の析出による強化と、SnやZnによる固溶強化作用により、硬度Hv200以上を得ることも可能である。
また、本発明の錫めっき銅合金材では、160℃で1000時間加熱後の応力緩和率30%以下が達成される。
In the present invention, the copper alloy base material contains Ni, Sn, and Zn, whereby a high tensile strength of 550 N / mm 2 or more and a high hardness of Hv 150 or more are obtained in the copper alloy base material. As the number of electric circuits increases and the electric wiring becomes smaller, a small terminal (for example, a width of 2 mm or less) is required, and high tensile strength and excellent bending workability are required. The base material is suitable for this. Further, since the hardness of the copper alloy base material is high, the tin-plated copper alloy material of the present invention has a high surface hardness and is a material suitable for a low insertion force terminal. In the present invention, surface hardness Hv90 (load 0.098N) or more is achieved, and even if the Sn layer is somewhat thick, the friction coefficient is 0.5 or less, and a low insertion force is obtained.
In a small terminal, the current that flows is limited and heat is generated. Therefore, the conductivity is as high as possible, and 20% IACS or more is desirable. In the copper alloy base material of the present invention, by adjusting the contents of Ni, Sn, and Zn and appropriately depositing Ni and other additive elements as intermetallic compounds, a conductivity of 20% IACS or higher can be easily achieved. . It is also possible to achieve 40% IACS or more by the same method, and in that case, it is possible to increase the standard of current that can be passed through the terminal. It is possible to obtain a hardness of Hv 200 or higher by strengthening by precipitation of Ni or the like and solid solution strengthening action by Sn or Zn.
In the tin-plated copper alloy material of the present invention, a stress relaxation rate of 30% or less after heating at 160 ° C. for 1000 hours is achieved.

本発明に係る銅合金母材の製造にあたっては、その鋳塊を850℃以上の温度で熱間圧延し、圧延後に650℃以上の温度から焼き入れ、急速冷却する。次に冷間圧延を行い、350〜600℃において析出硬化熱処理を行う。強度を高くする場合には、さらに中間で、冷間圧延と650℃以上での溶体化熱処理及び急速冷却する工程を1〜3回施すとよい。続いて冷間圧延と歪み取りを行って、所望の銅合金板条を得る。最後にばね性を向上させるため、低温焼鈍を行うこともある。急速冷却の冷却速度は10℃/min以上が望ましい。   In producing the copper alloy base material according to the present invention, the ingot is hot-rolled at a temperature of 850 ° C. or higher, quenched from a temperature of 650 ° C. or higher after rolling, and rapidly cooled. Next, cold rolling is performed, and precipitation hardening heat treatment is performed at 350 to 600 ° C. In the case of increasing the strength, it is preferable to further perform a cold rolling, a solution heat treatment at 650 ° C. or higher, and a rapid cooling step 1 to 3 times in the middle. Subsequently, cold rolling and distortion removal are performed to obtain a desired copper alloy strip. Finally, in order to improve the spring property, low temperature annealing may be performed. The cooling rate for rapid cooling is preferably 10 ° C./min or more.

製造過程においてCu−Sn合金層を加熱処理によって形成する場合、表面めっき層の残留応力が緩和され、Sn結晶粒径が大きくなることにより、Sn層のウイスカ発生を抑制することができる。加熱処理時間は、長くなると生産性が低下するため、100〜600℃の温度で10分以下の処理をすることが望ましく、特に10分以下のリフロー処理が望ましい。Cu−Sn合金めっきを行った場合でも、加熱処理することにより、ウイスカ発生を抑制することができる。
表面めっき層について、Cuめっき層やSnめっき層がそれぞれCu合金、Sn合金からなる場合、合金めっき液からめっきすることもできるが、合金層厚が1.0μm以下の場合には、当該合金を構成する個々の元素を層状にめっきし、加熱拡散することにより合金化して当該合金からなるめっき層を得ることもできる。
When the Cu—Sn alloy layer is formed by a heat treatment in the manufacturing process, the residual stress of the surface plating layer is relaxed and the Sn crystal grain size is increased, thereby suppressing the occurrence of whisker in the Sn layer. When the heat treatment time is increased, the productivity is lowered. Therefore, it is desirable to perform the treatment for 10 minutes or less at a temperature of 100 to 600 ° C., and particularly the reflow treatment for 10 minutes or less. Even when Cu—Sn alloy plating is performed, whisker generation can be suppressed by heat treatment.
As for the surface plating layer, when the Cu plating layer and the Sn plating layer are made of Cu alloy and Sn alloy, respectively, it can be plated from an alloy plating solution, but when the alloy layer thickness is 1.0 μm or less, the alloy It is also possible to obtain a plating layer made of the alloy by plating each constituent element in a layer and alloying it by heat diffusion.

銅合金母材として表1に示す組成を有する厚さ0.3mmの板材を用い、その引張強さ、導電率及び硬度を測定した。その測定値を表2に示す。
各銅合金母材の表面に、Ni、Cu、Sn、又はCu、Ni、Cu、Sn(No.4,10)の順にめっきした。各めっきのめっき浴及びめっき条件を表3〜表5に示す。続いて、250℃×1分又は300℃×10秒の加熱処理を施してCu−Sn合金層を形成し、表1に示す表面めっき層を有する錫めっき銅合金材を得た。なお、加熱処理前のSnめっき層の一部とその下のCuめっき層はこの加熱処理により合金化し、Cu−Sn合金層を形成していた。加熱処理前のCuめっき層の厚さは加熱処理後のCu−Sn合金層の厚さのほぼ1/2、合金化に消費されたSnめっき層の厚さも加熱処理後のCu−Sn合金層の厚さのほぼ1/2であった。
As a copper alloy base material, a plate material having a thickness of 0.3 mm having the composition shown in Table 1 was used, and its tensile strength, electrical conductivity, and hardness were measured. The measured values are shown in Table 2.
The surface of each copper alloy base material was plated with Ni, Cu, Sn, or Cu, Ni, Cu, Sn (No. 4, 10) in this order. Tables 3 to 5 show plating baths and plating conditions for each plating. Then, the heat processing of 250 degreeC x 1 minute or 300 degreeC x 10 second was performed, the Cu-Sn alloy layer was formed, and the tin plating copper alloy material which has the surface plating layer shown in Table 1 was obtained. In addition, a part of Sn plating layer before heat processing and the Cu plating layer under it were alloyed by this heat processing, and the Cu-Sn alloy layer was formed. The thickness of the Cu plating layer before the heat treatment is almost ½ of the thickness of the Cu—Sn alloy layer after the heat treatment, and the thickness of the Sn plating layer consumed for alloying is also the Cu—Sn alloy layer after the heat treatment. The thickness was almost ½.

Figure 0004397245
Figure 0004397245

Figure 0004397245
Figure 0004397245

Figure 0004397245
Figure 0004397245

Figure 0004397245
Figure 0004397245

Figure 0004397245
Figure 0004397245

この錫めっき銅合金材を供試材として、表面めっき層を構成する各層の厚さを測定し、さらに摩擦係数、高温放置後の接触抵抗、耐食性(耐亜硫酸ガス)、成形加工性、及びボイド発生状況を測定した。その結果を表2に示す。
各測定試験の方法を下記に示す。
[引張強さ] JIS5号試験片を用い、JISZ2201に準拠して引張試験を行って測定した。
[導電率] JISH0505に準拠し、電気抵抗の測定はダブルブリッジを用いた。
[硬度] JISZ2244に準拠して測定した。
[Ni層及びSn層の厚さ] 蛍光X線膜厚計(セイコー電子工業株式会社;型式SFT156A)を用いて測定した。
[Cu層の厚さ] ミクロトーム法にて加工した供試材の断面をSEM観察し、画像解析処理により平均厚さとして算出した。
[Cu−Sn合金層の厚さ] p−ニトロフェノール及び苛性ソーダを成分とする剥離液に10分間浸漬し、最表面のSn層を除去した後、蛍光X線膜厚計を用いて測定した。
Using this tin-plated copper alloy material as a test material, the thickness of each layer constituting the surface plating layer was measured, and the friction coefficient, contact resistance after standing at high temperature, corrosion resistance (sulfurous acid resistance), molding processability, and voids The occurrence situation was measured. The results are shown in Table 2.
The method of each measurement test is shown below.
[Tensile Strength] Using a JIS No. 5 test piece, a tensile test was performed according to JISZ2201 and measured.
[Conductivity] In accordance with JISH0505, the electrical resistance was measured using a double bridge.
[Hardness] Measured according to JISZ2244.
[Thickness of Ni layer and Sn layer] The thickness was measured using a fluorescent X-ray film thickness meter (Seiko Electronics Co., Ltd .; model SFT156A).
[Thickness of Cu layer] The cross section of the specimen processed by the microtome method was observed with an SEM and calculated as an average thickness by image analysis processing.
[Thickness of Cu-Sn Alloy Layer] After immersing in a stripping solution containing p-nitrophenol and caustic soda as components for 10 minutes to remove the outermost Sn layer, the thickness was measured using a fluorescent X-ray film thickness meter.

[高温放置後のボイド発生状況] 供試材を160℃で120時間加熱後に、ミクロトーム法にて被覆層と銅合金素材界面の断面をSEM観察し、ボイド発生状況を確認した。ボイドが界面の50%以下(界面の長さの半分以下でボイドが発生)のレベルを○とし、50%を超えて認められるレベルを×と評価した。
[動摩擦係数] 嵌合型端子の接点部の形状を模擬し、図2に示すように、供試材から切り出した板状のオス試験片5を水平な台6に固定し、その上に供試材を内径1.5mmで半球加工したメス試験片7を置いてめっき面同士を接触させ、メス試験片に2.94Nの荷重(錘8)をかけてオス試験片5を押さえ、横型荷重測定器(アイコーエンジニアリング株式会社製Model−2152)を用いて、オス試験片5を摺動速度80mm/minで水平方向に引っ張り、そのときの最大摩擦力Fを測定した。摩擦係数を下記式(1)により求めた。なお、9はロードセル、矢印は摺動方向である。
摩擦係数=F/P・・・・(1)
摩擦係数が0.5以下のものを優れる、0.5を超えるものを劣ると評価した。
[Void Generation Condition after Leaving at High Temperature] After the test material was heated at 160 ° C. for 120 hours, the cross section of the interface between the coating layer and the copper alloy material was observed by SEM by a microtome method to confirm the void generation condition. The level at which voids were 50% or less of the interface (voids were generated when the interface length was less than half of the interface length) was evaluated as ◯, and the level recognized above 50% was evaluated as x.
[Dynamic Friction Coefficient] The shape of the contact portion of the fitting type terminal is simulated, and as shown in FIG. 2, a plate-shaped male test piece 5 cut out from the test material is fixed to a horizontal base 6 and provided thereon. Place the female test piece 7 hemispherically processed with an inner diameter of 1.5 mm, bring the plating surfaces into contact with each other, apply a load of 2.94 N (weight 8) to the female test piece, hold down the male test piece 5, and load horizontally Using a measuring instrument (Model-2152 manufactured by Aiko Engineering Co., Ltd.), the male test piece 5 was pulled in the horizontal direction at a sliding speed of 80 mm / min, and the maximum frictional force F at that time was measured. The coefficient of friction was determined by the following formula (1). In addition, 9 is a load cell and the arrow is a sliding direction.
Friction coefficient = F / P (1)
A friction coefficient of 0.5 or less was evaluated as excellent, and a coefficient exceeding 0.5 was evaluated as inferior.

[高温放置後の接触抵抗] 供試材を160℃で120時間大気中で加熱後に、接触抵抗を四端子法により、解放電圧20mV、電流10mA、無摺動の条件にて測定した。接触抵抗が3mΩ以下を特性が優れると評価した。
[成形加工性] 試験片を圧延方向が長手となるように切出し、JISH3110に規定されるW曲げ試験治具を用い、圧延方向に対して直角方向となるように9.8×10Nの荷重で曲げ加工を施した。その後、ミクロトーム法にて、断面を切出し、観察を行った。試験後の曲げ加工部に発生したクラックが銅合金母材へ伝播しないレベルを○と評価し、銅合金母材へ伝播し銅合金母材にクラックが発生するレベルを×と評価した。
[高温放置後の耐食性] 供試材を160℃で120時間加熱後に、亜硫酸ガス試験を25ppm、35℃、75%RH、96hrの条件で行った。試験後の供試材の断面を観察し、母材の腐食が認められないレベルを○とし、腐食が認められるレベルを×と評価した。
[Contact resistance after standing at high temperature] After heating the test material in the atmosphere at 160 ° C for 120 hours, the contact resistance was measured by a four-terminal method under the conditions of an open voltage of 20 mV, a current of 10 mA, and no sliding. A contact resistance of 3 mΩ or less was evaluated as having excellent characteristics.
[Molding workability] The test piece was cut out so that the rolling direction was long, and a W-bending test jig specified in JISH3110 was used, and the test piece was 9.8 × 10 3 N so as to be perpendicular to the rolling direction. Bending was performed with a load. Then, the cross section was cut out and observed by the microtome method. The level at which cracks that occurred in the bent part after the test did not propagate to the copper alloy base material was evaluated as ◯, and the level at which cracks occurred in the copper alloy base material and cracks occurred was evaluated as x.
[Corrosion resistance after standing at high temperature] After heating the sample material at 160 ° C for 120 hours, a sulfurous acid gas test was conducted under conditions of 25 ppm, 35 ° C, 75% RH, and 96 hours. The cross section of the test material after the test was observed, and the level at which corrosion of the base material was not recognized was evaluated as ◯, and the level at which corrosion was recognized was evaluated as ×.

表1,2をみると、銅合金母材の組成と表面めっき層構成が適切なNo.1〜7はいずれも、動摩擦係数、加熱後の接触抵抗と耐食性及び成形加工性に優れ、かつ加熱後のボイド発生が抑えられている。
一方、表面めっき層構成が不足しているNo.8〜11は加熱後の接触抵抗が高く、Sn層の厚さが規定値を超えるNo.17は摩擦係数が高く、Ni層が厚いNo.15とCu−Sn合金層が厚いNo.16は成形加工性が劣る。また、銅合金母材の組成がNi及びZnを含まないNo.12、Znを含まないNo.14、Si含有量の高いNo.13は、ボイドが多く発生していた。
Tables 1 and 2 show that the composition of the copper alloy base material and the surface plating layer configuration are appropriate . All of Nos. 1 to 7 are excellent in the dynamic friction coefficient, the contact resistance and corrosion resistance after heating, and the moldability, and the generation of voids after heating is suppressed.
On the other hand, no. Nos. 8 to 11 have high contact resistance after heating, and the thickness of the Sn layer exceeds the specified value. No. 17 has a high coefficient of friction and a thick Ni layer. No. 15 and the Cu—Sn alloy layer is thick. No. 16 is inferior in moldability. Moreover, the composition of the copper alloy base material is No. which does not contain Ni and Zn. 12, no Zn. 14, No. with high Si content. No. 13 had many voids.

ボイドが発生した錫めっき銅合金材の断面の概念図である。It is a conceptual diagram of the cross section of the tin plating copper alloy material which the void generate | occur | produced. 動摩擦係数の測定方法を示す概念図である。It is a conceptual diagram which shows the measuring method of a dynamic friction coefficient.

符号の説明Explanation of symbols

3 ボイド
5 オス試験片
6 台
7 メス試験片
8 錘
9 ロードセル
3 Void 5 Male test piece 6 units 7 Female test piece
8 spindles 9 load cells

Claims (10)

Ni:0.5%以上(質量%、以下同じ)、9%以下、Sn:0.01%以上、5%以下、Zn:0.001%以上、1.0%以下を含有し、残部Cuと不純物からなり、導電率20%IACS以上の銅合金母材表面に、Ni層及びCu−Sn合金層からなる表面めっき層がこの順に形成されていることを特徴とする電気・電子部品用錫めっき銅合金材。 Ni: 0.5% or more (mass%, the same shall apply hereinafter), 9% or less , Sn: 0.01 % or more, 5% or less , Zn: 0.001 % or more, 1.0% or less , and the balance Cu A surface plating layer comprising a Ni layer and a Cu—Sn alloy layer is formed in this order on the surface of a copper alloy base material having a conductivity of 20% IACS or more. Plating copper alloy material. 前記銅合金母材表面に、Ni層及びCu−Sn合金層と、さらにSn層からなる表面めっき層がこの順に形成されていることを特徴とする請求項1に記載された電気・電子部品用錫めっき銅合金材。 2. The electric / electronic component according to claim 1, wherein a Ni plating layer, a Cu—Sn alloy layer, and a surface plating layer including a Sn layer are formed in this order on the surface of the copper alloy base material. Tin-plated copper alloy material. Ni層の厚さが0.1〜1.0μm、Cu−Sn合金層の厚さが0.1〜1.0μmであることを特徴とする請求項1に記載された電気・電子部品用錫めっき銅合金材。 2. The tin for electric / electronic parts according to claim 1, wherein the Ni layer has a thickness of 0.1 to 1.0 [mu] m, and the Cu-Sn alloy layer has a thickness of 0.1 to 1.0 [mu] m. Plating copper alloy material. Ni層の厚さが0.1〜1.0μm、Cu−Sn合金層の厚さが0.1〜1.0μm、Sn層の厚さが3.0μm以下であることを特徴とする請求項2に記載された電気・電子部品用錫めっき銅合金材。 The Ni layer has a thickness of 0.1 to 1.0 µm, the Cu-Sn alloy layer has a thickness of 0.1 to 1.0 µm, and the Sn layer has a thickness of 3.0 µm or less. 2. Tin-plated copper alloy material for electric and electronic parts described in 2. 前記表面めっき層として、前記銅合金母材とNi層の間にCu層が形成されていることを特徴とする請求項1〜4のいずれかに記載された電気・電子部品用錫めっき銅合金材。 5. The tin-plated copper alloy for electrical and electronic parts according to claim 1, wherein a Cu layer is formed between the copper alloy base material and the Ni layer as the surface plating layer. Wood. 前記銅合金母材が、さらにP:0.0001〜0.05%とSi:0.0001〜1%のいずれか一方又は双方を含有することを特徴とする請求項1〜5のいずれかに記載された電気・電子部品用錫めっき銅合金材。 The copper alloy base material further contains one or both of P: 0.0001 to 0.05% and Si: 0.0001 to 1%. The tin-plated copper alloy material for electrical and electronic parts described. 前記銅合金母材が、さらにMn、Cr、Mg、Be、Al、Ca、Ti、V、Fe、Co、Zr、Nb、Mo、Ag、In、Pb、Hf、Ta、B、S、C、Se、Te、Sbの1種又は2種以上を総量で3%以下含むことを特徴とする請求項1〜6のいずれかに記載された電気・電子部品用錫めっき銅合金材。 The copper alloy base material is further Mn, Cr, Mg, Be, Al, Ca, Ti, V, Fe, Co, Zr, Nb, Mo, Ag, In, Pb, Hf, Ta, B, S, C, The tin-plated copper alloy material for electrical / electronic parts according to any one of claims 1 to 6, comprising 1% or more of Se, Te, and Sb in a total amount of 3% or less. Ni、Fe及びTiの合計質量をaとし、PとSiの合計質量をbとしたとき、両者の質量比a/bが3.5以上であることを特徴とする請求項1〜7のいずれかに記載された電気・電子部品用錫めっき銅合金材。 The mass ratio a / b of both is 3.5 or more, where the total mass of Ni, Fe and Ti is a, and the total mass of P and Si is b. A tin-plated copper alloy material for electric and electronic parts as described above. 前記請求項1,6〜8のいずれかに記載された組成を有し、導電率20%IACS以上の銅合金母材表面に、Niめっき層、Cuめっき層、Snめっき層をこの順に形成した後、100〜600℃の温度で10分以下の加熱処理を行い、Cuめっき層とSnめっき層を合金化して、前記銅合金母材表面にNi層、Cu−Sn合金層がこの順に形成された表面めっき層、又はNi層、Cu−Sn合金層、Sn層がこの順に形成された表面めっき層を形成することを特徴とする電気・電子部品用錫めっき銅合金材の製造方法。 A Ni plating layer, a Cu plating layer, and a Sn plating layer are formed in this order on the surface of a copper alloy base material having the composition described in any one of claims 1 to 6 and having an electrical conductivity of 20% IACS or more. Thereafter, heat treatment is performed at a temperature of 100 to 600 ° C. for 10 minutes or less to alloy the Cu plating layer and the Sn plating layer, and the Ni layer and the Cu—Sn alloy layer are formed in this order on the surface of the copper alloy base material. A method for producing a tin-plated copper alloy material for electric / electronic parts, comprising forming a surface plating layer or a surface plating layer in which a Ni layer, a Cu-Sn alloy layer, and a Sn layer are formed in this order. 前記Cu合金母材表面とNiめっき層の間にCuめっき層を形成することを特徴とする請求項9に記載された電気・電子部品用錫めっき銅合金材の製造方法。 The method for producing a tin-plated copper alloy material for electric / electronic parts according to claim 9, wherein a Cu plating layer is formed between the surface of the Cu alloy base material and the Ni plating layer.
JP2004034282A 2004-02-10 2004-02-10 Tin-plated copper alloy material for electric and electronic parts and method for producing the same Expired - Fee Related JP4397245B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2004034282A JP4397245B2 (en) 2004-02-10 2004-02-10 Tin-plated copper alloy material for electric and electronic parts and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2004034282A JP4397245B2 (en) 2004-02-10 2004-02-10 Tin-plated copper alloy material for electric and electronic parts and method for producing the same

Publications (2)

Publication Number Publication Date
JP2005226097A JP2005226097A (en) 2005-08-25
JP4397245B2 true JP4397245B2 (en) 2010-01-13

Family

ID=35001045

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2004034282A Expired - Fee Related JP4397245B2 (en) 2004-02-10 2004-02-10 Tin-plated copper alloy material for electric and electronic parts and method for producing the same

Country Status (1)

Country Link
JP (1) JP4397245B2 (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007039789A (en) * 2005-03-29 2007-02-15 Nikko Kinzoku Kk Cu-Ni-Si-Zn-Sn BASED ALLOY STRIP EXCELLENT IN THERMAL PEELING RESISTANCE OF TIN PLATING, AND TIN PLATED STRIP THEREOF
JP2007063624A (en) * 2005-08-31 2007-03-15 Nikko Kinzoku Kk Copper alloy tinned strip having excellent insertion/withdrawal property and heat resistance
JP4538424B2 (en) * 2006-03-29 2010-09-08 日鉱金属株式会社 Cu-Zn-Sn alloy tin-plated strip
JP4934785B2 (en) * 2006-03-31 2012-05-16 Dowaメタルテック株式会社 Sn-plated copper alloy material and manufacturing method thereof
JP2007291459A (en) * 2006-04-26 2007-11-08 Nikko Kinzoku Kk TINNED STRIP OF Cu-Sn-P-BASED ALLOY
JP2007314859A (en) * 2006-05-29 2007-12-06 Nikko Kinzoku Kk Cu-Zn ALLOY STRIP WITH EXCELLENT RESISTANCE TO THERMAL PEELING OF Sn PLATING, AND Sn-PLATED STRIP THEREOF
JP5019596B2 (en) * 2007-06-29 2012-09-05 古河電気工業株式会社 Printed wiring board and printed circuit board
JP5311860B2 (en) * 2008-03-28 2013-10-09 株式会社神戸製鋼所 Copper alloy plate with Sn plating for PCB male terminals with excellent Pb-free solderability
CN101831566B (en) * 2010-06-10 2012-03-21 吉林大学 Method for preparing composite membrane for improving oxidation resistance of copper lead of integrated circuit
JP5278630B1 (en) * 2012-01-26 2013-09-04 三菱マテリアル株式会社 Tin-plated copper alloy terminal material excellent in insertion / extraction and manufacturing method thereof
WO2016031654A1 (en) * 2014-08-25 2016-03-03 株式会社神戸製鋼所 Conductive material for connection parts which has excellent minute slide wear resistance
JP5897084B1 (en) * 2014-08-27 2016-03-30 株式会社神戸製鋼所 Conductive material for connecting parts with excellent resistance to fine sliding wear
CN104513913B (en) * 2014-11-13 2016-08-24 无锡信大气象传感网科技有限公司 Sensor high strength copper alloy material
JP2019002056A (en) * 2017-06-19 2019-01-10 古河電気工業株式会社 Metallic material
JP7214451B2 (en) * 2018-02-13 2023-01-30 株式会社栗本鐵工所 Copper alloy
CN115011837B (en) * 2022-05-25 2023-02-03 江苏圣欣光电科技有限公司 Corrosion-resistant and oxidation-resistant tin-plated layer alloy wire, preparation method and application thereof in aerospace cable assembly

Also Published As

Publication number Publication date
JP2005226097A (en) 2005-08-25

Similar Documents

Publication Publication Date Title
JP4090302B2 (en) Conductive material plate for forming connecting parts
JP3880877B2 (en) Plated copper or copper alloy and method for producing the same
JP4397245B2 (en) Tin-plated copper alloy material for electric and electronic parts and method for producing the same
JP4538813B2 (en) Connector and charging socket using copper-based alloy material
US20180301838A1 (en) Copper alloy sheet with sn coating layer for a fitting type connection terminal and a fitting type connection terminal
JP6052829B2 (en) Copper alloy material for electrical and electronic parts
JP4413992B2 (en) Copper alloy sheet for electrical and electronic parts
JP4934785B2 (en) Sn-plated copper alloy material and manufacturing method thereof
JP6173943B2 (en) Copper alloy strip with surface coating layer with excellent heat resistance
JP3824884B2 (en) Copper alloy material for terminals or connectors
JP4522970B2 (en) Cu-Zn alloy heat resistant Sn plating strip with reduced whisker
JP5950499B2 (en) Copper alloy for electrical and electronic parts and copper alloy material with Sn plating
JP4090483B2 (en) Conductive connection parts
JP4756195B2 (en) Cu-Ni-Sn-P copper alloy
JP2007092173A (en) Cu-Ni-Si-Zn BASED ALLOY TINNED STRIP
JP5897084B1 (en) Conductive material for connecting parts with excellent resistance to fine sliding wear
JP4247256B2 (en) Cu-Zn-Sn alloy tin-plated strip
JPH07126779A (en) Copper-base alloy and its production
JP4090488B2 (en) Conductive material plate for connecting part forming process and manufacturing method thereof
JP6219553B2 (en) Plating material excellent in heat resistance and method for producing the same
JP7060514B2 (en) Conductive strip
JP5226032B2 (en) Cu-Zn alloy heat resistant Sn plating strip with reduced whisker
JP5367271B2 (en) Rolled plate
JP4566082B2 (en) Copper alloy plate for pre-plated electrical wiring connection
JP4570948B2 (en) Sn-plated strip of Cu-Zn alloy with reduced whisker generation and method for producing the same

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20060925

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20080618

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20090721

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20090917

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20091020

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20091020

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20121030

Year of fee payment: 3

R150 Certificate of patent or registration of utility model

Ref document number: 4397245

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20131030

Year of fee payment: 4

LAPS Cancellation because of no payment of annual fees