JP5715399B2 - Copper alloy material for electrical and electronic parts - Google Patents
Copper alloy material for electrical and electronic parts Download PDFInfo
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本発明は、例えば半導体リードフレームやコネクタ端子などの電気・電子部品の材料として用いられる電気・電子部品用銅合金材に関するものである。 The present invention relates to a copper alloy material for electrical / electronic components used as a material for electrical / electronic components such as semiconductor lead frames and connector terminals.
携帯電話やノートパソコンなどに使用される半導体パッケージの実装には、はんだを使用した接合を用いることが一般的に行われている。従来では、はんだは、Sn・Pb共晶系のものが主流であったが、近年においては、Pbが有害物質として規制され、従来よりもSn濃度が高い鉛フリーはんだが広く用いられるようになった。 For mounting a semiconductor package used in a mobile phone or a notebook computer, it is a common practice to use a solder joint. Conventionally, Sn / Pb eutectic solder has been the mainstream, but in recent years Pb is regulated as a harmful substance, and lead-free solder having a higher Sn concentration than before has been widely used. It was.
こうした半導体パッケージにおいては、小型化・薄型化が進んでいる。リードフレームにはより薄い板厚の材料が使用されており、それに伴って強度の高い材料が求められている。こうしたリードフレームに用いられる銅合金材料としては、FeおよびPを含有するCu−Fe−P系合金がある(例えば、特許文献1参照。)。 Such semiconductor packages are becoming smaller and thinner. A material having a thinner plate thickness is used for the lead frame, and accordingly, a material having high strength is required. As a copper alloy material used for such a lead frame, there is a Cu—Fe—P alloy containing Fe and P (see, for example, Patent Document 1).
その代表的な一例としては、例えばFe:2.1〜2.6質量%、P:0.015〜0.15質量%、Zn:0.05〜0.2質量%含有する銅合金(C19400)が標準的な合金として広く知られている。この合金は、熱処理することで銅の母相中にFe、あるいはFe−P化合物を析出させ、それにより導電性、熱伝導性や強度のそれぞれを同時に向上させるという利点を有している。 As a typical example, for example, a copper alloy containing Fe: 2.1 to 2.6 mass%, P: 0.015 to 0.15 mass%, and Zn: 0.05 to 0.2 mass% (C19400). ) Is widely known as a standard alloy. This alloy has the advantage that the heat treatment causes precipitation of Fe or Fe-P compounds in the copper matrix, thereby simultaneously improving the conductivity, thermal conductivity and strength.
従来、広く用いられてきたSn・Pb共晶はんだから鉛フリーはんだ化の進行に伴い、これまでにない問題が生じている。すなわち、大部分の鉛フリーはんだは、従来のSn・Pb共晶はんだに比べて融点が高い。そのため、鉛フリーはんだを使用することで部品接合時の加熱温度が従来よりも高温になる。 Conventionally, with the progress of lead-free soldering from Sn / Pb eutectic solder, which has been widely used, unprecedented problems have arisen. That is, most lead-free solders have a higher melting point than conventional Sn / Pb eutectic solders. Therefore, by using lead-free solder, the heating temperature at the time of joining the parts becomes higher than before.
電気・電子部品の組立工程において加熱が繰り返して行われる場合は、接合界面では高温であるがために材料中のCuと、はんだ中のSnの相互拡散が促進される。その結果、CuとSnの金属間化合物の形成、成長が従来以上に促進される。形成される金属間化合物は主に、Cu6Sn5とCu3Snである。特に、Cu3Snは脆い性質があり、接合界面での成長が進むと、はんだ接合の信頼性が大きく低下する。よって、はんだ接合の信頼性を高めるためには、この金属間化合物の成長を抑制することが重要なポイントになる。 When heating is repeatedly performed in the assembly process of the electric / electronic component, the interdiffusion between Cu in the material and Sn in the solder is promoted because of the high temperature at the bonding interface. As a result, formation and growth of an intermetallic compound of Cu and Sn are promoted more than ever. The intermetallic compounds that are formed are mainly Cu 6 Sn 5 and Cu 3 Sn. In particular, Cu 3 Sn has a brittle property, and as the growth at the joint interface proceeds, the reliability of the solder joint is greatly reduced. Therefore, in order to increase the reliability of solder bonding, it is important to suppress the growth of this intermetallic compound.
また、こうした材料に広く用いられているCu−Fe−P系合金に含まれるFeは、はんだ層への拡散速度が速く、CuとSnの金属間化合物の形成を助長する働きを持つ。よって、Cu−Fe−P系合金に含まれるFe量が多くなると、金属間化合物が成長しやすくなり、好ましくない。 In addition, Fe contained in Cu—Fe—P-based alloys widely used in such materials has a high diffusion rate into the solder layer and has a function of promoting the formation of an intermetallic compound of Cu and Sn. Therefore, when the amount of Fe contained in the Cu—Fe—P alloy increases, the intermetallic compound tends to grow, which is not preferable.
従って、本発明の目的は、金属間化合物の成長を安定して抑制することを可能とし、はんだ接合の信頼性を高めた電気・電子部品用銅合金材を提供することにある。 Accordingly, it is an object of the present invention to provide a copper alloy material for electric / electronic parts that can stably suppress the growth of intermetallic compounds and has improved solder joint reliability.
本発明者等が鋭意研究したところ、Fe、Ni、P、Zn、およびSnの含有量をある特定の範囲に規定するだけでは、金属間化合物の成長を安定して抑制するのには不十分であることを見いだした。本発明者等はさらに、金属間化合物の成長をより一層安定して抑制するための(Fe+Ni)/Pの質量比、Fe/Niの質量比、Zn/(Fe+Ni)の質量比、およびSn/(Fe+Ni)の質量比の関係を見いだし、本発明に至ったものである。 As a result of intensive studies by the present inventors, it is insufficient to stably suppress the growth of intermetallic compounds by merely defining the contents of Fe, Ni, P, Zn, and Sn within a specific range. I found out. The present inventors further have a mass ratio of (Fe + Ni) / P, a mass ratio of Fe / Ni, a mass ratio of Zn / (Fe + Ni), and Sn / The relationship of the mass ratio of (Fe + Ni) has been found and the present invention has been achieved.
すなわち、本発明は、0.05〜0.5質量%のFe、0.05〜0.5質量%のNi、0.02〜0.2質量%のP、0.1〜3質量%のZn、0.02〜0.3質量%のSnを含有し、それらの成分の質量比が(Fe+Ni)/P=3〜10、Fe/Ni=0.8〜1.2、Zn/(Fe+Ni)≧0.5、Sn/(Fe+Ni)≦0.5の関係にあり、残部がCuおよび不可避的不純物からなることを特徴とする電気・電子部品用銅合金材にある。 That is, the present invention includes 0.05 to 0.5 mass% Fe, 0.05 to 0.5 mass% Ni, 0.02 to 0.2 mass% P, and 0.1 to 3 mass%. Zn, containing 0.02 to 0.3% by mass of Sn, and the mass ratio of these components is (Fe + Ni) / P = 3 to 10, Fe / Ni = 0.8 to 1.2, Zn / (Fe + Ni ) ≧ 0.5, Sn / (Fe + Ni) ≦ 0.5, and the balance is made of copper and inevitable impurities, and is in a copper alloy material for electric / electronic parts.
本発明はさらに、0.05〜0.5質量%のFe、0.05〜0.5質量%のNi、0.02〜0.2質量%のP、0.1〜3質量%Zn、0.02〜0.3質量%のSnを含有し、それらの成分の質量比が(Fe+Ni)/P=3〜10、Fe/Ni=0.8〜1.2、Zn/(Fe+Ni)≧0.5、Sn/(Fe+Ni)≦0.5の関係にあり、さらにZr、Cr、Tiから選択された1種以上の成分を合計0.03〜1質量%含有し、残部がCuおよび不可避的不純物からなることを特徴とする電気・電子部品用銅合金材を提供する。 The present invention further includes 0.05 to 0.5 mass% Fe, 0.05 to 0.5 mass% Ni, 0.02 to 0.2 mass% P, 0.1 to 3 mass% Zn, 0.02 to 0.3% by mass of Sn, and the mass ratio of these components is (Fe + Ni) / P = 3 to 10, Fe / Ni = 0.8 to 1.2, Zn / (Fe + Ni) ≧ 0.5, Sn / (Fe + Ni) ≦ 0.5, further containing one or more components selected from Zr, Cr, Ti in total of 0.03 to 1% by mass, with the balance being Cu and inevitable Provided is a copper alloy material for electric and electronic parts, characterized by comprising a general impurity.
本発明によれば、高い強度と導電性を併せ持つとともに、はんだ接合において安定した接合品質を保持することが可能となる。 According to the present invention, it is possible to have both high strength and conductivity and to maintain stable joint quality in solder joint.
以下、本発明の好適な実施の形態を具体的に説明する。 Hereinafter, preferred embodiments of the present invention will be specifically described.
この実施の形態に係る電気・電子部品用の銅合金材は、例えば半導体パッケージのリードフレームの材料として好適に用いられる。 The copper alloy material for electric / electronic parts according to this embodiment is suitably used as a material for a lead frame of a semiconductor package, for example.
(銅合金の成分)
この実施の形態である銅合金は、0.05〜0.5質量%のFe、0.05〜0.5質量%のNi、0.02〜0.2質量%のP、0.1〜3質量%のZn、0.02〜0.3質量%のSnを含有し、残部がCuおよび不可避的不純物からなる銅合金をベースの材料とする。このような銅合金の組成によって、従来のCu−Fe−P系合金よりも優れた強度を持つとともに、強度と導電性をバランス良く兼備した材料を得ることができる。
(Copper alloy components)
The copper alloy according to this embodiment includes 0.05 to 0.5% by mass of Fe, 0.05 to 0.5% by mass of Ni, 0.02 to 0.2% by mass of P, 0.1 to A copper alloy containing 3% by mass of Zn and 0.02 to 0.3% by mass of Sn with the balance being Cu and inevitable impurities is used as a base material. With such a composition of the copper alloy, it is possible to obtain a material having a strength superior to that of a conventional Cu—Fe—P alloy and having a balance between strength and conductivity.
このNiおよびFeは、Pと一緒に添加することでP化合物を形成して材料中に分散析出し、材料の良好な導電率を維持しながら、強度を向上させる働きを有する。 Ni and Fe are added together with P to form a P compound and disperse and precipitate in the material, thereby improving the strength while maintaining good electrical conductivity of the material.
Pの添加量を0.02質量%未満にすると、十分な量のP化合物を形成することができず、満足できる強度が得られない。一方、Pの添加量が0.2質量%を超えて添加されると、鋳造時や熱間加工時にP化合物の偏析に起因する割れが起こりやすくなるので好ましくない。よって、Pの組成範囲を0.02〜0.2質量%の範囲に規定することが好適である。 If the addition amount of P is less than 0.02% by mass, a sufficient amount of P compound cannot be formed, and satisfactory strength cannot be obtained. On the other hand, it is not preferable that the amount of P added exceeds 0.2% by mass because cracking due to segregation of the P compound easily occurs during casting or hot working. Therefore, it is preferable to define the composition range of P in the range of 0.02 to 0.2% by mass.
このPの組成範囲に対して効果的に化合物を形成させ、高強度と高導電性をバランス良く両立させるためには、Feの組成範囲を0.05〜0.5質量%、Niの組成範囲を0.05〜0.5質量%に規定する必要がある。FeおよびNiの含有量が上記組成範囲の下限を下回る場合は、P化合物の形成量が不十分になり、強度が不足する。一方、FeおよびNiの含有量が上記組成範囲の上限を超える場合は、余剰のFe、NiがCu中に固溶して導電率を低下させる。 In order to effectively form a compound with respect to the composition range of P and achieve both high strength and high conductivity in a balanced manner, the composition range of Fe is 0.05 to 0.5% by mass, the composition range of Ni. Needs to be specified to be 0.05 to 0.5 mass%. When the content of Fe and Ni is below the lower limit of the composition range, the amount of P compound formed becomes insufficient and the strength is insufficient. On the other hand, when the content of Fe and Ni exceeds the upper limit of the above composition range, excess Fe and Ni are dissolved in Cu to lower the conductivity.
Znは、はんだとの接合界面において境界部分に濃縮し、CuおよびSnの相互拡散の障害となって金属間化合物の形成、成長を抑制する効果を持つ。Znはまた、強度の向上効果を持つとともに、電子部品材料として必要とするはんだ濡れ性、Snめっき密着性、および耐マイグレーション性の改善にも大きな効果がある。 Zn is concentrated at the boundary portion at the joint interface with the solder, and has an effect of inhibiting the interdiffusion of Cu and Sn and suppressing the formation and growth of intermetallic compounds. Zn also has an effect of improving strength, and also has a great effect in improving solder wettability, Sn plating adhesion, and migration resistance required as an electronic component material.
Znが0.1質量%の規定範囲より少ない含有量では、はんだ層との界面に濃縮してCuの拡散を阻害する効果が小さくなり、3質量%の規定範囲を超えて含有すると、導電率の低下などの悪影響が生じるので好ましくない。 When the Zn content is less than the specified range of 0.1% by mass, the effect of concentrating at the interface with the solder layer and inhibiting the diffusion of Cu is reduced. Adverse effects such as lowering of the temperature are undesirable.
Snは、強度向上に有効な働きを持つ。Snが0.02質量%の規定範囲より少ない含有量では、強度を向上させる効果が小さくなり、0.3質量%の規定範囲を超えて含有すると、導電率の低下などの悪影響が生じるとともに、はんだ層との界面で金属間化合物を過剰に成長させるので好ましくない。 Sn has an effective function for improving the strength. When the content of Sn is less than the specified range of 0.02% by mass, the effect of improving the strength is reduced. When the content exceeds the specified range of 0.3% by mass, adverse effects such as a decrease in conductivity occur. Since the intermetallic compound grows excessively at the interface with the solder layer, it is not preferable.
ところで、Fe、Ni、P、Zn、およびSnを含有する銅合金の組成だけでは、安定して金属間化合物の成長を抑えるには不十分である。この実施の形態の基本の構成は、(Fe+Ni)/Pの質量比、Fe/Niの質量比、Zn/(Fe+Ni)の質量比、およびSn/(Fe+Ni)の質量比を特定の範囲に規定することで、金属間化合物の成長を安定して抑制できることを見出したことにある。それらの質量比としては、(Fe+Ni)/P=3〜10、Fe/Ni=0.8〜1.2、Zn/(Fe+Ni)≧0.5、およびSn/(Fe+Ni)≦0.5を満足することが肝要である。 By the way, the composition of the copper alloy containing Fe, Ni, P, Zn, and Sn alone is insufficient to stably suppress the growth of the intermetallic compound. The basic configuration of this embodiment is that the mass ratio of (Fe + Ni) / P, the mass ratio of Fe / Ni, the mass ratio of Zn / (Fe + Ni), and the mass ratio of Sn / (Fe + Ni) are specified in specific ranges. Thus, it has been found that the growth of the intermetallic compound can be stably suppressed. As mass ratios thereof, (Fe + Ni) / P = 3 to 10, Fe / Ni = 0.8 to 1.2, Zn / (Fe + Ni) ≧ 0.5, and Sn / (Fe + Ni) ≦ 0.5 Satisfaction is essential.
(Fe+Ni)/P=3〜10、およびFe/Ni=0.8〜1.2の範囲に規定することで、導電率を低下させるCu中の固溶元素量を抑えながら、析出物の分散による強度の向上を効果的に利用して、導電率および強度を好ましいバランスで兼備した材料を得ることができる。 Dispersion of precipitates while suppressing the amount of solid solution elements in Cu, which lowers the conductivity, by defining in the range of (Fe + Ni) / P = 3 to 10 and Fe / Ni = 0.8 to 1.2 By effectively utilizing the strength improvement due to the above, it is possible to obtain a material having a favorable balance of conductivity and strength.
(Fe+Ni)/Pの質量比が3未満になる場合は、化合物形成時にPが過剰になり、(Fe+Ni)/Pの質量比が10を超える場合は、逆にFe、Niが過剰になる。このような過剰成分は、Cu中に固溶状態で存在するため、導電率を害する結果となるので好ましくない。より好ましくは、過剰成分をより少なくするため、(Fe+Ni)/P=3〜6の範囲を選択することが望ましい。 When the mass ratio of (Fe + Ni) / P is less than 3, P becomes excessive during compound formation, and when the mass ratio of (Fe + Ni) / P exceeds 10, conversely, Fe and Ni become excessive. Such an excess component is not preferable because it exists in a solid solution state in Cu and results in a deterioration of electrical conductivity. More preferably, it is desirable to select a range of (Fe + Ni) / P = 3-6 in order to reduce excess components.
FeとNiは、強度と導電率に対して同様の効果を期待して添加するものである。しかしながら、Feのみを添加したCu−Fe−P系合金では、低強度、高導電率の特性になりやすく、逆にNiだけの添加では、高強度、低導電率の特性になりやすい。よって、強度と導電率のバランスが良い材料を得るためには、FeとNiを組み合わせて添加することが有効である。その配合比率を検討した結果、ほぼ1対1の比率で添加することで、望ましい特性が得られることが分かった。そこで実用上に支障がない範囲としては、FeとNiの質量比をFe/Ni=0.8〜1.2に規定する。 Fe and Ni are added in anticipation of the same effect on strength and conductivity. However, Cu—Fe—P based alloys to which only Fe is added tend to have low strength and high conductivity characteristics. Conversely, addition of Ni alone tends to have high strength and low conductivity characteristics. Therefore, in order to obtain a material having a good balance between strength and conductivity, it is effective to add Fe and Ni in combination. As a result of examining the blending ratio, it was found that desirable characteristics can be obtained by adding at a ratio of about 1: 1. Therefore, as a range where there is no practical problem, the mass ratio of Fe and Ni is defined as Fe / Ni = 0.8 to 1.2.
また、Zn/(Fe+Ni)の質量比を0.5以上に規定することで、金属間化合物の成長を促進する効果を持つFeとNiに対して一定以上の割合で成長抑制効果を持つZnが添加されることになり、総合的に金属間化合物の成長を抑えることができる。また、Zn/(Fe+Ni)の質量比を0.5以上に規定することで、適正量のSnを添加することが可能になる。 Further, by defining the mass ratio of Zn / (Fe + Ni) to 0.5 or more, Zn having an effect of suppressing growth at a certain ratio or more with respect to Fe and Ni having an effect of promoting the growth of intermetallic compounds. As a result, the growth of intermetallic compounds can be suppressed comprehensively. In addition, by defining the mass ratio of Zn / (Fe + Ni) to 0.5 or more, an appropriate amount of Sn can be added.
Zn/(Fe+Ni)の質量比が0.5未満になる場合は、はんだ層との界面においてZn成分の濃縮が不十分となり、CuとSnの相互拡散に対する阻害効果が小さいために、金属間化合物の成長抑制効果が十分に得られないので好ましくない。 When the mass ratio of Zn / (Fe + Ni) is less than 0.5, the concentration of the Zn component is insufficient at the interface with the solder layer, and the interdiffusion effect of Cu and Sn is small, so the intermetallic compound This is not preferable because the growth suppressing effect cannot be sufficiently obtained.
一方、Sn/(Fe+Ni)の質量比が0.5を超える場合は、適正な(Fe+Ni)量に対してSn量が多くなるため、はんだ層との界面において金属間化合物の成長が促進されるので好ましくない。 On the other hand, when the mass ratio of Sn / (Fe + Ni) exceeds 0.5, the amount of Sn increases with respect to the appropriate amount of (Fe + Ni), so that the growth of the intermetallic compound is promoted at the interface with the solder layer. Therefore, it is not preferable.
Snは、過剰に添加すると、金属間化合物の成長を促進する働きをする。しかしながら、添加量が少ないと、強度向上の効果も少ない。Sn/(Fe+Ni)の質量比を0.5以下の範囲に規定することで、適正量のSnを添加することができる。 When Sn is added excessively, it functions to promote the growth of intermetallic compounds. However, when the addition amount is small, the effect of improving the strength is also small. By defining the mass ratio of Sn / (Fe + Ni) in the range of 0.5 or less, an appropriate amount of Sn can be added.
以上より、Fe、Ni、P、Zn、Snを含有する銅合金の組成成分の質量比を特定することで、金属間化合物の成長を安定して抑制することができるようになる。 From the above, by specifying the mass ratio of the composition components of the copper alloy containing Fe, Ni, P, Zn, and Sn, the growth of the intermetallic compound can be stably suppressed.
(銅合金の副成分)
この実施の形態に係る銅合金はさらに、Zr、Cr、およびTiから選択された1種以上の成分を合計0.03質量%〜1質量%の範囲で添加してもよい。これらのZr、Cr、およびTiの元素は、強度の向上に効果的に働くとともに、耐熱性を向上させて高温下での強度低下を防ぐ作用を持つ。金属間化合物の成長を安定して抑制する良好な特性をより一層期待することができる。
(Subcomponent of copper alloy)
The copper alloy according to this embodiment may further contain one or more components selected from Zr, Cr, and Ti in a total range of 0.03% by mass to 1% by mass. These elements of Zr, Cr, and Ti effectively work to improve the strength, and have an action of improving the heat resistance and preventing the strength from being lowered at a high temperature. Good characteristics that stably suppress the growth of intermetallic compounds can be further expected.
ZrとCrは、強度や耐熱性を向上させる働きを持つとともに、導電率に与える悪影響が比較的少ないことを特徴とする副成分である。ただし、含有量が多すぎると、鋳造性の悪化などの悪影響が生じる。Tiにあっても、強度や耐熱性を向上させる効果に優れた副成分である。 Zr and Cr are subcomponents that have the function of improving strength and heat resistance and have relatively little adverse effect on conductivity. However, when there is too much content, bad influences, such as deterioration of castability, will arise. Even if it is in Ti, it is a subcomponent excellent in the effect of improving strength and heat resistance.
これらのZr、Cr、およびTiの元素は、単独もしくは組み合わせて添加することで、金属間化合物の成長を安定して抑制するという効果を期待することができる。しかしながら、その合計含有量が1質量%を超えると、導電率の低下や鋳造性の悪化などの悪影響が顕著になるので好ましくない。よって、Zr、Cr、およびTiの合計の組成範囲としては、1質量%以下に規定することが好ましい。 By adding these elements of Zr, Cr, and Ti alone or in combination, an effect of stably suppressing the growth of the intermetallic compound can be expected. However, if the total content exceeds 1% by mass, adverse effects such as a decrease in conductivity and a deterioration in castability become remarkable, which is not preferable. Therefore, the total composition range of Zr, Cr, and Ti is preferably specified to be 1% by mass or less.
(実施の形態の効果)
上記実施の形態に係る銅合金は、以下の効果を有する。
(1)従来のCu−Fe−P系合金に比べて、より優れた強度を持ち、導電性においても良好な特性を維持する。
(2)はんだ接合後に界面に生じる金属間化合物の成長を抑制して接合部の脆化を防止し、鉛フリーはんだを使用した実装において良好な接合品質を有する特徴を持つ。
(3)このような材料は、リードフレームとして最適であり、特に、半導体パッケージなどの電気・電子部品について、安価で高特性の材料を供給するように材料面から支え、その発展に大きく寄与することができる。
(Effect of embodiment)
The copper alloy according to the above embodiment has the following effects.
(1) Compared to conventional Cu-Fe-P alloys, it has superior strength and maintains good characteristics in terms of conductivity.
(2) It has the characteristics of suppressing the growth of intermetallic compounds generated at the interface after solder bonding and preventing the brittleness of the joint, and having good joint quality in mounting using lead-free solder.
(3) Such a material is optimal as a lead frame. In particular, electrical and electronic parts such as semiconductor packages are supported from the material side so as to supply inexpensive and high-performance materials, and contribute greatly to their development. be able to.
以下に、表1および2を参照しながら、本発明の更に具体的な実施の形態として、実施例1〜13(試料No.1〜13)および比較例1〜13(試料No.1〜13)を挙げて詳細に説明する。なお、この実施例では、上記実施の形態の典型的な一例を挙げており、本発明は、これらの実施例および比較例に限定されるものではないことは勿論である。 Below, referring to Tables 1 and 2, as more specific embodiments of the present invention, Examples 1 to 13 (Sample Nos. 1 to 13) and Comparative Examples 1 to 13 (Sample Nos. 1 to 13) ) Will be described in detail. In addition, in this Example, the typical example of the said embodiment is given and, of course, this invention is not limited to these Examples and a comparative example.
下記の表1は、実施例1〜13、および比較例1〜13として用いた試料の組成および質量比を、下記の表2は、実施例1〜13、および比較例1〜13の特性値をそれぞれ示す。 Table 1 below shows the compositions and mass ratios of the samples used as Examples 1 to 13 and Comparative Examples 1 to 13, and Table 2 below shows the characteristic values of Examples 1 to 13 and Comparative Examples 1 to 13. Respectively.
[実施例1]
無酸素銅を母材にして、Fe:0.2質量%、Ni:0.2質量%、P:0.1質量%、Zn:0.4質量%、Sn:0.1質量%を含有した銅合金素材を高周波溶解炉で溶製し、厚さ25mm、幅30mm、長さ150mmのインゴットに鋳造した。これを950℃に加熱して厚さ8mmまで熱間圧延した後、厚さ2mmに冷間圧延して450℃で1分間焼鈍した。さらに、これを厚さ0.25mmに冷間圧延して450℃で1分間焼鈍することにより、表1の実施例1に示す銅合金を製作した。
[Example 1]
Using oxygen-free copper as a base material, Fe: 0.2 mass%, Ni: 0.2 mass%, P: 0.1 mass%, Zn: 0.4 mass%, Sn: 0.1 mass% The resulting copper alloy material was melted in a high frequency melting furnace and cast into an ingot having a thickness of 25 mm, a width of 30 mm, and a length of 150 mm. This was heated to 950 ° C. and hot-rolled to a thickness of 8 mm, then cold-rolled to a thickness of 2 mm and annealed at 450 ° C. for 1 minute. Further, this was cold-rolled to a thickness of 0.25 mm and annealed at 450 ° C. for 1 minute to produce a copper alloy shown in Example 1 of Table 1.
以上のように製作した実施例1の銅合金について、引張強さ、伸び、導電率の各特性値を測定した。その結果、引張強さ612MPa、伸び10%、導電率64%IACSという本発明の目的に適合する良好な特性を得ることができた。 About the copper alloy of Example 1 manufactured as mentioned above, each characteristic value of tensile strength, elongation, and electrical conductivity was measured. As a result, it was possible to obtain good characteristics suitable for the purpose of the present invention, such as tensile strength of 612 MPa, elongation of 10%, and conductivity of 64% IACS.
さらに、実施例1の試料No.1を脱脂酸洗した後、溶融したSn−3質量%Ag−0.5質量%Cuはんだ中に浸漬して、試料No.1の両面にはんだを塗布した。これを200℃に保持した恒温槽に入れて、1時間加熱を施した。加熱後の試料No.1を樹脂に埋め込んで切断し、断面の観察を行い、樹脂材料とはんだとの間の界面部分に形成されたCu−Sn金属間化合物層の厚みを測定した。そして、金属間化合物層の内部や界面における欠陥(クラック、ボイド)の有無を観察した。その結果、金属間化合物層は4μmと薄く、クラックやボイドなどの欠陥も見られなかった。 Furthermore, sample No. 1 in Example 1 was used. 1 was degreased and pickled, and then immersed in molten Sn-3 mass% Ag-0.5 mass% Cu solder. Solder was applied to both sides of 1. This was put into a thermostat kept at 200 ° C. and heated for 1 hour. Sample No. after heating 1 was embedded in the resin and cut, the cross-section was observed, and the thickness of the Cu—Sn intermetallic compound layer formed at the interface between the resin material and the solder was measured. And the presence or absence of the defect (a crack, a void) in the inside of an intermetallic compound layer or an interface was observed. As a result, the intermetallic compound layer was as thin as 4 μm, and no defects such as cracks and voids were observed.
[実施例2〜13]
次に、表1に示す組成を有する試料No.2〜13(実施例2〜13)の銅合金を溶解鋳造し、上記実施例1と同じ工程で加工熱処理を行い、厚さ0.25mmの試料を製作した。これらの試料No.2〜13についても、上記実施例1と同様の方法で引張強さ、伸び、および導電率の各特性値を測定するとともに、はんだを塗布して加熱した時の金属間化合物層の厚みと欠陥の有無を調査した。
[Examples 2 to 13]
Next, Sample No. having the composition shown in Table 1 was used. Copper alloys of 2 to 13 (Examples 2 to 13) were melt cast and subjected to thermomechanical treatment in the same process as in Example 1 to produce a sample having a thickness of 0.25 mm. These sample Nos. As for 2 to 13, while measuring each characteristic value of tensile strength, elongation, and conductivity in the same manner as in Example 1, the thickness and defects of the intermetallic compound layer when solder was applied and heated The presence or absence of was investigated.
各実施例2〜13における銅合金の特性を表2にまとめて示す。表2から明らかなように、実施例2〜13のいずれも、60%IACSを超える高い導電率と、600MPaを超える高強度を併せ持っており、薄型パッケージのリードフレームとして十分な導電性と強度を有する銅合金が得られた。また、はんだとの界面における金属間化合物層も薄くなり、クラックやボイドなどの欠陥も見られず、実施例2〜13のいずれも、本発明の目的に適合した良好な特性を兼備していることが確認できた。 The characteristics of the copper alloys in Examples 2 to 13 are summarized in Table 2. As is clear from Table 2, each of Examples 2 to 13 has both high conductivity exceeding 60% IACS and high strength exceeding 600 MPa, and has sufficient conductivity and strength as a lead frame for a thin package. A copper alloy was obtained. In addition, the intermetallic compound layer at the interface with the solder is also thinned, and defects such as cracks and voids are not seen, and all of Examples 2 to 13 have good characteristics suitable for the purpose of the present invention. I was able to confirm.
[比較例]
次に、上記実施の形態に係る銅合金の組成の限定理由を、比較例を挙げて説明する。
[Comparative example]
Next, the reason for limiting the composition of the copper alloy according to the above embodiment will be described with reference to a comparative example.
表1に示す組成を有する比較例1〜13(試料No.1〜13)の銅合金を溶解鋳造し、上記実施例1と同じ工程で加工熱処理を行い、厚さ0.25mmの試料No.1〜13を製作した。 The copper alloys of Comparative Examples 1 to 13 (Sample Nos. 1 to 13) having the compositions shown in Table 1 were melt-cast and subjected to thermomechanical processing in the same process as in Example 1 above. 1-13 were produced.
得られた比較例の試料No.1〜13について、上記実施例1と同様の方法で引張強さ、伸び、および導電率の各特性値を測定するとともに、はんだを塗布して加熱した時の金属間化合物層の厚みと欠陥の有無を調査した。比較例1〜13における銅合金の特性を表2にまとめて示す。 Sample No. of Comparative Example obtained was obtained. About 1-13, while measuring each characteristic value of tensile strength, elongation, and electrical conductivity by the method similar to the said Example 1, the thickness and defect of an intermetallic compound layer when apply | coating and heating a solder The presence or absence was investigated. The characteristics of the copper alloys in Comparative Examples 1 to 13 are summarized in Table 2.
[比較例1および2]
比較例の試料No.1およびNo.2は、表1に示すように、Fe、Ni、およびPの添加量が上記実施の形態に係る銅合金成分の規定範囲から外れたものである。比較例の試料No.1は、Fe、Ni、およびP成分の添加量が低すぎる一例である。この場合は、表2から明らかなように、上記実施例に比べて引張強さが低く、十分な強度が得られない結果となった。
[Comparative Examples 1 and 2]
Sample No. of Comparative Example 1 and no. As shown in Table 1, the addition amount of Fe, Ni, and P deviates from the specified range of the copper alloy component according to the above embodiment. Sample No. of Comparative Example 1 is an example in which the amount of Fe, Ni, and P component added is too low. In this case, as apparent from Table 2, the tensile strength was lower than that of the above example, and sufficient strength could not be obtained.
一方、比較例の試料No.2は、表1に示すように、Fe、Ni、およびPの添加量が多すぎる一例である。この場合は、表2から明らかなように、上記実施例に比べて導電率が低くなるとともに、伸びの値が低くなった。伸びの低い材料は、リードフレームの曲げ加工で割れが発生しやすくなることから、本発明の目的を満足させることはできない。 On the other hand, Sample No. As shown in Table 1, 2 is an example in which the added amounts of Fe, Ni, and P are too large. In this case, as is clear from Table 2, the conductivity was lower than that of the above example, and the elongation value was lower. A material with low elongation cannot easily satisfy the object of the present invention because cracking is likely to occur in the lead frame bending process.
[比較例3および4]
比較例の試料No.3およびNo.4は、表1に示すように、(Fe+Ni)/Pの質量比が上記実施の形態に係る銅合金成分の規定範囲から外れた一例である。表2から明らかなように、FeとNiが過剰になった場合も、Pが過剰になった場合も、上記実施例に比べて導電率が低下する結果となった。また、引張強さについてみても、上記実施例に比べて低い値となった。
[Comparative Examples 3 and 4]
Sample No. of Comparative Example 3 and no. As shown in Table 1, 4 is an example in which the mass ratio of (Fe + Ni) / P deviates from the specified range of the copper alloy component according to the above embodiment. As is clear from Table 2, both Fe and Ni were excessive and P was excessive, resulting in a decrease in conductivity compared to the above examples. Also, the tensile strength was lower than that in the above example.
[比較例5および6]
比較例の試料No.5およびNo.6は、表1に示すように、Fe/Niの質量比が上記実施の形態に係る銅合金成分の規定範囲から外れた一例である。表2から明らかなように、Feの比率が高すぎる比較例の試料No.5は、上記実施例に比べて引張強さが不足する結果となった。Niの比率が高すぎる比較例の試料No.6は、上記実施例に比べて導電率が低くなった。
[Comparative Examples 5 and 6]
Sample No. of Comparative Example 5 and no. As shown in Table 1, 6 is an example in which the mass ratio of Fe / Ni deviates from the specified range of the copper alloy component according to the above embodiment. As is apparent from Table 2, the sample No. of the comparative example in which the ratio of Fe is too high. No. 5 resulted in insufficient tensile strength compared to the above example. Sample No. of the comparative example in which the ratio of Ni is too high. 6 had a lower conductivity than the above example.
[比較例7および8]
比較例の試料No.7およびNo.8は、表1に示すように、Znの添加量、またはZn/(Fe+Ni)の質量比が上記実施の形態に係る銅合金成分の規定範囲から外れた一例である。Znの添加量が少なく、Zn/(Fe+Ni)の質量比が不足する比較例の試料No.7は、表2から明らかなように、Znによる金属間化合物層の成長抑制効果が不十分であり、金属間化合物層が厚く成長した。また、材料と金属間化合物層の界面にボイドが観察されており、はんだ接合の信頼性が不十分であった。Znの添加量が多すぎる比較例の試料No.8は、上記実施例に比べて導電率が悪化した。
[Comparative Examples 7 and 8]
Sample No. of Comparative Example 7 and no. As shown in Table 1, 8 is an example in which the addition amount of Zn or the mass ratio of Zn / (Fe + Ni) deviates from the specified range of the copper alloy component according to the above embodiment. Sample No. of Comparative Example in which the amount of Zn added is small and the mass ratio of Zn / (Fe + Ni) is insufficient. As is clear from Table 2, the effect of suppressing the growth of the intermetallic compound layer by Zn was insufficient, and the intermetallic compound layer grew thick. In addition, voids were observed at the interface between the material and the intermetallic compound layer, and the reliability of solder bonding was insufficient. Sample No. in Comparative Example in which the added amount of Zn is too large. In Example 8, the conductivity was deteriorated compared to the above example.
[比較例9および10]
比較例の試料No.9およびNo.10は、表1に示すように、Snの添加量、またはSn/(Fe+Ni)の質量比が上記実施の形態に係る銅合金成分の規定範囲から外れ、Snが過剰に添加された一例である。表2から明らかなように、試料No.9およびNo.10のいずれも、上記実施例に比べて導電率が低下するとともに、はんだ界面の金属間化合物層が厚く成長した。また、材料と金属間化合物層の界面にボイドが観察され、はんだ接合の信頼性が不十分であった。
[Comparative Examples 9 and 10]
Sample No. of Comparative Example 9 and no. As shown in Table 1, No. 10 is an example in which the addition amount of Sn or the mass ratio of Sn / (Fe + Ni) is out of the specified range of the copper alloy component according to the above embodiment, and Sn is added excessively. . As apparent from Table 2, the sample No. 9 and no. In all cases, the conductivity decreased as compared with the above example, and the intermetallic compound layer at the solder interface grew thick. In addition, voids were observed at the interface between the material and the intermetallic compound layer, and the reliability of solder bonding was insufficient.
[比較例11〜13]
比較例の試料No.11〜13は、表1に示すように、副成分として添加したZr、Cr、およびTiの添加量が上記実施の形態に係る銅合金成分の規定範囲から外れ、過剰になった一例である。この場合は、表2から明らかなように、上記実施例に比べて導電率が悪化するとともに、伸びも大きく低下しており、曲げ加工などの加工性が悪化する問題が生じる。
[Comparative Examples 11 to 13]
Sample No. of Comparative Example As shown in Table 1, 11 to 13 are examples in which the added amounts of Zr, Cr, and Ti added as subcomponents deviated from the specified range of the copper alloy component according to the above embodiment and became excessive. In this case, as is clear from Table 2, the conductivity is deteriorated as compared with the above examples, and the elongation is also greatly reduced, which causes a problem that workability such as bending is deteriorated.
以上より、上記実施の形態に係る銅合金で規定した組成範囲、および質量比を外れた上記比較例のいずれもが、上記各実施例に比べて不十分な特性しか得られないということが分かった。 From the above, it can be seen that any of the composition examples defined by the copper alloy according to the above embodiment and the above comparative examples that deviate from the mass ratio can provide only insufficient properties compared to the above examples. It was.
上記実施例に係る銅合金によると、従来の銅合金に比べて良好な強度、導電率を維持しつつ、鉛フリーはんだを使用した接合において安定した接合品質を保持することができた。こうした特性は、小型化が進む電気・電子機器に有効に活用できるものであり、設計の自由度を大幅に広げることができる。また、製造コストの面でも、上記実施例に係る銅合金は、従来の銅合金と同等のコストで製造することが可能であり、実用上の問題とはならない。 According to the copper alloy according to the above example, it was possible to maintain stable bonding quality in bonding using lead-free solder while maintaining good strength and conductivity as compared with the conventional copper alloy. Such characteristics can be effectively utilized for electrical and electronic devices that are becoming smaller in size, and can greatly increase the degree of freedom in design. Also, in terms of manufacturing cost, the copper alloy according to the above embodiment can be manufactured at a cost equivalent to that of the conventional copper alloy, which is not a practical problem.
Claims (2)
0.05〜0.5質量%のFe、0.05〜0.5質量%のNi、0.02〜0.2質量%のP、0.1〜3質量%のZn、0.02〜0.3質量%のSnを含有し、それらの成分の質量比が(Fe+Ni)/P=3〜10、Fe/Ni=0.8〜1.2、Zn/(Fe+Ni)≧0.5、Sn/(Fe+Ni)≦0.5の関係にあり、残部がCuおよび不可避的不純物からなり、
前記電気・電子部品用銅合金材を溶融したSn−3質量%Ag−0.5質量%Cuはんだ中に浸漬し、当該Sn−3質量%Ag−0.5質量%Cuはんだが両面に塗布された前記電気・電子部品用銅合金材を200℃に保持した恒温槽に入れ、1時間加熱を施したときに、前記Sn−3質量%Ag−0.5質量%Cuはんだと前記電気・電子部品用銅合金材との界面に形成されるCu−Sn金属間化合物層の厚みが4μm以下であることを特徴とする電気・電子部品用銅合金材(ただし、Cu−0.20質量%Fe−0.18質量%Ni−0.09質量%Sn−0.082質量%P−0.30質量%Znからなる電気・電子部品用銅合金材、Cu−0.3質量%Fe−0.3質量%Ni−0.3質量%Sn−0.15質量%P−0.5質量%Znからなる電気・電子部品用銅合金材、及びCu−0.4質量%Fe−0.4質量%Ni−0.3質量%Sn−0.18質量%P−0.5質量%Znからなる電気・電子部品用銅合金材は除く。)。 A copper alloy material for electrical and electronic parts used for joining using lead-free solder containing Sn,
0.05-0.5 mass% Fe, 0.05-0.5 mass% Ni, 0.02-0.2 mass% P, 0.1-3 mass% Zn, 0.02- 0.3% by mass of Sn, and the mass ratio of these components is (Fe + Ni) / P = 3 to 10, Fe / Ni = 0.8 to 1.2, Zn / (Fe + Ni) ≧ 0.5, Sn / (Fe + Ni) ≦ 0.5, the balance being made of Cu and inevitable impurities,
The copper alloy material for electric / electronic parts is immersed in a molten Sn-3 mass% Ag-0.5 mass% Cu solder, and the Sn-3 mass% Ag-0.5 mass% Cu solder is applied on both sides. The obtained copper alloy material for electric / electronic parts was put in a thermostat kept at 200 ° C., and when heated for 1 hour, the Sn-3 mass% Ag-0.5 mass% Cu solder and the electric / electronic components were The thickness of the Cu—Sn intermetallic compound layer formed at the interface with the copper alloy material for electronic parts is 4 μm or less. The copper alloy material for electric and electronic parts (however, Cu−0.20 mass%) Fe-0.18 mass% Ni-0.09 mass% Sn-0.082 mass% P-0.30 mass% Copper alloy material for electric and electronic parts made of Zn , Cu-0.3 mass% Fe-0 .3% by mass Ni-0.3% by mass Sn-0.15% by mass P-0.5% by mass Z electric and electronic parts for the copper alloy material consisting of n,及 Beauty Cu-0.4 wt% Fe-0.4 wt% Ni-0.3 wt% Sn-0.18 mass% P-0.5 wt% Zn (Excluding copper alloy materials for electrical and electronic parts.)
0.05〜0.5質量%のFe、0.05〜0.5質量%のNi、0.02〜0.2質量%のP、0.1〜3質量%Zn、0.02〜0.3質量%のSnを含有し、それらの成分の質量比が(Fe+Ni)/P=3〜10、Fe/Ni=0.8〜1.2、Zn/(Fe+Ni)≧0.5、Sn/(Fe+Ni)≦0.5の関係にあり、さらにZr、Cr、Tiから選択された1種以上の成分を合計0.03〜1質量%含有し、残部がCuおよび不可避的不純物からなり、
前記電気・電子部品用銅合金材を溶融したSn−3質量%Ag−0.5質量%Cuはんだ中に浸漬し、当該Sn−3質量%Ag−0.5質量%Cuはんだが両面に塗布された前記電気・電子部品用銅合金材を200℃に保持した恒温槽に入れ、1時間加熱を施したときに、前記Sn−3質量%Ag−0.5質量%Cuはんだと前記電気・電子部品用銅合金材との界面に形成されるCu−Sn金属間化合物層の厚みが4μm以下であることを特徴とする電気・電子部品用銅合金材(ただし、Cu−0.20質量%Fe−0.18質量%Ni−0.09質量%Sn−0.082質量%P−0.30質量%Znからなる電気・電子部品用銅合金材、Cu−0.3質量%Fe−0.3質量%Ni−0.3質量%Sn−0.15質量%P−0.5質量%Znからなる電気・電子部品用銅合金材、及びCu−0.4質量%Fe−0.4質量%Ni−0.3質量%Sn−0.18質量%P−0.5質量%Znからなる電気・電子部品用銅合金材は除く。)。
A copper alloy material for electrical and electronic parts used for joining using lead-free solder containing Sn,
0.05 to 0.5 mass% Fe, 0.05 to 0.5 mass% Ni, 0.02 to 0.2 mass% P, 0.1 to 3 mass% Zn, 0.02 to 0 .3% by mass of Sn, and the mass ratio of these components is (Fe + Ni) / P = 3 to 10, Fe / Ni = 0.8 to 1.2, Zn / (Fe + Ni) ≧ 0.5, Sn /(Fe+Ni)≦0.5, further containing one or more components selected from Zr, Cr and Ti in a total amount of 0.03 to 1% by mass, with the balance consisting of Cu and inevitable impurities,
The copper alloy material for electric / electronic parts is immersed in a molten Sn-3 mass% Ag-0.5 mass% Cu solder, and the Sn-3 mass% Ag-0.5 mass% Cu solder is applied on both sides. The obtained copper alloy material for electric / electronic parts was put in a thermostat kept at 200 ° C., and when heated for 1 hour, the Sn-3 mass% Ag-0.5 mass% Cu solder and the electric / electronic components were The thickness of the Cu—Sn intermetallic compound layer formed at the interface with the copper alloy material for electronic parts is 4 μm or less. The copper alloy material for electric and electronic parts (however, Cu−0.20 mass%) Fe-0.18 mass% Ni-0.09 mass% Sn-0.082 mass% P-0.30 mass% Copper alloy material for electric and electronic parts made of Zn , Cu-0.3 mass% Fe-0 .3% by mass Ni-0.3% by mass Sn-0.15% by mass P-0.5% by mass Z electric and electronic parts for the copper alloy material consisting of n,及 Beauty Cu-0.4 wt% Fe-0.4 wt% Ni-0.3 wt% Sn-0.18 mass% P-0.5 wt% Zn (Excluding copper alloy materials for electrical and electronic parts.)
Priority Applications (2)
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JP5475914B1 (en) * | 2012-09-28 | 2014-04-16 | Jx日鉱日石金属株式会社 | Copper alloy sheet with excellent heat dissipation and repeated bending workability |
CN103088229B (en) * | 2012-11-06 | 2015-04-15 | 北京有色金属研究总院 | Low-cost copper alloy for socket connectors and processing method thereof |
JP5572753B2 (en) * | 2012-12-26 | 2014-08-13 | 三菱マテリアル株式会社 | Copper alloy for electronic and electrical equipment, copper alloy sheet for electronic and electrical equipment, conductive parts and terminals for electronic and electrical equipment |
JP5572754B2 (en) * | 2012-12-28 | 2014-08-13 | 三菱マテリアル株式会社 | Copper alloy for electronic and electrical equipment, copper alloy sheet for electronic and electrical equipment, conductive parts and terminals for electronic and electrical equipment |
JP5417523B1 (en) * | 2012-12-28 | 2014-02-19 | 三菱マテリアル株式会社 | Copper alloy for electronic and electrical equipment, copper alloy sheet for electronic and electrical equipment, conductive parts and terminals for electronic and electrical equipment |
JP5417539B1 (en) * | 2013-01-28 | 2014-02-19 | 三菱マテリアル株式会社 | Copper alloy for electronic and electrical equipment, copper alloy sheet for electronic and electrical equipment, conductive parts and terminals for electronic and electrical equipment |
JP5604549B2 (en) * | 2013-03-18 | 2014-10-08 | 三菱マテリアル株式会社 | Copper alloy for electronic and electrical equipment, copper alloy sheet for electronic and electrical equipment, conductive parts and terminals for electronic and electrical equipment |
JP5501495B1 (en) * | 2013-03-18 | 2014-05-21 | 三菱マテリアル株式会社 | Copper alloy for electronic and electrical equipment, copper alloy sheet for electronic and electrical equipment, conductive parts and terminals for electronic and electrical equipment |
CN103667770B (en) * | 2013-11-27 | 2015-11-11 | 余姚市士森铜材厂 | A kind of precipitation hardenable copper alloy |
CN103667775B (en) * | 2013-11-27 | 2016-04-13 | 余姚市士森铜材厂 | A kind of Copper alloy semiconductor lead frame |
CN103643076B (en) * | 2013-11-27 | 2016-01-06 | 余姚市士森铜材厂 | A kind of preparation method of precipitation hardenable copper alloy |
CN105063418B (en) * | 2015-07-24 | 2017-04-26 | 宁波金田铜业(集团)股份有限公司 | Preparation method of low-alloying copper belt |
CN105220007A (en) * | 2015-10-29 | 2016-01-06 | 安徽鑫科新材料股份有限公司 | A kind of high-strength copper ferrophosphor(us) and production method thereof |
JP6579264B2 (en) * | 2016-04-15 | 2019-09-25 | 株式会社村田製作所 | Semiconductor package manufacturing method and Cu alloy cutting method |
CN106011522A (en) * | 2016-08-03 | 2016-10-12 | 苏州市虎丘区浒墅关弹簧厂 | High elasticity copper alloy material for springs |
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JPH1112714A (en) * | 1997-06-25 | 1999-01-19 | Dowa Mining Co Ltd | Copper and copper base alloy excellent in direct bonding property and soldering property and production thereof |
JP2005029826A (en) * | 2003-07-10 | 2005-02-03 | Hitachi Cable Ltd | Method for manufacturing copper alloy foil for electronic component |
JP3807387B2 (en) * | 2003-07-31 | 2006-08-09 | 日立電線株式会社 | Copper alloy for terminal / connector and manufacturing method thereof |
JP2008024995A (en) * | 2006-07-21 | 2008-02-07 | Kobe Steel Ltd | Copper alloy plate for electrical/electronic component having excellent heat resistance |
JP4157898B2 (en) * | 2006-10-02 | 2008-10-01 | 株式会社神戸製鋼所 | Copper alloy sheet for electrical and electronic parts with excellent press punchability |
JP4197717B2 (en) * | 2006-10-05 | 2008-12-17 | 株式会社神戸製鋼所 | Copper alloy plate for electrical and electronic parts with excellent plating properties |
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 |
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