JP2012201905A - Co-Si BASED COPPER ALLOY SHEET - Google Patents
Co-Si BASED COPPER ALLOY SHEET Download PDFInfo
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 36
- 229910020711 Co—Si Inorganic materials 0.000 title claims abstract description 29
- 238000005096 rolling process Methods 0.000 claims abstract description 46
- 230000003746 surface roughness Effects 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 7
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- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
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- 229910052748 manganese Inorganic materials 0.000 claims description 4
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Abstract
Description
本発明は、Co-Si系銅合金板に関する。 The present invention relates to a Co—Si based copper alloy sheet.
コネクタ等の電気・電子機器の小型化が要求されており、強度に優れたCo-Si系銅合金（コルソン合金）が開発されている。ところで、Co-Si系のコルソン合金はＣｏとＳｉから析出物を生成させるために高温での溶体化や時効処理を必要とし、その表面に強固な酸化皮膜が形成され、はんだ濡れ性を劣化させる。又、コルソン合金においては、最終圧延後に歪取焼鈍を行う場合もあるため、酸化皮膜がさらに成長する。このため、最終熱処理後に酸洗して酸化皮膜を溶解させ、さらにバフ研磨によって酸化皮膜を除去することが行われている（以下、適宜「酸洗バフ研磨」という）。
このようなことから、表面粗度をＲａを０．２μｍ以下、かつＲｔを２μｍ以下に規定し、はんだ濡れ性を向上させた銅合金材料が開発されている（特許文献１）。
又、上記した酸洗バフ研磨を行うと、バフによる畝状の凹凸が表面に生じてはんだ濡れ性を低下させることから、仕上げ圧延前に酸洗又は脱脂処理を施し、はんだ濡れ性を向上させた銅合金材料が開発されている（特許文献２）。仕上げ圧延前に酸洗又は脱脂処理を行うと、表面の凹凸成分を表す度数分布図におけるピーク位置が、粗さ曲線のための平均線（度数分布図におけるゼロの位置）よりプラス側（凸成分）に現れ、はんだ濡れ性やめっき性が向上するとされる。
Miniaturization of electrical and electronic devices such as connectors is required, and Co-Si based copper alloys (Corson alloys) with excellent strength have been developed. By the way, the Co-Si-based Corson alloy requires solution treatment and aging treatment at high temperature to generate precipitates from Co and Si, and a strong oxide film is formed on the surface, which deteriorates solder wettability. . In the Corson alloy, since the stress relief annealing may be performed after the final rolling, the oxide film further grows. For this reason, pickling is performed after the final heat treatment to dissolve the oxide film, and further, the oxide film is removed by buffing (hereinafter referred to as “pickling buff polishing” as appropriate).
For this reason, a copper alloy material having a surface roughness Ra of 0.2 μm or less and Rt of 2 μm or less and improved solder wettability has been developed (Patent Document 1).
Also, when the above pickling buffing is performed, wrinkle-like irregularities due to the buff are generated on the surface and the solder wettability is lowered. Copper alloy materials have been developed (Patent Document 2). When pickling or degreasing treatment is performed before finish rolling, the peak position in the frequency distribution diagram representing the surface irregularity component is on the plus side (convex component) from the average line for the roughness curve (zero position in the frequency distribution diagram) ) Appears to improve solder wettability and plating properties.
しかしながら、特許文献１記載の技術の場合、はんだ濡れ性が良好であっても材料表面の酸化皮膜が取りきれていなかったり、最終圧延前に酸洗，研磨を行っているため，圧延で異物が押し込まれた場合に、ピンホール（部分的にはんだが付着しない領域）が発生する。ピンホールが多くなると半田付け不良が生じ易く、特にコルソン合金を端子に成形したときのはんだ付け部分にピンホールが生じると半田付け不良となる。
又、特許文献２記載の技術の場合、仕上げ圧延前に酸洗又は脱脂処理が必要となることから工程が複雑となり、生産性に劣る。又、Co−Si系のコルソン合金の酸化皮膜は非常に堅固なため、酸洗だけでは落ちにくいが、特許文献２記載の技術は熱処理後に酸洗のみを行い研磨を行わない工程、又は酸洗と研磨を行わない工程であるため、材料表面の酸化皮膜が十分に取りきれていないと考えられ、ピンホールが生じ易い。
すなわち、本発明は上記の課題を解決するためになされたものであり、はんだ濡れ性に優れ、かつ半田付けの際のピンホールが少ないCo-Si系銅合金板の提供を目的とする。
However, in the case of the technique described in Patent Document 1, even if the solder wettability is good, the oxide film on the surface of the material is not completely removed, or pickling and polishing are performed before the final rolling. When it is pushed in, a pinhole (a region where solder does not partially adhere) is generated. If the number of pinholes increases, soldering defects are likely to occur. In particular, if a pinhole is generated in a soldered portion when a Corson alloy is formed on a terminal, soldering defects occur.
In the case of the technique described in Patent Document 2, pickling or degreasing treatment is required before finish rolling, resulting in a complicated process and poor productivity. In addition, since the oxide film of the Co-Si-based Corson alloy is very firm, it is difficult to remove by pickling alone. However, the technique described in Patent Document 2 is a process in which only pickling is performed after heat treatment and polishing is not performed, or pickling. Therefore, it is considered that the oxide film on the surface of the material is not sufficiently removed, and pinholes are likely to occur.
That is, the present invention has been made to solve the above-described problems, and an object thereof is to provide a Co—Si based copper alloy plate having excellent solder wettability and few pinholes during soldering.
本発明者らは種々検討した結果、最終熱処理後の酸洗バフ研磨を、比較的目（研磨砥粒）の細かいバフを用いて十分な回数行うことにより、材料表面の酸化皮膜や、圧延により押し込まれた異物を除去すると共に、表面を所定の異方性をもった平滑面とすることにより、はんだ濡れ性に優れ、かつピンホールが低減することを見出した。
上記の目的を達成するために、本発明のCo-Si系銅合金板は、Co：0.5〜3.0質量％、Si：0.1〜1.0質量％を含有し残部がCu及び不可避不純物からなるCo-Si系銅合金板であって、(圧延平行方向の表面粗さRa(RD)/圧延直角方向の表面粗さRa(TD))≦0.8である。
As a result of various studies, the present inventors have conducted pickling buff polishing after the final heat treatment a sufficient number of times using a buff having a relatively fine eye (abrasive grains), thereby allowing an oxide film on the surface of the material or rolling. It has been found that by removing the pushed-in foreign matter and making the surface a smooth surface having a predetermined anisotropy, the solder wettability is excellent and pinholes are reduced.
In order to achieve the above object, the Co—Si based copper alloy plate of the present invention contains Co: 0.5 to 3.0 mass%, Si: 0.1 to 1.0 mass%, and the balance is Co—Si consisting of Cu and inevitable impurities. A copper alloy sheet, wherein (surface roughness Ra (RD) in the direction parallel to rolling / surface roughness Ra (TD) in the direction perpendicular to rolling) ≦ 0.8.
又、本発明のCo-Si系銅合金板は、Co：0.5〜3.0質量％、Si：0.1〜1.0質量％を含有し残部がCu及び不可避不純物からなるCo-Si系銅合金板であって、(圧延平行方向の表面粗さRz(RD)/圧延直角方向の表面粗さRz(TD))≦0.8である。 The Co—Si based copper alloy sheet of the present invention is a Co—Si based copper alloy sheet containing Co: 0.5 to 3.0 mass%, Si: 0.1 to 1.0 mass%, and the balance being Cu and inevitable impurities. (Surface roughness Rz (RD) in the rolling parallel direction / Surface roughness Rz (TD) in the direction perpendicular to the rolling) ≦ 0.8.
請求項１記載のCo-Si系銅合金板において、圧延平行方向の表面粗さRa(RD)≦0.07μmであることが好ましい。 In the Co—Si based copper alloy sheet according to claim 1, it is preferable that the surface roughness Ra (RD) ≦ 0.07 μm in the rolling parallel direction.
請求項２記載のCo-Si系銅合金板において、圧延平行方向の表面粗さRz(RD)≦0.50μmであることが好ましい。 In the Co—Si-based copper alloy sheet according to claim 2, it is preferable that the surface roughness Rz (RD) ≦ 0.50 μm in the rolling parallel direction.
圧延直角方向の表面の凹凸成分を表す度数分布図におけるピーク位置が、粗さ曲線のための平均線よりマイナス側（凹成分側）にあることが好ましい。
さらに、Ｍｎ、Ｆｅ、Ｍｇ、Ｎｉ、Ｃｒ、Ｖ、Ｎｂ、Ｍｏ、Ｚｒ、Ｂ、Ａｇ、Ｂｅ、Ｚｎ、Ｓｎ、ミッシュメタル及びＰからなる群から選択される１種又は２種以上を、２．０質量％以下含有することが好ましい。
It is preferable that the peak position in the frequency distribution diagram representing the concavo-convex component on the surface in the direction perpendicular to the rolling is on the minus side (concave component side) from the average line for the roughness curve.
Further, one or more selected from the group consisting of Mn, Fe, Mg, Ni, Cr, V, Nb, Mo, Zr, B, Ag, Be, Zn, Sn, Misch metal, and P are selected from 2 It is preferable to contain 0.0 mass% or less.
本発明によれば、はんだ濡れ性に優れ、かつ半田付けの際のピンホールが少ないCo-Si系銅合金板が得られる。 According to the present invention, a Co—Si based copper alloy plate having excellent solder wettability and few pinholes during soldering can be obtained.
以下、本発明の実施形態に係るCo-Si系銅合金板について説明する。なお、本発明において％とは、特に断らない限り、質量％を示すものとする。
又、表面粗さＲａとは、ＪＩＳ−Ｂ０６０１（２００１年）に規格する中心線平均粗さであり、表面粗さＲｚとは、同ＪＩＳに規格する最大高さである。
Hereinafter, the Co—Si based copper alloy plate according to the embodiment of the present invention will be described. In the present invention, “%” means “% by mass” unless otherwise specified.
The surface roughness Ra is the centerline average roughness specified in JIS-B0601 (2001), and the surface roughness Rz is the maximum height specified in the JIS.
まず、図１を参照して、本発明の技術思想について説明する。図１は本発明の実施形態に係るCo-Si系銅合金板の製造工程の一例を示す。
まず、最終熱処理後の銅合金板２を酸洗槽４に導入して酸洗すると、圧延平行方向（ＲＤ）及び圧延直角方向（ＴＤ）にほぼ均一に酸化皮膜が溶解して減肉される。このため、酸洗後の圧延平行方向の表面粗さＲａ（ＲＤ）及び圧延直角方向の表面粗さＲａ（ＴＤ）はほぼ同一であり、これらの比｛Ｒａ（ＲＤ）／Ｒａ（ＴＤ）｝≒１となる（図１（ａ）参照）。
First, the technical idea of the present invention will be described with reference to FIG. FIG. 1 shows an example of a manufacturing process of a Co—Si based copper alloy sheet according to an embodiment of the present invention.
First, when the copper alloy plate 2 after the final heat treatment is introduced into the pickling tank 4 and pickled, the oxide film dissolves and is thinned substantially uniformly in the rolling parallel direction (RD) and the rolling perpendicular direction (TD). . For this reason, the surface roughness Ra (RD) in the rolling parallel direction after pickling and the surface roughness Ra (TD) in the direction perpendicular to the rolling are substantially the same, and their ratio {Ra (RD) / Ra (TD)} ≈1 (see FIG. 1A).
次に、バフ６を用いて酸洗後の銅合金板を研磨すると、バフによる研磨目の傷が付く。バフ６の回転方向である圧延平行方向（ＲＤ）においては、材料表面の研磨が進むに従って、酸洗で溶けきらなかった酸化皮膜が材料表面から無くなるため、Ra（RD）が小さくなる。一方、圧延直角方向（ＴＤ）に材料表面の研磨が進んでも、ＴＤ方向の粗さはバフによる研磨目の粗さを測定することになり，バフによる研磨目の傷が付いた後には、Ｒａ（ＴＤ）は大きく変化しない。従って、｛Ｒａ（ＲＤ）／Ｒａ（ＴＤ）｝＜１となるが、｛Ｒａ（ＲＤ）／Ｒａ（ＴＤ）｝≦０．８になるとバフ研磨が進行して酸化皮膜が十分に除去され、はんだ濡れ性が向上し、かつ半田付けの際のピンホールが低減することが判明した。｛Ｒａ（ＲＤ）／Ｒａ（ＴＤ）｝の下限は特に規定されないが、実用的には０．１以上である。
なお、バフ６は円筒状であり、その表面に研磨砥粒が付着している。そして、バフ６を銅合金板２の通板方向（図１の左から右へ）と順方向に回転させることでバフ６の研磨砥粒が銅合金板２の表面を削るようになっている。従って、バフ研磨の進行による酸化皮膜の除去度合は、研磨砥粒の粒径（番手）、銅合金板２の通板回数、通板速度（ライン速度）、バフ６の回転数等によって調整することができる。
Next, if the copper alloy plate after pickling is polished using the buff 6, scratches on the polished eyes due to the buff are attached. In the rolling parallel direction (RD), which is the rotation direction of the buff 6, as the polishing of the surface of the material proceeds, the oxide film that could not be dissolved by pickling disappears from the surface of the material, so Ra (RD) decreases. On the other hand, even if the polishing of the surface of the material proceeds in the direction perpendicular to the rolling direction (TD), the roughness in the TD direction is to measure the roughness of the polishing eye due to the buff. (TD) does not change greatly. Therefore, {Ra (RD) / Ra (TD)} <1, but when {Ra (RD) / Ra (TD)} ≦ 0.8, buffing proceeds and the oxide film is sufficiently removed, It has been found that solder wettability is improved and pinholes during soldering are reduced. The lower limit of {Ra (RD) / Ra (TD)} is not particularly specified, but is practically 0.1 or more.
The buff 6 has a cylindrical shape, and abrasive grains are attached to the surface thereof. Then, the buff 6 is rotated in the forward direction of the copper alloy plate 2 (from left to right in FIG. 1) and the abrasive grains of the buff 6 scrape the surface of the copper alloy plate 2. . Therefore, the degree of removal of the oxide film due to the progress of the buffing is adjusted by the grain size (count) of the abrasive grains, the number of times of passing the copper alloy plate 2, the passing speed (line speed), the number of rotations of the buff 6, etc. be able to.
又、圧延平行方向の表面粗さＲａ（ＲＤ）が0.07μm以下であることが好ましい。Ｒａ（ＲＤ）が0.07μm以下の場合、ゼロクロスタイムが小さくなる場合がある。 The surface roughness Ra (RD) in the rolling parallel direction is preferably 0.07 μm or less. When Ra (RD) is 0.07 μm or less, the zero cross time may be reduced.
本発明は、圧延直角方向の表面の凹凸成分の度数分布図におけるピーク位置を規定する。ここで，表面の凹凸成分の度数分布図は特許文献２に記載されたのと同一であり、横軸を粗さ曲線のための平均線からの高さとし、縦軸を頻度（測定データ数）としてプロットした図である。又、本発明においては、横軸を粗さ曲線のための平均線からの高さ0.05μｍ間隔（きざみ）とし、この間隔ごとの測定データ数を頻度として合計し、プロットしている。なお、「粗さ曲線のための平均線」はＪＩＳ−Ｂ０６０１に規格されている。 The present invention defines the peak position in the frequency distribution diagram of the concavo-convex component on the surface in the direction perpendicular to the rolling direction. Here, the frequency distribution diagram of the surface unevenness component is the same as that described in Patent Document 2, the horizontal axis is the height from the average line for the roughness curve, and the vertical axis is the frequency (number of measurement data). FIG. Further, in the present invention, the horizontal axis is an interval (step) of 0.05 μm in height from the average line for the roughness curve, and the number of measurement data for each interval is totaled as a frequency and plotted. The “average line for roughness curve” is standardized in JIS-B0601.
度数分布図は、具体的には以下のように作成する。（１）まず、試料の圧延直角方向に沿い、「粗さ曲線のための平均線からの高さ」を測定する。つまり、表面の位置毎に粗さ曲線のための平均線からの高さデータ（以下、適宜「測定データ」という）が得られるので、得られた測定データからピーク位置等を求めると共に、測定データを数値処理をしてＲａ，Ｒｚを算出している。（２）「粗さ曲線のための平均線」からの高さを0.05μｍ間隔に区切る。（３）上記0.05μｍ間隔ごとに、該当する測定データ数（度数）をカウントする。
なお、測定データは、標準の長さ1.25ｍｍ、カットオフ値25ｍｍ（ＪＩＳ−Ｂ０６０１に準拠）、走査速度０．１ｍｍ／ｓｅｃで測定する。測定は、小坂研究所社製の表面粗さ測定機（Ｓｕｒｆｃｏｒｄｅｒ ＳＥ３４００）を用い、測定長1.25ｍｍで測定データ数が７５００点である。
Specifically, the frequency distribution chart is created as follows. (1) First, along the direction perpendicular to the rolling direction of the sample, the “height from the average line for the roughness curve” is measured. That is, height data from the average line for the roughness curve (hereinafter referred to as “measurement data” as appropriate) is obtained for each surface position, so that the peak position and the like are obtained from the obtained measurement data and the measurement data Ra and Rz are calculated by numerical processing. (2) The height from the “average line for the roughness curve” is divided into 0.05 μm intervals. (3) The number of corresponding measurement data (frequency) is counted for each 0.05 μm interval.
Measurement data is measured at a standard length of 1.25 mm, a cutoff value of 25 mm (conforming to JIS-B0601), and a scanning speed of 0.1 mm / sec. For the measurement, a surface roughness measuring machine (Surfcoder SE3400) manufactured by Kosaka Laboratory Ltd. is used, the measurement length is 1.25 mm, and the number of measurement data is 7500 points.
上記ピーク位置の具体的な測定方法も特許文献２に記載されたのと同一であり、得られた測定データのうち、「粗さ曲線のための平均線」からの高さが0より大きいものを上（プラス）の成分とし、0より小さいものを下（マイナス）の成分に分類して度数分布をプロットする。横軸を「粗さ曲線のための平均線」からの高さ（μｍ）とし、縦軸として測定データ数を0.05μmごとに合計した頻度をプロットし直すと、図２及び図３が得られる（特許文献２の図３に対応）。図２及び図３で、横軸の「粗さ曲線のための平均線」からの高さが０μｍの位置に線を引くと、頻度のピーク位置が凹成分（マイナス側）か凸成分（プラス側）か、（又は０か）が判別できる。
ここで、上記「ピーク位置」の判別は次のようにして行う。まず、頻度―粗さ曲線のための平均線からの高さのグラフ（図２、図３参照）にて、値が最も高い頻度をＰ１、値が次に高い頻度をＰ２とする。そして、（１）ピーク位置が凹成分（マイナス側）とは、P1とP2が両方ともマイナス側にある場合、又は、P2/P1<99％ かつP1がマイナス側にある場合をいう。（２）ピーク位置が凸成分（プラス側）とは、P1とP2が両方ともプラス側にある場合、又は、P2/P1<99％ かつP1がプラスにある場合をいう。（３）ピーク位置が０とは、P2/P1≧99％である場合（但し、P1とP2が両方ともマイナス側にある場合、及びP1とP2が両方ともプラス側にある場合を除く）をいう。
なお、粗さ曲線のための平均線からの高さが０μｍの線は、粗さ曲線のための平均線を意味する。
なお、３回測定した結果からそれぞれ求めたピーク位置がプラスとマイナスにばらついた場合、２回の測定が上（プラス）成分にピークがあれば，凸成分側とみなした。
The specific method for measuring the peak position is also the same as that described in Patent Document 2, and among the obtained measurement data, the height from the “average line for roughness curve” is greater than zero. The frequency distribution is plotted with the upper (plus) component classified as less than 0 and the lower (minus) component. When the horizontal axis is the height (μm) from the “average line for roughness curve” and the vertical axis is plotted again with the frequency of totaling the number of measurement data every 0.05 μm, FIG. 2 and FIG. 3 are obtained. (Corresponding to FIG. 3 of Patent Document 2). 2 and 3, when a line is drawn at a position where the height from the “average line for roughness curve” on the horizontal axis is 0 μm, the peak position of the frequency is a concave component (minus side) or a convex component (plus Side) or (or 0).
Here, the determination of the “peak position” is performed as follows. First, in the graph of height from the average line for the frequency-roughness curve (see FIGS. 2 and 3), the frequency with the highest value is P1, and the frequency with the next highest value is P2. (1) The peak position is a concave component (minus side) means that both P1 and P2 are on the minus side, or P2 / P1 <99% and P1 is on the minus side. (2) The peak position is a convex component (plus side) when P1 and P2 are both on the plus side, or when P2 / P1 <99% and P1 is on the plus side. (3) The peak position is 0 when P2 / P1 ≧ 99% (except when both P1 and P2 are on the negative side and when both P1 and P2 are on the positive side) Say.
A line having a height of 0 μm from the average line for the roughness curve means an average line for the roughness curve.
In addition, when the peak position calculated | required from the result measured 3 times varied to plus and minus, if the measurement of 2 times had a peak in the upper (plus) component, it was considered as the convex component side.
図２は、後述する実施例４の実際の測定データにつき、縦軸を頻度（％）、横軸を粗さ曲線のための平均線からの高さ（μｍ）でプロットし直したグラフである。
又、図３は、後述する実施例１８の実際の測定データにつき、縦軸を頻度（％）、横軸を粗さ曲線のための平均線からの高さ（μｍ）でプロットし直したグラフである。
図３の場合、表面の凹凸成分の度数分布図におけるピーク位置が、粗さ曲線のための平均線よりもプラス側（凸成分側）にあり、図２の場合、上記ピーク位置が粗さ曲線のための平均線よりマイナス側（凹成分側）にあることがわかる。つまり、本発明（例えば図２、実施例４）においては、ピーク位置がマイナス側（凹成分側）にあっても濡れ特性が良好であり、濡れ特性はピーク位置によらない。なお、実施例18は酸洗時の酸洗液を変更したことにより、ピーク位置がプラスとなっている。
FIG. 2 is a graph in which the vertical axis represents frequency (%) and the horizontal axis represents height (μm) from the average line for the roughness curve for actual measurement data of Example 4 to be described later. .
FIG. 3 is a graph in which the vertical axis represents frequency (%) and the horizontal axis represents height (μm) from the average line for the roughness curve for actual measurement data of Example 18 described later. It is.
In the case of FIG. 3, the peak position in the frequency distribution diagram of the surface unevenness component is on the plus side (convex component side) from the average line for the roughness curve, and in the case of FIG. 2, the peak position is the roughness curve. It can be seen that it is on the minus side (concave component side) from the average line for. That is, in the present invention (for example, FIG. 2, Example 4), the wetting characteristic is good even if the peak position is on the minus side (concave component side), and the wetting characteristic does not depend on the peak position. In Example 18, the peak position is positive by changing the pickling solution during pickling.
上記表面粗さＲａ，Ｒｚの測定方法は特許文献２に記載されたのと同一であり、標準の長さ1.25ｍｍ、カットオフ値25ｍｍ（ＪＩＳ−Ｂ０６０１に準拠）、走査速度０．１ｍｍ／ｓｅｃで測定する。測定は、小坂研究所社製の表面粗さ測定機（Ｓｕｒｆｃｏｒｄｅｒ ＳＥ３４００）を用い、測定長1.25ｍｍで測定データ数が７５００点である。なお，表面粗さＲａ，Ｒｚは３回測定し，その平均値をとった。 The measuring method of the surface roughness Ra, Rz is the same as described in Patent Document 2, standard length 1.25 mm, cutoff value 25 mm (conforms to JIS-B0601), scanning speed 0.1 mm / sec. Measure with For the measurement, a surface roughness measuring machine (Surfcoder SE3400) manufactured by Kosaka Laboratory Ltd. is used, the measurement length is 1.25 mm, and the number of measurement data is 7500 points. In addition, surface roughness Ra and Rz were measured 3 times, and the average value was taken.
次に、本発明のCo-Si系銅合金板のその他の規定及び組成について説明する。
＜組成＞
Co：0.5〜3.0質量％、Si：0.1〜1.0質量％を含有し残部がCu及び不可避不純物とする。
Co及びSiの含有量が上記範囲より少ないと、Co2Siによる析出強化が十分でなく、強度の向上が図れない。一方、Co及びSiの含有量が上記範囲を超えると、導電性を劣化させ，熱間加工性も劣化させる。Coの好ましい含有量は1.5〜2.5質量％であり、より好ましい含有量は1.7〜2.2質量％である。Siの好ましい含有量は0.3〜0.7質量％であり、より好ましい含有量は0.4〜0.55質量％である。
Co/Siの質量比は3.5〜5.0が好ましく、3.8〜4.6がより好ましい。Co/Siの質量比がこの範囲であれば、Co2Siを十分に析出させることができる。
Next, other rules and compositions of the Co—Si based copper alloy plate of the present invention will be described.
<Composition>
Co: 0.5 to 3.0% by mass, Si: 0.1 to 1.0% by mass, with the balance being Cu and inevitable impurities.
If the content of Co and Si is less than the above range, precipitation strengthening by Co 2 Si is not sufficient, and the strength cannot be improved. On the other hand, when the content of Co and Si exceeds the above range, the conductivity is deteriorated and the hot workability is also deteriorated. The preferable content of Co is 1.5 to 2.5% by mass, and the more preferable content is 1.7 to 2.2% by mass. The preferable content of Si is 0.3 to 0.7% by mass, and the more preferable content is 0.4 to 0.55% by mass.
The mass ratio of Co / Si is preferably 3.5 to 5.0, more preferably 3.8 to 4.6. If the Co / Si mass ratio is within this range, Co 2 Si can be sufficiently precipitated.
さらに、Ｍｎ、Ｍｇ、Ａｇ、Ｐ，Ｂ、Ｚｒ、Ｆｅ、Ｎｉ、Ｃｒ、Ｖ、Ｎｂ、Ｍｏ、Ｂｅ、Ｚｎ、Ｓｎ及びミッシュメタルからなる群から選択される１種又は２種以上を、合計２．０質量％以下含有すると好ましい。上記元素の合計量が２．０質量％を超えると、下記の効果が飽和すると共に、生産性が劣る。但し、上記元素の合計量が０．００１質量％未満の場合、効果が小さいので、好ましくは上記元素の合計量を０．００１〜２．０質量％、より好ましくは０．０１〜２．０質量％、最も好ましくは０．０４〜２．０質量％とする。 Furthermore, one or more selected from the group consisting of Mn, Mg, Ag, P, B, Zr, Fe, Ni, Cr, V, Nb, Mo, Be, Zn, Sn, and Misch metal, It is preferable to contain 2.0% by mass or less. When the total amount of the above elements exceeds 2.0% by mass, the following effects are saturated and productivity is inferior. However, since the effect is small when the total amount of the above elements is less than 0.001% by mass, the total amount of the above elements is preferably 0.001 to 2.0% by mass, more preferably 0.01 to 2.0%. % By mass, most preferably 0.04 to 2.0% by mass.
ここで、Ｍｎ、Ｍｇ、Ａｇ及びＰは、微量の添加で、導電率を損なわずに強度、応力緩和特性等の製品特性を改善する。これらの元素は主に母相へ固溶することにより上記効果が発揮されるが、第二相粒子に含有されることで一層の効果が発揮される。
Ｂ、Ｚｒ及びＦｅの添加によっても、強度、導電率，応力緩和特性、めっき性等の製品特性が改善する。これらの元素は主に母相へ固溶することにより上記効果が発揮されるが、第二相粒子に含有されることで、又は新たな組成の第二相粒子を形成することで一層の効果が発揮される。
Ｎｉ、Ｃｒ、Ｖ、Ｎｂ、Ｍｏ、Ｂｅ、Ｚｎ、Ｓｎ及びミッシュメタルは相互に特性を補完し、強度、導電率だけでなく，応力緩和特性，曲げ加工性、めっき性や鋳塊組織の微細化による熱間加工性の改善のような製造性をも改善する。
なお、本発明の合金の特性に悪影響を与えない範囲で、本明細書に具体的に記載されていない元素が添加されてもよい。
Here, Mn, Mg, Ag, and P improve the product characteristics such as strength and stress relaxation characteristics without adding conductivity by adding a small amount. These elements mainly exhibit the above-mentioned effects when they are dissolved in the mother phase, but when they are contained in the second-phase particles, further effects are exhibited.
Addition of B, Zr and Fe also improves product properties such as strength, electrical conductivity, stress relaxation properties, and plating properties. The above effects are exerted mainly by dissolving these elements in the mother phase, but by adding them in the second phase particles or forming the second phase particles having a new composition, further effects can be obtained. Is demonstrated.
Ni, Cr, V, Nb, Mo, Be, Zn, Sn, and misch metal complement each other's properties, not only strength and conductivity, but also stress relaxation properties, bending workability, plating properties, and fine ingot structure. It also improves manufacturability such as improvement of hot workability by chemical conversion.
It should be noted that elements not specifically described in the present specification may be added as long as the properties of the alloy of the present invention are not adversely affected.
次に、本発明のＣｏ-Ｓｉ系銅合金板の製造方法の一例について説明する。まず、銅及び必要な合金元素、さらに不可避不純物からなる鋳塊を熱間圧延後、面削して冷間圧延し、溶体化処理した後で時効処理してCo2Siを析出させる。次に最終冷間圧延で所定厚みに仕上げ、必要に応じてさらに歪取り焼鈍し、最後に酸洗して直ちにバフ研磨する。
溶体化処理は例えば、７００℃以上１０００℃以下の範囲で選択とすることができる。又、時効処理は例えば、400℃〜650℃で1〜20時間とすることができる。
又、最終圧延加工度は，好ましくは5〜５０％，さらに好ましくは２０％〜３０％である。本発明の合金材の結晶粒径は特に限定されないが，一般的には３〜20μｍ以下である。析出物の粒径は５ｎｍ〜１０μｍである。
Next, an example of a method for producing the Co—Si based copper alloy plate of the present invention will be described. First, an ingot made of copper, necessary alloy elements, and inevitable impurities is hot-rolled, face-cut and cold-rolled, solution-treated, and then subjected to aging treatment to precipitate Co 2 Si. Next, it is finished to a predetermined thickness by final cold rolling, further subjected to strain relief annealing as necessary, finally pickled and immediately buffed.
The solution treatment can be selected, for example, in the range of 700 ° C. or higher and 1000 ° C. or lower. Moreover, an aging treatment can be made into 400 to 650 degreeC for 1 to 20 hours, for example.
The final rolling degree is preferably 5 to 50%, more preferably 20% to 30%. The crystal grain size of the alloy material of the present invention is not particularly limited, but is generally 3 to 20 μm or less. The particle size of the precipitate is 5 nm to 10 μm.
なお、本発明のCo-Si系銅合金板は、上記したＲａを用いて規定することができるが、Ｒｚを用いて規定してもよい。 The Co—Si based copper alloy sheet of the present invention can be defined using Ra described above, but may be defined using Rz.
表１に示す組成のインゴットを鋳造し、900℃以上で厚さ10ｍｍまで熱間圧延を行い、表面の酸化スケールを面削した後、冷間圧延し、７００℃以上１０００℃以下で溶体化処理した後で４００℃〜６５０℃で1〜20時間の時効処理を施した。次に加工率5〜40％で最終冷間圧延で所定厚みに仕上げ、さらに３００〜６００℃で０．０５〜３時間の歪取り焼鈍を行い、最後に表１に示す条件で酸洗して直ちにバフ研磨した。なお、バフ研磨前の酸洗に用いる酸洗液は、濃度２０〜３０質量％でｐＨ＝１以下の希硫酸、塩酸又は希硝酸の水溶液とし、酸洗の浸漬時間を60〜180秒とした。バフ研磨に用いるバフ材は、アルミナ製の砥粒を用い，ナイロン不織布にアルミナ含有させたものを用いた。そして、それぞれバフ目粗さ（研磨砥粒の番手）を変化させたバフ材を用いた。研磨砥粒の番手は、砥粒を１インチ当たりの網の目の数を示し、JIS R6001に規格されている。例えば、番手が１０００であれば、砥粒の平均粒径が18〜14.5μｍとなる。なお、実施例１８は、酸洗バフ研磨の酸洗液として濃度４０〜５０質量％でｐＨ＝１以下の硝酸の水溶液を用いたこと以外は他の実施例と同様である。 Cast an ingot having the composition shown in Table 1 and hot-roll at 900 ° C or higher to a thickness of 10mm. After that, an aging treatment was performed at 400 ° C. to 650 ° C. for 1 to 20 hours. Next, it is finished to a predetermined thickness by final cold rolling at a processing rate of 5 to 40%, further subjected to strain relief annealing at 300 to 600 ° C. for 0.05 to 3 hours, and finally pickled under the conditions shown in Table 1. Immediately buffed. The pickling solution used for pickling before buffing is an aqueous solution of dilute sulfuric acid, hydrochloric acid or dilute nitric acid having a concentration of 20 to 30% by mass and pH = 1 or less, and the dipping time for pickling is 60 to 180 seconds. . The buffing material used for the buffing was an alumina abrasive grain and a nylon nonwoven fabric containing alumina. And the buffing material in which the buffing roughness (count of abrasive grains) was changed was used. The count of the abrasive grains indicates the number of meshes per inch of the abrasive grains, and is specified in JIS R6001. For example, if the count is 1000, the average grain size of the abrasive grains is 18 to 14.5 μm. Example 18 is the same as the other examples except that an aqueous solution of nitric acid having a concentration of 40 to 50% by mass and pH = 1 or less was used as the pickling solution for pickling buffing.
このようにして得られた各試料について、諸特性の評価を行った。
（１）Ｒａ及びＲｚ
ＪＩＳ−Ｂ０６０１（２００１年）に従い、中心線平均粗さＲａ及び最大高さＲｚを測定した。測定は、圧延平行方向（ＲＤ）及び圧延直角方向（ＴＤ）についてそれぞれ測定した。測定は、標準の長さは1.25ｍｍ、カットオフ値0.25ｍｍ（上記ＪＩＳに準拠）、走査速度０．１ｍｍ／ｓｅｃとし、小坂研究所社製の表面粗さ測定機（Ｓｕｒｆｃｏｒｄｅｒ ＳＥ３４００）を用い、測定長1.25ｍｍで測定データ数が７５００点とした。
Various characteristics of each sample thus obtained were evaluated.
(1) Ra and Rz
According to JIS-B0601 (2001), the center line average roughness Ra and the maximum height Rz were measured. The measurement was performed for the rolling parallel direction (RD) and the rolling perpendicular direction (TD). The standard length is 1.25 mm, the cut-off value is 0.25 mm (conforms to the above JIS), the scanning speed is 0.1 mm / sec, and a surface roughness measuring machine (Surfcoder SE3400) manufactured by Kosaka Laboratory is used. The measurement length was 1.25 mm and the number of measurement data was 7500 points.
（２）度数分布図
（１）で得られた圧延直角方向の測定データにつき、測定データのうち、「粗さ曲線のための平均線」から上（プラス）の成分と下（マイナス）の成分に分類し、粗さ曲線のための平均線からの高さを0.05μmきざみとして度数分布をプロットした。測定データから、縦軸を頻度（％）、横軸を粗さ曲線のための平均線からの高さ（μｍ）でプロットし直し、図２及び図３が得られた。図２及び図３で、横軸の粗さ曲線のための平均線からの高さの０μｍに線を引くと、頻度のピークが凹成分（マイナス側）か凸成分（プラス側）か、（又は０か）が判別できる。
(2) Frequency distribution diagram Regarding the measurement data in the direction perpendicular to the rolling obtained in (1), among the measurement data, the upper (plus) component and the lower (minus) component from the “average line for roughness curve” The frequency distribution was plotted with the height from the average line for the roughness curve in increments of 0.05 μm. From the measurement data, the vertical axis is plotted with frequency (%), and the horizontal axis is plotted with the height (μm) from the average line for the roughness curve, and FIGS. 2 and 3 are obtained. 2 and 3, when a line is drawn to 0 μm in height from the average line for the roughness curve on the horizontal axis, whether the frequency peak is a concave component (minus side) or a convex component (plus side), ( Or 0).
図２は、実施例４の実際の測定データにつき、縦軸を頻度（％）、横軸を粗さ曲線のための平均線からの高さ（μｍ）でプロットし直したグラフである。
又、図３は、後述する実施例１８の実際の測定データにつき、縦軸を頻度（％）、横軸を粗さ曲線のための平均線からの高さ（μｍ）でプロットし直したグラフである。
FIG. 2 is a graph in which actual measurement data of Example 4 is re-plotted with frequency (%) on the vertical axis and height (μm) from the average line for the roughness curve on the horizontal axis.
FIG. 3 is a graph in which the vertical axis represents frequency (%) and the horizontal axis represents height (μm) from the average line for the roughness curve for actual measurement data of Example 18 described later. It is.
（３）はんだ特性
（３−１）ピンホール数
ピンホール数は、はんだが濡れずに，下地（銅合金材）がみえる穴の数をいう。ピンホール数が多くなると半田付け不良が生じ易くなる。ピンホール数の試験は、10mm幅の試料を10質量％の希硫酸水溶液で酸洗した後に、浸漬深さ１２ｍｍ、浸漬速度２５ｍｍ／ｓ，浸漬時間１０ｓｅｃで、はんだ浴に浸漬して引き上げたとき、表裏を光学顕微鏡（倍率50倍）で観察して下地が目視された数をカウントし、5個以下を良好とした。
はんだ試験はJIS-C60068-2-54に準拠して実施した．はんだ浴の組成は、スズ60wt%,鉛40wt%とし、さらにフラックス（ロジン25wt%,エタノール75wt%）を適量加え、はんだ温度235℃±3℃とした。
（３−１）ゼロクロスタイム（Ｔ2値）
ゼロクロスタイム（Ｔ2値）は、濡れ応力値がゼロになるまでの時間であり、ゼロクロスタイムが短いほど、はんだに濡れやすい。試験は、試料を10wt％の希硫酸水溶液で酸洗した後に、浸漬深さ４ｍｍ,浸漬速度２５ｍｍ／ｓ，浸漬時間１０ｓｅｃで、235℃±3℃の上記はんだ浴に浸漬し、JISC60068-2-54に準拠して実施し、メニスコグラフ法でゼロクロスタイムを求めた。ゼロクロスタイムが2.0秒以下をはんだ濡れ性良好とした。
(3) Solder characteristics (3-1) Number of pinholes The number of pinholes refers to the number of holes in which the base (copper alloy material) can be seen without solder getting wet. If the number of pinholes increases, soldering defects are likely to occur. The test for the number of pinholes was performed when a 10 mm wide sample was pickled with a 10% by weight dilute sulfuric acid solution, then immersed in a solder bath at an immersion depth of 12 mm, an immersion speed of 25 mm / s, and an immersion time of 10 sec. The front and back sides were observed with an optical microscope (magnification 50 times), and the number of bases that were visually observed was counted.
The solder test was conducted according to JIS-C60068-2-54. The composition of the solder bath was tin 60 wt%, lead 40 wt%, and an appropriate amount of flux (rosin 25 wt%, ethanol 75 wt%) was added to make the solder temperature 235 ° C. ± 3 ° C.
(3-1) Zero cross time (T2 value)
The zero cross time (T2 value) is the time until the wetting stress value becomes zero, and the shorter the zero cross time, the easier it is to get wet with the solder. In the test, the sample was pickled with a 10 wt% dilute sulfuric acid solution, immersed in the above-mentioned solder bath at 235 ° C. ± 3 ° C. at an immersion depth of 4 mm, an immersion speed of 25 mm / s, and an immersion time of 10 sec. The measurement was conducted in accordance with No. 54, and the zero cross time was determined by the meniscograph method. A zero cross time of 2.0 seconds or less was considered good solder wettability.
得られた結果を表１〜表３に示す。なお、表１、表２の「仕上圧延の前処理」において、Ａ法、Ｂ法は以下の条件で酸洗バフ研磨を行ったものである。例えば、実施例９は、仕上圧延前に酸洗バフ研磨を行い、さらに仕上圧延後も酸洗バフ研磨を行った。仕上圧延前の酸洗バフ研磨にて酸洗に用いる酸洗液は、上記した仕上圧延後の酸洗バフ研磨に用いた酸洗液と同一である。
Ａ法：バフ研磨回数１回、通板速度40m/min、バフ目粗さ（研磨砥粒）1000番手、バフ回転数５００rpm
Ｂ法：バフ研磨回数３回、通板速度10m/min、バフ目粗さ（研磨砥粒）2000番手、バフ回転数１４００rpm
なお、一部の試料については、仕上圧延前に、１０％硫酸水溶液に３０秒浸漬させる酸洗のみ行った。また、一部の試料については、仕上圧延前に、ヘキサンに３０秒浸漬させる脱脂のみ行った。又、他の試料は仕上圧延前に何ら処理を行わなかった。
The obtained results are shown in Tables 1 to 3. In Tables 1 and 2, in “Pre-treatment of finish rolling”, the A method and the B method are pickling buff polishing under the following conditions. For example, in Example 9, pickling buff polishing was performed before finish rolling, and pickling buff polishing was further performed after finish rolling. The pickling liquid used for pickling in the pickling buff polishing before finish rolling is the same as the pickling liquid used for the pickling buff polishing after finish rolling described above.
Method A: Number of times of buffing, one plate speed of 40 m / min, buffing roughness (abrasive grain) of 1000, buffing speed of 500 rpm
Method B: Number of times of buffing 3 times, plate speed 10 m / min, buffing roughness (abrasive grain) 2000, buffing speed 1400 rpm
Note that some samples were only pickled soaking in a 10% aqueous sulfuric acid solution for 30 seconds before finish rolling. In addition, some samples were only degreased soaked in hexane for 30 seconds before finish rolling. Further, the other samples were not subjected to any treatment before finish rolling.
表１〜表３から明らかなように、最終熱処理（歪取焼鈍）後の酸洗バフ研磨を、比較的目（研磨砥粒）の細かいバフを用いて十分な回数行った各実施例の場合、はんだ濡れ性に優れ、かつピンホールが低減した。各実施例はいずれも(Ra(RD)/ Ra(TD))≦0.8、(Rz(RD)/ Rz(TD))≦0.8であり、材料表面の酸化皮膜，異物の押し込みを十分に除去すると共に表面が平滑になったものと考えられる。
なお、各実施例では、酸洗バフ研磨を、研磨砥粒が２０００番以上、通板回数２回以上、通板速度１０ｍｐｍ以下、回転数１２００回転／分以上の条件で行ったが、勿論、製造装置に応じてこれらの最適範囲は変化する。
As is clear from Tables 1 to 3, in the case of each Example in which pickling buff polishing after final heat treatment (strain relief annealing) was performed a sufficient number of times using buffs with relatively fine eyes (polishing abrasive grains) Excellent solder wettability and reduced pinholes. In each example, (Ra (RD) / Ra (TD)) ≦ 0.8 and (Rz (RD) / Rz (TD)) ≦ 0.8, which sufficiently removes the oxide film on the material surface and the indentation of foreign matter. At the same time, the surface is thought to be smooth.
In each example, the pickling buff polishing was performed under the conditions that the abrasive grains were 2000 or more, the number of plate passing was 2 times or more, the plate passing speed was 10 mpm or less, and the number of rotations was 1200 rpm / min. These optimum ranges vary depending on the manufacturing equipment.
一方，各比較例では酸洗バフ研磨が十分に行われず，材料表面の酸化皮膜や、異物の押し込みを十分に除去できなかった。このため、各比較例では、(Ra(RD)/ Ra(TD))＞0.8、(Rz(RD)/ Rz(TD))＞0.8となり、ピンホールが増加し，酸化皮膜が多く残存していたものははんだぬれ性が劣化した。 On the other hand, pickling buffing was not sufficiently performed in each comparative example, and the oxide film on the surface of the material and indentation of foreign matters could not be removed sufficiently. For this reason, in each comparative example, (Ra (RD) / Ra (TD))> 0.8 and (Rz (RD) / Rz (TD))> 0.8, pinholes increase, and many oxide films remain. The solder wettability deteriorated.
これらの劣化原因は、比較例１，２，１５，１７，１９の場合，酸洗バフ研磨の通板速度が２０ｍｐｍを超えたためと考えられる。
比較例３、５，８，２０の場合，酸洗バフ研磨の通板回数が２回未満であるためと考えられる。なお、比較例２０は、最終圧延後に上述A法で酸洗研磨を実施した。
比較例１３の場合，酸洗は行ったが，バフ研磨を行わなかったためと考えられる。
比較例６，７の場合，酸洗バフ研磨の研磨砥粒を４０００番としたために研磨砥粒が細か過ぎ、あまり研磨されないため，Ra(RD)の低減効果が少なかったと考えられる。
比較例１１，１２の場合，酸洗バフ研磨の回転数が１２００回転／分未満であるためと考えられる。
比較例９，１０の場合，研磨砥粒が粗過ぎて酸洗バフ研磨面が荒れ、(Ra(RD)/ Ra(TD))＞0.8、(Rz(RD)/ Rz(TD))＞0.8となりピンホールが増加し，ゼロクロスタイムが悪くなった。これは，酸洗バフ研磨の研磨砥粒を５００番としたために研磨砥粒が粗すぎたためと考えられる。
比較例４、１４、１６、１８，２１の場合、最終圧延後に酸洗バフ研磨をしなかったため表面の酸化皮膜，異物の押し込みが除去されずに圧延された表面ままの状態が維持されたためと考えられる。なお、比較例２１は、最終圧延のロールの粗さを細かくしたこと以外は各実施例と同様にして製造した。
The reason for these deteriorations is considered to be that in the case of Comparative Examples 1, 2, 15, 17, and 19, the plate speed of pickling buffing exceeded 20 mpm.
In the case of Comparative Examples 3, 5, 8, and 20, it is considered that the number of pickling buffing passes is less than two. In Comparative Example 20, pickling was performed by the above-described A method after final rolling.
In the case of Comparative Example 13, it is considered that pickling was performed but buffing was not performed.
In the case of Comparative Examples 6 and 7, it is considered that the effect of reducing Ra (RD) was small because the abrasive grains for pickling buff polishing were set to No. 4000 and the abrasive grains were too fine and not polished much.
In the case of Comparative Examples 11 and 12, it is considered that the rotational speed of pickling buffing is less than 1200 revolutions / minute.
In Comparative Examples 9 and 10, the abrasive grains were too rough and the pickled buff polished surface was rough, (Ra (RD) / Ra (TD))> 0.8, (Rz (RD) / Rz (TD))> 0.8 As a result, pinholes increased and the zero crossing time worsened. This is presumably because the abrasive grains for pickling buff polishing were set to No. 500 and the abrasive grains were too coarse.
In the case of Comparative Examples 4, 14, 16, 18, and 21, since pickling buffing was not performed after the final rolling, the surface of the rolled surface was maintained without removing the oxide film on the surface and the indentation of foreign matter. Conceivable. In addition, Comparative Example 21 was manufactured in the same manner as each Example except that the roughness of the roll of final rolling was fine.
なお、比較例１６，１８，場合、仕上げ圧延前に処理（酸洗又は脱脂）を行い、かつ酸洗バフ研磨を行わなかったため、ピーク位置が粗さ曲線のための平均線（表面の凹凸成分を表す度数分布図におけるゼロの位置）よりプラス側（凸成分側）となった。つまり、これら比較例は、特許文献２による銅合金板を示している。
又、比較例４、１３、１６，２１の場合、ゼロクロスタイムが2.0秒を超え、はんだ濡れ性も劣化したが、この理由は、酸洗およびバフ研磨を1回も行っていないため，酸化皮膜が金属表面に多く残存したためと考えられる。（なお，比較例１６が特許文献２記載の条件に該当している）
In Comparative Examples 16 and 18, since the treatment (pickling or degreasing) was performed before finish rolling and the pickling buffing was not performed, the peak line was an average line for the roughness curve (surface unevenness component) It was on the plus side (convex component side) from the zero position in the frequency distribution diagram representing. That is, these comparative examples show copper alloy sheets according to Patent Document 2.
In Comparative Examples 4, 13, 16, and 21, the zero cross time exceeded 2.0 seconds and the solder wettability was deteriorated because the pickling and buffing were not performed once. It is considered that a large amount of was left on the metal surface. (Note that Comparative Example 16 corresponds to the conditions described in Patent Document 2)
Claims (6)
(圧延平行方向の表面粗さRa(RD)/圧延直角方向の表面粗さRa(TD))≦0.8であるCo-Si系銅合金板。 Co: 0.5-3.0% by mass, Si: 0.1-1.0% by mass, the balance being a Co-Si based copper alloy plate made of Cu and inevitable impurities,
Co-Si copper alloy sheet in which (surface roughness Ra (RD) in the direction parallel to rolling / surface roughness Ra (TD) in the direction perpendicular to rolling) ≦ 0.8.
(圧延平行方向の表面粗さRz(RD)/圧延直角方向の表面粗さRz(TD))≦0.8であるCo-Si系銅合金板。 Co: 0.5-3.0% by mass, Si: 0.1-1.0% by mass, the balance being a Co-Si based copper alloy plate made of Cu and inevitable impurities,
Co-Si copper alloy sheet in which (surface roughness Rz (RD) in the direction parallel to rolling / surface roughness Rz (TD) in the direction perpendicular to rolling) ≦ 0.8.
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| JP2008056977A (en) * | 2006-08-30 | 2008-03-13 | Mitsubishi Electric Corp | Copper alloy and its production method |
| WO2010013790A1 (en) * | 2008-07-31 | 2010-02-04 | 古河電気工業株式会社 | Copper alloy material for electrical and electronic components, and manufacturing method therefor |
| WO2010016428A1 (en) * | 2008-08-05 | 2010-02-11 | 古河電気工業株式会社 | Copper alloy material for electrical/electronic component |
| JP2010236071A (en) * | 2009-03-31 | 2010-10-21 | Nippon Mining & Metals Co Ltd | Cu-Co-Si COPPER ALLOY FOR ELECTRONIC MATERIAL, AND METHOD OF MANUFACTURING THE SAME |
| JP2011017072A (en) * | 2009-07-10 | 2011-01-27 | Furukawa Electric Co Ltd:The | Copper alloy material |
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| JP2008056977A (en) * | 2006-08-30 | 2008-03-13 | Mitsubishi Electric Corp | Copper alloy and its production method |
| WO2010013790A1 (en) * | 2008-07-31 | 2010-02-04 | 古河電気工業株式会社 | Copper alloy material for electrical and electronic components, and manufacturing method therefor |
| WO2010016428A1 (en) * | 2008-08-05 | 2010-02-11 | 古河電気工業株式会社 | Copper alloy material for electrical/electronic component |
| JP2010236071A (en) * | 2009-03-31 | 2010-10-21 | Nippon Mining & Metals Co Ltd | Cu-Co-Si COPPER ALLOY FOR ELECTRONIC MATERIAL, AND METHOD OF MANUFACTURING THE SAME |
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