JP2007063624A - Copper alloy tinned strip having excellent insertion/withdrawal property and heat resistance - Google Patents
Copper alloy tinned strip having excellent insertion/withdrawal property and heat resistance Download PDFInfo
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本発明は、コネクタ、端子、リレ−、スイッチ等の導電性ばね材として好適な、良好な挿抜性及び耐熱性を有する銅合金すずめっき条に関する。 The present invention relates to a copper alloy tin plating strip having good insertability and heat resistance suitable as a conductive spring material for connectors, terminals, relays, switches and the like.
コネクタ、端子、リレ−、スイッチ等の導電性ばね材には、Ｓｎめっきを施した銅合金が用いられる。銅合金のＳｎめっき条は、一般的に、連続めっきラインにおいて、脱脂及び酸洗の後、電気めっき法によりＣｕ下地めっき相を形成し、次に電気めっき法によりＳｎめっき相を形成し、最後にリフロー処理を施しＳｎめっき相を溶融させる工程で製造される。
近年、電子・電気部品の回路数増大により、回路に電気信号を供給するコネクタの多極化が進んでいる。Ｓｎめっき材は、その軟らかさからコネクタの接点においてオスとメスを凝着させるガスタイト（気密）構造が採られるため、金めっき等で構成されるコネクタに比べ、コネクタの挿入力が高い。このためコネクタの多極化によるコネクタ挿入力の増大が問題となっている。
例えば、自動車の組み立てラインでは、コネクタを嵌合させる作業は、現在ほとんど人力で行われている。コネクタの挿入力が大きくなると、組み立てラインで作業者に負担がかかり、作業効率の低下に直結する。更に、作業者の健康を損なう可能性も指摘されている。このことから、Ｓｎめっき材の挿入力の低減が強く望まれている。
For conductive spring materials such as connectors, terminals, relays, and switches, a copper alloy with Sn plating is used. In general, the Sn plating strip of a copper alloy is formed in a continuous plating line after degreasing and pickling, forming a Cu undercoat phase by electroplating, and then forming an Sn plating phase by electroplating. It is manufactured in a process in which a reflow treatment is applied to melt the Sn plating phase.
In recent years, with the increase in the number of circuits of electronic / electrical components, the number of connectors for supplying electric signals to the circuits has been increasing. Since the Sn plating material adopts a gas tight (airtight) structure in which male and female are adhered to each other at the contact point of the connector due to its softness, the insertion force of the connector is higher than a connector constituted by gold plating or the like. For this reason, an increase in connector insertion force due to the increase in the number of connectors is a problem.
For example, in an automobile assembly line, the work of fitting a connector is currently almost done manually. When the insertion force of the connector is increased, a burden is imposed on the worker on the assembly line, which directly leads to a decrease in work efficiency. Furthermore, the possibility of damaging the health of workers has been pointed out. For this reason, reduction of the insertion force of Sn plating material is strongly desired.
一方、Ｓｎめっき材では、経時的に、母材や下地めっきの成分がＳｎ相に拡散して合金相を形成することによりＳｎ相が消失し、接触抵抗、半田付け性といった諸特性が劣化する。銅合金のＣｕ下地Ｓｎめっきの場合、この合金相は主としてＣｕ3Ｓｎ、Ｃｕ6Ｓｎ5等の金属間化合物である。特性の経時劣化は、高温ほど促進され、自動車のエンジン回り等では特に顕著になる。
このような状況の中で、米国の３大自動車メーカーにより設立された自動車部品の規格を決定しているＵＳＣＡＲにおいて、コネクタ材の耐熱性の要求が高まってきており、最も厳しい使用条件では、常時の使用温度が１５５℃、最高使用温度が１７５℃での耐熱性が要求されている。また、国内においても、特に自動車関連のコネクター材でやはり耐熱性の要求が高まってきており、１５０℃以下での耐熱性が求められてきている。
更に、コネクタメーカーの生産拠点の海外への移転により、素材がめっきされた後、長期間放置されてから使用されるケースがある。このため、長期間保存しても、めっき材の諸特性が劣化しない材料、すなわち耐時効性が高い材料が求められてきている。なお、めっき材の特性劣化は高温下で促進される。したがって高温下での特性劣化が少ない材料は長期間保存しても特性が劣化しない材料と言い換えることができる。したがってこの分野でも耐熱性の高いめっき材が求められていることになる。
On the other hand, in the Sn plating material, with time, the base material and the base plating components diffuse into the Sn phase to form an alloy phase, so that the Sn phase disappears and various characteristics such as contact resistance and solderability deteriorate. . In the case of Cu-based Sn plating of a copper alloy, this alloy phase is mainly an intermetallic compound such as Cu 3 Sn or Cu 6 Sn 5 . The deterioration of characteristics with time is accelerated as the temperature increases, and becomes particularly noticeable around an automobile engine.
Under such circumstances, the requirements for heat resistance of connector materials are increasing at USCAR, which is the standard for automotive parts established by three major automakers in the United States. Heat resistance is required at a use temperature of 155 ° C. and a maximum use temperature of 175 ° C. In Japan as well, there is an increasing demand for heat resistance especially for automobile-related connector materials, and heat resistance at 150 ° C. or lower has been demanded.
Furthermore, there is a case where the material is plated and then left for a long period of time due to the relocation of the connector manufacturer's production base to overseas. For this reason, there has been a demand for a material that does not deteriorate the properties of the plated material even when stored for a long period of time, that is, a material with high aging resistance. In addition, the characteristic deterioration of the plating material is promoted at a high temperature. Therefore, a material with little property deterioration at high temperatures can be rephrased as a material whose properties do not deteriorate even when stored for a long period of time. Therefore, a plating material having high heat resistance is also required in this field.
以上のように、Ｓｎめっき材においては、挿入力の低減及び耐熱性の改善が近年の課題になっている。コネクタの挿入力を低減するための有効な方法は、特許文献１〜３等で開示されている通り、Ｓｎめっき相を薄くすることである。しかし、Ｓｎめっき相を薄くすると、Ｓｎ相消失による特性劣化が早期に進行する。すなわち、単にＳｎめっきを薄くするだけでは、挿入力が低減する反面、耐熱性が劣化する。したがって、Ｓｎ相を薄くする場合には、Ｓｎめっきの耐熱性を改善する技術を適用することが必要となる。 As described above, in the Sn plated material, reduction of insertion force and improvement of heat resistance have become issues in recent years. An effective method for reducing the insertion force of the connector is to thin the Sn plating phase as disclosed in Patent Documents 1 to 3 and the like. However, when the Sn plating phase is thinned, characteristic deterioration due to disappearance of the Sn phase proceeds at an early stage. That is, simply thinning the Sn plating reduces the insertion force, but deteriorates the heat resistance. Therefore, when the Sn phase is thinned, it is necessary to apply a technique for improving the heat resistance of Sn plating.
Ｓｎめっきの耐熱性を改善する技術として、下地めっきによりＳｎ中へのＣｕ等の拡散を防止する技術が検討されている。例えば、特許文献４〜７等では、Ｃｕ／Ｎｉの二相下地めっきを施す技術が開示されている。このＳｎめっきをリフローすると、Ｓｎ／Ｃｕ−Ｓｎ合金／Ｎｉ／銅合金母材の構造となる。Ｎｉ相により母材ＣｕのＳｎ相中への拡散が抑制され、またＣｕ−Ｓｎ合金相の存在によりＮｉのＳｎ相中に拡散が抑制されるため、Ｓｎ相の消失が遅れる。
上述したように薄Ｓｎめっきと高耐熱下地めっきとを組み合わせることにより、Ｓｎめっき材の低挿入力化が図られてきたが、この手法も限界に近づいてきた。一方、低挿入力化への要求はますます高まっており、新たな視点からのめっき技術の開発が望まれるようになった。本発明の課題は、新たな手法により、Ｓｎめっき銅合金条の挿抜性及び耐熱性を改善することである。 As described above, by combining the thin Sn plating and the high heat-resistant base plating, the insertion force of the Sn plating material has been reduced, but this method has also approached the limit. On the other hand, the demand for lower insertion force has been increasing, and the development of plating technology from a new perspective has been desired. The subject of this invention is improving the insertion / extraction property and heat resistance of Sn plating copper alloy strip by a new method.
本発明者は、Ｓｎめっき銅合金条のリフロー処理後のＣｕ−Ｓｎ合金相の粗さに着目し、その平均粗さと挿抜性及び耐熱性との関係を調査した。
図１はリフロー後のＣｕ下地Ｓｎめっき材断面を模式的に示したものであり、Ｃｕ−Ｓｎ合金相の平均粗さが小さい場合（ａ）と大きい場合（ｂ）を比較している。両者のめっき相全体の厚みは同じである。ここで、ａ１、ｂ１はそれぞれのＣｕ−Ｓｎ合金相の平均厚み、ａ２、ｂ２はめっき表面からＣｕ−Ｓｎ合金相に達するまでのＳｎ相の厚みを示す。両者のＣｕ−Ｓｎ合金相の平均厚さが同じ場合（ａ１＝ｂ１）、Ｃｕ−Ｓｎ合金相の平均粗さが小さいほど、表面からＣｕ−Ｓｎ合金相に達するまでの厚みは大きくなる（ａ２＞ｂ２）。Ｓｎは柔らかい金属であるために、めっき表面に接触した接点を摺動させる場合には、Ｓｎ相は摺動の抵抗として作用する。そのため、Ｃｕ−Ｓｎ合金相に達するまでのＳｎの厚みが薄いほど挿抜力は低下する。したがってＣｕ−Ｓｎ合金相の平均粗さが大きいほど、挿抜性は良好である。
図２は図１の（ａ）及び（ｂ）を加熱した後の母材とめっき相の断面をそれぞれ模式的に示したものである。加熱すると母材である銅合金からＣｕが拡散し、Ｃｕ−Ｓｎ合金相は加熱前の平均粗さを保ちながら成長する。加熱によるＣｕ−Ｓｎ拡散相の成長速度が同じ場合は、加熱により成長したＣｕ−Ｓｎ合金相の厚みが等しく（ａ３＝ｂ３）、Ｃｕ−Ｓｎ合金相の平均粗さが小さいほど、Ｃｕ−Ｓｎ合金相が表面に達するまでの加熱時間が長い。Ｃｕ−Ｓｎ合金相が表面に達すると、表面に酸化銅が生成し、半田濡れ性の劣化や接触抵抗の増大が生じる。したがってＣｕ−Ｓｎ合金相の平均粗さが小さいほど、耐熱性は良好である。
The inventor paid attention to the roughness of the Cu—Sn alloy phase after the reflow treatment of the Sn-plated copper alloy strip, and investigated the relationship between the average roughness and the insertability / heat resistance.
FIG. 1 schematically shows a cross section of a Cu-based Sn plating material after reflow, and the case where the average roughness of the Cu—Sn alloy phase is small (a) and the case where it is large (b) are compared. The thicknesses of both plating phases are the same. Here, a1 and b1 indicate the average thickness of each Cu—Sn alloy phase, and a2 and b2 indicate the thickness of the Sn phase from the plating surface until reaching the Cu—Sn alloy phase. When the average thickness of both Cu-Sn alloy phases is the same (a1 = b1), the smaller the average roughness of the Cu-Sn alloy phase, the larger the thickness from the surface to the Cu-Sn alloy phase (a2 > B2). Since Sn is a soft metal, the Sn phase acts as a sliding resistance when sliding the contact point in contact with the plating surface. Therefore, the insertion / extraction force decreases as the thickness of Sn until the Cu—Sn alloy phase is reached. Therefore, the greater the average roughness of the Cu—Sn alloy phase, the better the insertion / extraction.
FIG. 2 schematically shows cross sections of the base material and the plating phase after heating (a) and (b) of FIG. When heated, Cu diffuses from the base copper alloy, and the Cu—Sn alloy phase grows while maintaining the average roughness before heating. When the growth rate of the Cu—Sn diffusion phase by heating is the same, the Cu—Sn alloy phase grown by heating has the same thickness (a3 = b3), and the smaller the average roughness of the Cu—Sn alloy phase, the smaller the Cu—Sn alloy phase. The heating time until the alloy phase reaches the surface is long. When the Cu—Sn alloy phase reaches the surface, copper oxide is generated on the surface, and solder wettability is deteriorated and contact resistance is increased. Therefore, the smaller the average roughness of the Cu—Sn alloy phase, the better the heat resistance.
以上のように、Ｃｕ−Ｓｎ合金相の平均粗さが、大きくなると挿抜性が向上し、小さくなると耐熱性が向上する。本発明者は、この発見に基づき、良好な挿抜性と耐熱性が同時に得られる平均粗さの条件を見出した。すなわち本発明は、下記めっき条を提供する。
（１）銅合金条の表面に、Ｃｕ、Ｓｎの電気めっきを施し、その後、リフロー処理を施すことにより得られるＣｕ−Ｓｎ合金相の平均粗さＲａが０．０５〜０．３μｍであることを特徴とする、挿抜性及び耐熱性に優れる銅合金すずめっき条。
（２）表面から銅合金条母材にかけて、Ｓｎ相、Ｃｕ−Ｓｎ合金相、Ｃｕ相の各相でめっき皮膜が構成され、Ｓｎ相の平均厚みが０．０２〜２．０μｍ、Ｃｕ−Ｓｎ合金相の厚みが０．１〜２．０μｍ、Ｃｕ相の厚みが０〜２．０μｍであることを特徴とする上記（１）の挿抜性及び耐熱性に優れる銅合金すずめっき条。
（３）表面から銅合金条母材にかけて、Ｓｎ相、Ｃｕ−Ｓｎ合金相、Ｎｉ相の各相でめっき皮膜が構成され、Ｓｎ相の平均厚みが０．０２〜２．０μｍ、Ｃｕ−Ｓｎ合金相の厚みが０．１〜２．０μｍ、Ｎｉ相の厚みが０．１〜２．０μｍであることを特徴とする上記（１）の挿抜性及び耐熱性に優れる銅合金すずめっき条。
（４）該銅合金条は、１．０〜４．５質量％のＮｉを含有し、Ｎｉの質量％に対し１／６〜１／４のＳｉを含有し、更に必要に応じてＺｎ、Ｓｎ、Ｍｇ、Ｃｏ、Ａｇ、Ｃｒ及びＭｎの群から選ばれた１種以上を合計で２．０質量％以下含有し、残部が銅及び不可避的不純物から構成されることを特徴とする上記（１）〜（３）いずれか１項記載の挿抜性及び耐熱性に優れる銅合金すずめっき条。
（５）該銅合金条は、１〜１１質量％のＳｎ及び０．０１〜０．２質量％のＰを含有し、更に必要に応じてＺｎ、Ｎｉ、Ｃｏ、Ｆｅ、Ａｇ、及びＭｎの群から選ばれた１種以上を合計で２．０質量％以下含有し、残部が銅及び不可避的不純物から構成されることを特徴とする上記（１）〜（３）いずれか１項記載の挿抜性及び耐熱性に優れる銅合金すずめっき条。
（６）該銅合金条は、２５〜４０質量％のＺｎを含有し、更に必要に応じてＮｉ、Ｃｒ、Ｃｏ、Ｓｎ、Ｆｅ、Ａｇ、及びＭｎの群から選ばれた１種以上を合計で２．０質量％以下含有し、残部が銅及び不可避的不純物から構成されることを特徴とする上記（１）〜（３）いずれか１項記載の挿抜性及び耐熱性に優れる銅合金すずめっき条。
（７）該銅合金条は、２〜２２質量％のＺｎを含有し、更に必要に応じてＮｉ、Ｃｒ、Ｃｏ、Ｓｎ、Ｆｅ、Ａｇ、及びＭｎの群から選ばれた１種以上を合計で２．０質量％以下含有し、残部が銅及び不可避的不純物から構成されることを特徴とする上記（１）〜（３）いずれか１項記載の挿抜性及び耐熱性に優れる銅合金すずめっき条。
（８）該銅合金条は、１．０〜５．０質量％のＴｉを含有し、更に必要に応じてＺｎ、Ｎｉ、Ｃｏ、Ｐ、Ｃｒ、Ｆｅ、Ａｇ、及びＭｎの群から選ばれた１種以上を合計で２．０質量％以下含有し、残部が銅及び不可避的不純物から構成されることを特徴とする上記（１）〜（３）いずれか１項記載の挿抜性及び耐熱性に優れる銅合金すずめっき条。
As described above, when the average roughness of the Cu—Sn alloy phase is increased, the insertability is improved, and when it is decreased, the heat resistance is improved. Based on this discovery, the present inventor has found a condition of average roughness that can simultaneously provide good insertion / extraction and heat resistance. That is, the present invention provides the following plating strips.
(1) The average roughness Ra of the Cu—Sn alloy phase obtained by electroplating Cu and Sn on the surface of the copper alloy strip and then performing a reflow treatment is 0.05 to 0.3 μm. A copper alloy tin plating strip excellent in insertion / extraction and heat resistance.
(2) From the surface to the copper alloy strip base material, a plating film is composed of each of the Sn phase, the Cu—Sn alloy phase, and the Cu phase, and the average thickness of the Sn phase is 0.02 to 2.0 μm, Cu—Sn The copper alloy tin-plated strip having excellent insertability and heat resistance according to (1) above, wherein the alloy phase has a thickness of 0.1 to 2.0 μm and the Cu phase has a thickness of 0 to 2.0 μm.
(3) From the surface to the copper alloy strip base material, a plating film is composed of each phase of Sn phase, Cu—Sn alloy phase, and Ni phase, the average thickness of Sn phase is 0.02 to 2.0 μm, Cu—Sn The copper alloy tin plating strip excellent in insertion / extraction and heat resistance of (1) above, wherein the alloy phase has a thickness of 0.1 to 2.0 μm and the Ni phase has a thickness of 0.1 to 2.0 μm.
(4) The copper alloy strip contains 1.0 to 4.5% by mass of Ni, contains 1/6 to 1/4 of Si with respect to the mass% of Ni, and further contains Zn, if necessary. One or more selected from the group consisting of Sn, Mg, Co, Ag, Cr and Mn is contained in a total amount of 2.0% by mass or less, and the remainder is composed of copper and inevitable impurities ( 1) to (3) A copper alloy tin-plated strip excellent in insertion / removability and heat resistance according to any one of the items.
(5) The copper alloy strip contains 1 to 11% by mass of Sn and 0.01 to 0.2% by mass of P, and further contains Zn, Ni, Co, Fe, Ag, and Mn as required. One or more types selected from the group are contained in a total of 2.0% by mass or less, and the balance is composed of copper and unavoidable impurities, (1) to (3) above, Copper alloy tin-plated strip with excellent insertability and heat resistance.
(6) The copper alloy strip contains 25 to 40% by mass of Zn, and further includes at least one selected from the group of Ni, Cr, Co, Sn, Fe, Ag, and Mn as required. The copper alloy tin excellent in insertion / extraction and heat resistance according to any one of the above (1) to (3), wherein the content is 2.0% by mass or less, and the balance is composed of copper and inevitable impurities Plating strip.
(7) The copper alloy strip contains 2 to 22% by mass of Zn, and further includes at least one selected from the group of Ni, Cr, Co, Sn, Fe, Ag, and Mn as required. The copper alloy tin excellent in insertion / extraction and heat resistance according to any one of the above (1) to (3), wherein the content is 2.0% by mass or less, and the balance is composed of copper and inevitable impurities Plating strip.
(8) The copper alloy strip contains 1.0 to 5.0% by mass of Ti, and is further selected from the group of Zn, Ni, Co, P, Cr, Fe, Ag, and Mn as necessary. 1 or more in total and 2.0 mass% or less in total, The remainder is comprised from copper and an unavoidable impurity, The insertion / extraction property and heat resistance of any one of said (1)-(3) characterized by the above-mentioned Copper alloy tin plating strip with excellent properties.
本発明は、良好な挿抜性及び耐熱性を有するすずめっき銅合金条を提供する。 The present invention provides a tin-plated copper alloy strip having good insertability and heat resistance.
Ｃｕ−Ｓｎ合金相の平均粗さ
Ｃｕ−Ｓｎ合金相の平均粗さＲａが、０．０５μｍ以上になると挿抜性が向上し、０．３μｍ以下になると耐熱性が向上する。そこで、Ｃｕ−Ｓｎ合金相の平均粗さＲａを０．０５〜０．３μｍ、好ましくは０．１０〜０．２５μｍとなるように制御する。
Average Roughness of Cu—Sn Alloy Phase When the average roughness Ra of the Cu—Sn alloy phase is 0.05 μm or more, insertability is improved, and when it is 0.3 μm or less, heat resistance is improved. Therefore, the average roughness Ra of the Cu—Sn alloy phase is controlled to be 0.05 to 0.3 μm, preferably 0.10 to 0.25 μm.
めっきの種類
本発明を適用できる下地めっき、Ｓｎめっきの仕様として、次のものが挙げられる。
（１）Ｃｕ下地リフローＳｎめっき
請求項２に該当するめっき構造であり、表面から母材にかけて、Ｓｎ相、Ｃｕ−Ｓｎ合金相、Ｃｕ相の各相でめっき皮膜が構成されることを特徴とする。Ｃｕ下地めっき、Ｓｎめっきの順に電気めっきを行い、リフロー処理を施すことにより、このめっき皮膜構造が得られる。
リフロー後のＳｎ相の平均厚みは０．０２〜２．０μｍとする。Ｓｎ相が０．０２μｍ未満になると半田濡れ性が低下し、２．０μｍを超えると、挿入力が増大する。
リフロー後のＣｕ−Ｓｎ合金相の厚みは０．１〜２．０μｍとする。Ｃｕ−Ｓｎ合金相は硬質なため、０．１μｍ以上の厚さで存在すると、挿入力の低減に寄与する。一方、Ｃｕ−Ｓｎ合金相の厚さが２．０μｍを超えると、加熱したときの接触抵抗の増大や半田濡れ性の劣化が顕著になる。すなわち、耐熱性が低下する。
電気めっきで形成したＣｕ下地めっきは、リフロー時にＣｕ−Ｓｎ合金（相）形成に消費され、その厚みがゼロになっても良い。一方、リフロー後のＣｕ相の厚みが２．０μｍを超えるめっき材では、リフロー後のＣｕ−Ｓｎ合金相のＲａが０．３μｍを超える。これは、Ｃｕ下地めっきが厚くなるに従い、Ｃｕの電着粒が局部的に粗大化するためと考えられる。そこで、リフロー後のＣｕ相の厚みは２．０μｍ以下とする。
電気めっき時の各めっきの厚みを、Ｓｎめっきは０．４〜２．２μｍの範囲、Ｃｕめっきは０．１〜２．２μｍの範囲で適宜調整し、その次に２３０〜６００℃、３〜３０秒間の範囲のなかの適当な条件でリフロー処理を行うことにより、上記めっき構造が得られる。
Types of plating The following are listed as specifications of the base plating and Sn plating to which the present invention can be applied.
(1) Cu underlayer reflow Sn plating A plating structure corresponding to claim 2, characterized in that a plating film is composed of Sn phase, Cu—Sn alloy phase, and Cu phase from the surface to the base material. To do. This plating film structure can be obtained by performing electroplating in the order of Cu base plating and Sn plating and performing reflow treatment.
The average thickness of the Sn phase after reflowing is 0.02 to 2.0 μm. When the Sn phase is less than 0.02 μm, the solder wettability is lowered, and when it exceeds 2.0 μm, the insertion force is increased.
The thickness of the Cu—Sn alloy phase after reflowing is 0.1 to 2.0 μm. Since the Cu—Sn alloy phase is hard, if it exists with a thickness of 0.1 μm or more, it contributes to a reduction in insertion force. On the other hand, when the thickness of the Cu—Sn alloy phase exceeds 2.0 μm, the contact resistance increases when heated and the solder wettability deteriorates. That is, heat resistance is reduced.
The Cu base plating formed by electroplating may be consumed to form a Cu—Sn alloy (phase) during reflow, and the thickness thereof may be zero. On the other hand, in the plated material in which the thickness of the Cu phase after reflow exceeds 2.0 μm, the Ra of the Cu—Sn alloy phase after reflow exceeds 0.3 μm. This is thought to be because the electrodeposited grains of Cu are locally coarsened as the thickness of the Cu undercoat increases. Therefore, the thickness of the Cu phase after reflowing is set to 2.0 μm or less.
The thickness of each plating at the time of electroplating is appropriately adjusted in the range of 0.4 to 2.2 μm for Sn plating and 0.1 to 2.2 μm for Cu plating, and then 230 to 600 ° C., 3 to The above-described plating structure can be obtained by performing a reflow process under an appropriate condition within a range of 30 seconds.
（２）Ｃｕ／Ｎｉ下地リフローＳｎめっき
請求項３に該当するめっき構造であり、表面から母材にかけて、Ｓｎ相、Ｃｕ−Ｓｎ合金相、Ｎｉ相の各相でめっき皮膜が構成されることを特徴とする。Ｎｉ下地めっき、Ｃｕ下地めっき、Ｓｎめっきの順に電気めっきを行い、リフロー処理を施すことにより、このめっき皮膜構造が得られる。このめっきに関する技術は、特許文献４、６及び７等に開示されている。
リフロー後のＳｎ相の平均厚みは０．０２〜２．０μｍとする。Ｓｎ相が０．０２μｍ未満になると半田濡れ性が低下し、２．０μｍを超えると、挿入力が増大する。
リフロー後のＣｕ−Ｓｎ合金相の厚みは０．１〜２．０μｍとする。Ｃｕ−Ｓｎ合金相は硬質なため、０．１μｍ以上の厚さで存在すると、挿入力の低減に寄与する。一方、Ｃｕ−Ｓｎ合金相の厚さが２．０μｍを超えると、Ｃｕ下地の場合と同様に耐熱性が低下する。
リフロー後のＮｉ相の厚みは０．１〜２．０μｍとする。Ｎｉの厚みが０．１μｍ未満ではめっきの耐食性や耐熱性が低下する。一方、リフロー後のＮｉの厚みが２．０μｍを超えるめっき材では、リフロー後のＣｕ−Ｓｎ合金相のＲａが０．３μｍを超え、耐熱性が低下する。これは、Ｎｉ下地めっきが厚くなるに従い、Ｎｉ相の表面粗さが増加するためである。
電気めっき時の各めっきの厚みを、Ｓｎめっきは０．４〜２．５μｍの範囲、Ｃｕめっきは０．１〜０．４μｍ、Ｎｉめっきは０．１〜２．０μｍの範囲で適宜調整し、その次に２３０〜６００℃、３〜３０秒間の範囲のなかの適当な条件でリフロー処理を行うことにより、上記めっき構造が得られる。Ｃｕめっき相はリフロー後にＣｕ−Ｓｎ合金相へ完全に転換されてもよく、０．１μｍ以下の厚みで残存しても良い。
(2) Cu / Ni underlayer reflow Sn plating It is a plating structure corresponding to claim 3, and the plating film is composed of Sn phase, Cu-Sn alloy phase and Ni phase from the surface to the base material. Features. This plating film structure is obtained by performing electroplating in the order of Ni base plating, Cu base plating, and Sn plating, and performing reflow treatment. Techniques related to this plating are disclosed in
The average thickness of the Sn phase after reflowing is 0.02 to 2.0 μm. When the Sn phase is less than 0.02 μm, the solder wettability is lowered, and when it exceeds 2.0 μm, the insertion force is increased.
The thickness of the Cu—Sn alloy phase after reflowing is 0.1 to 2.0 μm. Since the Cu—Sn alloy phase is hard, if it exists with a thickness of 0.1 μm or more, it contributes to a reduction in insertion force. On the other hand, when the thickness of the Cu—Sn alloy phase exceeds 2.0 μm, the heat resistance decreases as in the case of the Cu base.
The thickness of the Ni phase after reflowing is 0.1 to 2.0 μm. If the thickness of Ni is less than 0.1 μm, the corrosion resistance and heat resistance of the plating deteriorate. On the other hand, in the plated material in which the thickness of Ni after reflow exceeds 2.0 μm, Ra of the Cu—Sn alloy phase after reflow exceeds 0.3 μm, and the heat resistance decreases. This is because the surface roughness of the Ni phase increases as the Ni base plating becomes thicker.
The thickness of each plating at the time of electroplating is appropriately adjusted within the range of 0.4 to 2.5 μm for Sn plating, 0.1 to 0.4 μm for Cu plating, and 0.1 to 2.0 μm for Ni plating. Then, the above-described plated structure is obtained by performing a reflow process under appropriate conditions in the range of 230 to 600 ° C. and 3 to 30 seconds. The Cu plating phase may be completely converted into a Cu—Sn alloy phase after reflow, or may remain in a thickness of 0.1 μm or less.
銅合金母材の種類
本発明を適用できる銅合金母材として、次のものが挙げられる。
（１）Ｃｕ−Ｎｉ−Ｓｉ系合金
請求項４に該当する銅合金であり、コルソン合金と呼ばれる。時効処理を行うことによりＣｕ中にＮｉとＳｉの化合物粒子が析出し、高い強度と導電率が得られる。実用合金として、Ｃ７０２５０、Ｃ６４７２５、Ｃ６４７６０（ＣＤＡ番号、以下同様）等がある。本発明の銅合金条がＣｕ−Ｎｉ−Ｓｉ系合金である場合について下記に説明する。
Ｎｉは１．０〜４．５質量％の範囲で添加する。Ｎｉが１．０未満であると充分な強度が得られない。Ｎｉが４．５質量％を超えると、鋳造や熱間圧延で割れが発生する。
Ｓｉの添加濃度（質量％）は、Ｎｉの添加濃度（質量％）の１／６〜１／４の範囲とする。Ｓｉがこの範囲から外れると、導電率が低下する。
強度、耐熱性等の特性を改善するために、更に必要に応じてＺｎ、Ｓｎ、Ｍｇ、Ｃｏ、Ａｇ、Ｃｒ及びＭｎの群から選ばれた１種以上を添加することができる。ただし、添加量が増えると導電率が低下するため、合計添加量を２．０質量％以下とする。
Types of Copper Alloy Base Material Examples of the copper alloy base material to which the present invention can be applied include the following.
(1) Cu—Ni—Si-based alloy This is a copper alloy corresponding to claim 4 and is called a Corson alloy. By performing the aging treatment, Ni and Si compound particles are precipitated in Cu, and high strength and electrical conductivity are obtained. Practical alloys include C70250, C64725, C64760 (CDA number, the same applies hereinafter) and the like. The case where the copper alloy strip of the present invention is a Cu-Ni-Si alloy will be described below.
Ni is added in the range of 1.0 to 4.5 mass%. If Ni is less than 1.0, sufficient strength cannot be obtained. When Ni exceeds 4.5 mass%, a crack generate | occur | produces by casting or hot rolling.
The addition concentration (mass%) of Si is in the range of 1/6 to 1/4 of the addition concentration (mass%) of Ni. If Si deviates from this range, the conductivity decreases.
In order to improve properties such as strength and heat resistance, one or more selected from the group of Zn, Sn, Mg, Co, Ag, Cr and Mn can be added as necessary. However, since the electrical conductivity decreases as the amount added increases, the total amount added is 2.0% by mass or less.
（２）りん青銅
請求項５に該当し、実用合金としてＣ５２４００、Ｃ５２１００、Ｃ５１９１０、Ｃ５１０２０等がある。本発明の銅合金条がりん青銅である場合について下記に説明する。
Ｓｎは１〜１１質量％の範囲で添加する。Ｓｎの添加量を増やすと強度が増加する反面、導電率が低下する。添加量が１．０質量％未満であると強度が不充分となり、１１質量％を超えると導電率が不充分となる。
Ｐは脱酸等を目的とし０．０１〜０．２質量％の範囲で添加する。添加量が０．０１質量％未満であると酸素濃度が高くなり、鋳肌の劣化、介在物の増加等を招く。添加量が０．２質量％を超えると導電率が低下する。
強度、耐熱性等の特性を改善するために、更に必要に応じてＺｎ、Ｎｉ、Ｃｏ、Ｆｅ、Ａｇ、及びＭｎの群から選ばれた１種以上を添加することができる。ただし、添加量が増えると導電率が低下するため、合計添加量を２．０質量％以下とする。
(2) Phosphor bronze Corresponding to claim 5, there are C52400, C52100, C51910, C51020, etc. as practical alloys. The case where the copper alloy strip of the present invention is phosphor bronze will be described below.
Sn is added in the range of 1 to 11% by mass. Increasing the amount of Sn added increases the strength but decreases the conductivity. If the addition amount is less than 1.0% by mass, the strength becomes insufficient, and if it exceeds 11% by mass, the conductivity becomes insufficient.
P is added in the range of 0.01 to 0.2% by mass for the purpose of deoxidation and the like. If the amount added is less than 0.01% by mass, the oxygen concentration increases, leading to deterioration of the casting surface, increase in inclusions, and the like. If the amount added exceeds 0.2% by mass, the electrical conductivity will decrease.
In order to improve properties such as strength and heat resistance, one or more selected from the group of Zn, Ni, Co, Fe, Ag, and Mn can be further added as necessary. However, since the electrical conductivity decreases as the amount added increases, the total amount added is 2.0% by mass or less.
（３）黄銅
請求項６に該当し、実用合金としてＣ２６０００、Ｃ２６８００等がある。本発明の銅合金条が黄銅である場合について下記に説明する。
Ｚｎは２５〜４０質量％の範囲で添加する。Ｚｎの添加量を増やすと強度が増加する反面、導電率が低下する。添加量が２５質量％未満であると強度が不充分となり、４０質量％を超えると導電率が不充分となる。
強度、耐熱性等の特性を改善するために、更に必要に応じてＮｉ、Ｃｒ、Ｃｏ、Ｓｎ、Ｆｅ、Ａｇ、及びＭｎの群から選ばれた１種以上を添加することができる。ただし、添加量が増えると導電率が低下するため、合計添加量を２．０質量％以下とする。
(3) Brass Corresponding to claim 6 and practical alloys include C26000, C26800, and the like. The case where the copper alloy strip of the present invention is brass will be described below.
Zn is added in the range of 25 to 40% by mass. Increasing the amount of Zn added increases the strength but decreases the conductivity. If the amount added is less than 25% by mass, the strength will be insufficient, and if it exceeds 40% by mass, the electrical conductivity will be insufficient.
In order to improve properties such as strength and heat resistance, one or more selected from the group of Ni, Cr, Co, Sn, Fe, Ag, and Mn can be added as necessary. However, since the electrical conductivity decreases as the amount added increases, the total amount added is 2.0% by mass or less.
（４）丹銅
請求項７に該当し、実用合金としてＣ２３０００、Ｃ２２０００、Ｃ２１０００等がある。本発明の銅合金条が丹銅である場合について下記に説明する。
Ｚｎは２〜２２質量％の範囲で添加する。Ｚｎの添加量を増やすと強度が増加する反面、導電率が低下する。添加量が２質量％未満であると強度が不充分となり、２２質量％を超えると導電率が不充分となる。
強度、耐熱性等の特性を改善するために、更に必要に応じてＮｉ、Ｃｒ、Ｃｏ、Ｓｎ、Ｆｅ、Ａｇ、及びＭｎの群から選ばれた１種以上を添加することができる。ただし、添加量が増えると導電率が低下するため、合計添加量を２．０質量％以下とする。
(4) Red copper Corresponds to claim 7, and practical alloys include C23000, C22000, C21000, and the like. The case where the copper alloy strip of the present invention is a brass is described below.
Zn is added in the range of 2 to 22% by mass. Increasing the amount of Zn added increases the strength but decreases the conductivity. If the addition amount is less than 2% by mass, the strength is insufficient, and if it exceeds 22% by mass, the conductivity is insufficient.
In order to improve properties such as strength and heat resistance, one or more selected from the group of Ni, Cr, Co, Sn, Fe, Ag, and Mn can be added as necessary. However, since the electrical conductivity decreases as the amount added increases, the total amount added is 2.0% by mass or less.
（５）チタン銅
請求項８に該当し、実用合金としてＣ１９９００等がある。時効処理を行うことによりＴｉとＣｕの化合物がＣｕ中に析出し、非常に高い強度が得られる。本発明の銅合金条がチタン銅である場合について下記に説明する。
Ｔｉは１．０〜５．０質量％の範囲で添加する。Ｔｉが１．０未満であると充分な強度が得られない。Ｔｉが５．０質量％を超えると、鋳造や熱間圧延で割れが発生する。
強度、耐熱性等の特性を改善するために、更に必要に応じてＺｎ、Ｎｉ、Ｃｏ、Ｐ、Ｃｒ、Ｆｅ、Ａｇ、及びＭｎの群から選ばれた１種以上を添加することができる。ただし、添加量が増えると導電率が低下するため、合計添加量を２．０質量％以下とする。
(5) Titanium copper Corresponding to claim 8, C19900 and the like are practical alloys. By performing the aging treatment, a compound of Ti and Cu is precipitated in Cu, and a very high strength is obtained. The case where the copper alloy strip of the present invention is titanium copper will be described below.
Ti is added in the range of 1.0 to 5.0 mass%. If Ti is less than 1.0, sufficient strength cannot be obtained. If Ti exceeds 5.0% by mass, cracking occurs during casting or hot rolling.
In order to improve properties such as strength and heat resistance, one or more selected from the group of Zn, Ni, Co, P, Cr, Fe, Ag, and Mn can be added as necessary. However, since the electrical conductivity decreases as the amount added increases, the total amount added is 2.0% by mass or less.
Ｃｕ−Ｓｎ合金相の平均粗さの制御方法
Ｃｕの電気めっきでは、Ｃｕイオンを含む溶液中で、被めっき材を陰極として通電することにより、被めっき材表面にＣｕを還元析出させる。その際、Ｃｕ電着粒の大きさを制御することにより、Ｓｎ電気めっき後のリフロー処理で形成されるＣｕ−Ｓｎ合金相の平均粗さを調整できる。このＣｕ−Ｓｎ合金相の平均粗さがＳｎめっき銅合金条の挿抜性及び耐熱性に強い影響を及ぼす。
Ｃｕ電着粒が粗大になるとＣｕ−Ｓｎ合金相表面が粗くなる。反対に、Ｃｕ電着粒が微細になるとＣｕ−Ｓｎ合金相表面が平滑になる。Ｃｕ電着粒を小さくするためには、
（１）電流密度を大きくすること
（２）めっき浴液の撹拌速度を上げること
（３）めっき浴に適当な界面活性剤を加えること
（４）めっき浴の温度を下げること
（５）めっき浴の濃度を上げること
等が効果的である。
Control Method of Average Roughness of Cu—Sn Alloy Phase In Cu electroplating, Cu is reduced and deposited on the surface of the material to be plated by energizing the material to be plated as a cathode in a solution containing Cu ions. In that case, the average roughness of the Cu-Sn alloy phase formed by the reflow process after Sn electroplating can be adjusted by controlling the magnitude | size of Cu electrodeposition grain. The average roughness of the Cu—Sn alloy phase has a strong effect on the insertability and heat resistance of the Sn-plated copper alloy strip.
When Cu electrodeposited grains become coarse, the Cu-Sn alloy phase surface becomes rough. On the contrary, when the Cu electrodeposited grains become finer, the Cu-Sn alloy phase surface becomes smooth. In order to reduce Cu electrodeposition grains,
(1) Increasing the current density (2) Increasing the stirring speed of the plating bath solution (3) Adding an appropriate surfactant to the plating bath (4) Lowering the temperature of the plating bath (5) Plating bath It is effective to increase the concentration.
表１の５種類の銅合金（厚み０．２５ｍｍ）に、Ｃｕ下地めっき又はＣｕ／Ｎｉ下地めっきを施した後、リフローＳｎめっきを行った。Ｃｕ下地めっき材では、表２の条件でＣｕめっきを行った。Ｃｕ／Ｎｉ下地めっき材では、表２の条件でＣｕめっきを行った後、表３の条件でＮｉめっきを行った。Ｓｎめっきは表４の条件で行い、Ｓｎめっき後のリフロー処理では５００℃で５秒加熱後、６０℃の水中に投入した。Ｃｕ下地めっき、Ｃｕ／Ｎｉ下地めっきの場合とも、表２に示すようにＣｕの電気めっき条件をａ〜ｄと変えることにより、Ｃｕ−Ｓｎ合金相の平均粗さを変化させた。 After five types of copper alloys (thickness: 0.25 mm) in Table 1 were subjected to Cu base plating or Cu / Ni base plating, reflow Sn plating was performed. For the Cu base plating material, Cu plating was performed under the conditions shown in Table 2. For the Cu / Ni base plating material, Cu plating was performed under the conditions in Table 2, and then Ni plating was performed under the conditions in Table 3. Sn plating was performed under the conditions shown in Table 4. In the reflow treatment after Sn plating, heating was performed at 500 ° C. for 5 seconds and then poured into water at 60 ° C. In the case of Cu undercoating and Cu / Ni undercoating, the average roughness of the Cu—Sn alloy phase was changed by changing the Cu electroplating conditions to a to d as shown in Table 2.
リフロー後の材料について、以下の評価を行った。
（１）めっき厚
Ｓｎ相、Ｃｕ−Ｓｎ合金相、Ｃｕ相、Ｎｉ相の各相の厚みを求めた。測定には主として電解式膜厚計を用い、蛍光Ｘ線膜厚計、断面からのＳＥＭ観察、表面からのＧＤＳ（グロー放電発光分光分析装置）分析等も必要に応じて用いた。Ｃｕ／Ｎｉ下地リフローＳｎめっきの測定を行う際には、特開２００４−０６８０２６号公報に開示された測定技術も参考にした。
（２）平均粗さ
リフロー後に形成されるＣｕ−Ｓｎ拡散相の平均粗さを求めた。Ｍｅｌｔｅｘ社製エンストリップＴＬ−１０５液に２５℃で１分浸漬させ、Ｓｎ相を溶解除去し、Ｃｕ−Ｓｎ合金相を表面に現出させた後、Ｃｕ−Ｓｎ拡散相の平均粗さＲａをＥＬＩＯＮＩＸ社製凹凸ＳＥＭ（ＥＲＡ−８０００）により求めた。測定は圧延方向と平行に行った。５０００倍の倍率のＳＥＭ画像を図３に、図３画像中の直線に沿って測定したＣｕ−Ｓｎ合金相の表面粗さプロファイルを図４に示す。このプロファイルよりＲａを計算した。
（３）接触抵抗に関する耐熱性
耐熱性の評価として、加熱前及び１００、５００、１０００ｈ加熱した後の接触抵抗を測定した。なお、Ｃｕ下地めっきは１４５℃で加熱し、Ｃｕ／Ｎｉ下地めっきは１７５℃で加熱した。接触抵抗は、山崎精機研究所製電気接点シュミレータＣＲＳ−１１３−Ａｕ型を用い、四端子法により、電圧２００ｍＶ、電流１０ｍＡ、摺動荷重０．４９Ｎ、摺動速度１ｍｍ／ｍｉｎ、摺動距離１ｍｍで測定した。
The following evaluation was performed about the material after reflow.
(1) Plating thickness The thickness of each phase of Sn phase, Cu-Sn alloy phase, Cu phase, and Ni phase was determined. For the measurement, an electrolytic film thickness meter was mainly used, and a fluorescent X-ray film thickness meter, SEM observation from a cross section, GDS (glow discharge emission spectroscopy analyzer) analysis from the surface, and the like were used as needed. When measuring Cu / Ni foundation reflow Sn plating, the measurement technique disclosed in Japanese Patent Application Laid-Open No. 2004-0668026 was also referred to.
(2) Average roughness The average roughness of the Cu-Sn diffusion phase formed after reflow was determined. After immersion in Meltex Enstrip TL-105 solution at 25 ° C. for 1 minute, the Sn phase was dissolved and removed, and the Cu—Sn alloy phase appeared on the surface. Then, the average roughness Ra of the Cu—Sn diffusion phase was determined. It calculated | required by the uneven | corrugated SEM (ERA-8000) by ELIONIX. The measurement was performed in parallel with the rolling direction. FIG. 3 shows an SEM image at a magnification of 5000 times, and FIG. 4 shows a surface roughness profile of the Cu—Sn alloy phase measured along a straight line in the image of FIG. Ra was calculated from this profile.
(3) Heat resistance regarding contact resistance As evaluation of heat resistance, contact resistance before heating and after heating for 100, 500, and 1000 hours was measured. Note that the Cu undercoat was heated at 145 ° C., and the Cu / Ni undercoat was heated at 175 ° C. The contact resistance is an electric contact simulator CRS-113-Au type manufactured by Yamazaki Seiki Laboratories, and by a four-terminal method, a voltage of 200 mV, a current of 10 mA, a sliding load of 0.49 N, a sliding speed of 1 mm / min, and a sliding distance of 1 mm. Measured with
（４）挿抜性
コネクタ勘合時の挿入力は、動摩擦係数により評価した。図５に示すように、Ｓｎめっき材の板試料を試料台上に固定し、そのＳｎめっき面に接触子を荷重Ｗで押し付けた。次に、移動台を水平方向に移動させ、このとき接触子に作用する抵抗加重Ｆをロードセルにより測定した。そして、動摩擦係数μをμ＝Ｆ／Ｗより算出した。
Ｗは４．９Ｎとし、接触子の摺動速度（試料台の移動速度）は５０ｍｍ／ｍｉｎとした。摺動は板試料の圧延方向に対し平行な方向に行った。摺動距離は１００ｍｍとし、この間のＦの平均値を求めた。
接触子は、上記板試料と同じＳｎめっき材を用い、図６のように作製した。すなわち、直径７ｍｍのステンレス球を試料に押し付けて、板試料と接触する部分を半球状に成形した。
(4) Insertion / Removability The insertion force at the time of connector fitting was evaluated by the dynamic friction coefficient. As shown in FIG. 5, a plate sample of Sn plating material was fixed on a sample table, and a contact was pressed against the Sn plating surface with a load W. Next, the moving table was moved in the horizontal direction, and the resistance weight F acting on the contact at this time was measured with a load cell. The dynamic friction coefficient μ was calculated from μ = F / W.
W was 4.9 N, and the sliding speed of the contact (moving speed of the sample stage) was 50 mm / min. The sliding was performed in a direction parallel to the rolling direction of the plate sample. The sliding distance was 100 mm, and the average value of F during this period was obtained.
The contact was produced as shown in FIG. 6 using the same Sn plating material as the plate sample. That is, a stainless steel sphere having a diameter of 7 mm was pressed against the sample, and a portion in contact with the plate sample was formed into a hemisphere.
実施例１
銅合金Ａ〜Ｅに対し、Ｃｕ下地めっき又はＣｕ／Ｎｉ下地めっき後にリフローＳｎめっきを行った。Ｃｕ下地めっきは表２のａ〜ｄの４条件で行った。
表５、６に各めっき厚み、平均粗さ、加熱前後の接触抵抗及び動摩擦係数を示す。表５はＣｕ下地めっきの実施例、表６はＣｕ／Ｎｉ下地めっきの実施例である。ｂ、ｃの条件でＣｕ下地めっきを施した場合、Ｃｕ−Ｓｎ合金相の平均粗さＲａは０．０５〜０．３μｍを満たした。ｄの条件ではＲａが本発明の上限値（０．３μｍ）を超え、ａの条件ではＲａが下限値（０．０５μｍ）未満であった。
図７Ａ〜Ｅは、それぞれ銅合金Ａ〜ＥにＣｕ下地を採用してＳｎめっきした場合のＣｕ−Ｓｎ合金相の平均粗さに対する、動摩擦係数及び接触抵抗（１４５℃で１０００ｈ加熱後）の変化を示したものである。例えば、図７Ａは、銅合金ＡにＣｕ下地を採用した比較例１、発明例２、３及び比較例４の平均粗さに対する、動摩擦係数及び接触抵抗（１４５℃で１０００ｈ加熱後）の変化を示す。同様に、図８Ａ〜Ｅは、それぞれ銅合金Ａ〜ＥにＣｕ／Ｎｉ下地を採用してＳｎめっきした場合のＣｕ−Ｓｎ合金相の平均粗さに対する、動摩擦係数及び接触抵抗（１４５℃で１０００ｈ加熱後）の変化を示したものである。下地めっきの種類及び銅合金の種類によらず、Ｃｕ−Ｓｎ合金相の平均粗さが０．０５μｍより小さくなると動摩擦係数が急激に高くなった。反対に、Ｃｕ−Ｓｎ合金相の平均粗さが０．３μｍより大きくなると加熱後の接触抵抗が急激に高くなった。Ｃｕ−Ｓｎ合金相の平均粗さが０．０５〜０．３μｍの範囲では、動摩擦係数、接触抵抗ともに低く、良好な挿抜性と耐熱性が得られている。
Example 1
The copper alloys A to E were subjected to reflow Sn plating after Cu undercoating or Cu / Ni undercoating. Cu underplating was performed under the four conditions a to d in Table 2.
Tables 5 and 6 show the plating thickness, average roughness, contact resistance before and after heating, and dynamic friction coefficient. Table 5 shows examples of Cu base plating, and Table 6 shows examples of Cu / Ni base plating. When Cu base plating was performed under the conditions of b and c, the average roughness Ra of the Cu—Sn alloy phase satisfied 0.05 to 0.3 μm. Under the condition d, Ra exceeded the upper limit (0.3 μm) of the present invention, and under the condition a, Ra was less than the lower limit (0.05 μm).
FIGS. 7A to E show changes in the dynamic friction coefficient and contact resistance (after heating at 145 ° C. for 1000 h) with respect to the average roughness of the Cu—Sn alloy phase when Sn plating is performed on copper alloys A to E, respectively. Is shown. For example, FIG. 7A shows changes in the dynamic friction coefficient and the contact resistance (after heating at 145 ° C. for 1000 h) with respect to the average roughness of Comparative Examples 1, Invention Examples 2, 3 and Comparative Example 4 in which a Cu base is used for the copper alloy A. Show. Similarly, FIGS. 8A to E show the dynamic friction coefficient and the contact resistance (1000 h at 145 ° C.) with respect to the average roughness of the Cu—Sn alloy phase in the case of Sn plating using a Cu / Ni base for the copper alloys A to E, respectively. The change after heating is shown. Regardless of the type of base plating and the type of copper alloy, the dynamic friction coefficient increased rapidly when the average roughness of the Cu—Sn alloy phase was smaller than 0.05 μm. On the other hand, when the average roughness of the Cu—Sn alloy phase was larger than 0.3 μm, the contact resistance after heating rapidly increased. When the average roughness of the Cu—Sn alloy phase is in the range of 0.05 to 0.3 μm, both the dynamic friction coefficient and the contact resistance are low, and good insertability and heat resistance are obtained.
実施例２
めっき各相の厚みが特性に及ぼす影響を、請求項２または３に関しての発明例と比較例とを対比することにより説明する。表７はＣｕ／Ｎｉ下地めっきの場合について、Ｎｉ相、Ｃｕ−Ｓｎ合金相及びＳｎ相の厚みの影響を示すデータである。銅合金Ａ〜Ｅに対し、Ｎｉ下地めっき、ｂの条件のＣｕ下地めっきを順に行った後、リフローＳｎめっきを施している。ただし、比較例４５、５３、６１、６９及び７７はリフローでの加熱時間を長くしている。Ｓｎ相の厚みが２．０μｍを超えた比較例４４、５２、６０、６８及び７６の動摩擦係数は他の試料の動摩擦係数より高い。Ｃｕ−Ｓｎ合金相の厚みが２．０μｍを超えた比較例４５、５３、６１、６９及び７７とリフロー後のＮｉ相の厚みが０．１μｍ未満である比較例４７、５５、６３、７１及び７９の接触抵抗値は他の試料の接触抵抗値より高い傾向にある。リフロー後のＮｉ相の厚みが２．０μｍを超えた比較例４８、５６、６４、７２及び８０ではＣｕ−Ｓｎ合金相のＲａが０．３μｍを超えた。このため比較例４８、５６、６４、７２及び８０の接触抵抗は他の試料より著しく高い。
次に、表８はＣｕ下地めっきの場合について、Ｃｕ相、Ｃｕ−Ｓｎ合金相及びＳｎ相の厚みの影響を示すデータである。銅合金Ａ〜Ｅに対し、ｂの条件のＣｕ下地めっきを行った後、リフローＳｎめっきを施している。ただし、比較例８５、９３、１０１、１０９及び１１７はリフローでの加熱時間を長くしている。Ｓｎ相の厚みが２．０μｍを超えた比較例８４、９２、１００、１０８及び１１６の動摩擦係数は他の試料の動摩擦係数より高い。Ｃｕ−Ｓｎ合金相の厚みが２．０μｍを超えた比較例８５、９３、１０１、１０９及び１１７の接触抵抗値は他の試料の接触抵抗値より高い傾向にある。比較例８８、９６、１０４、１１２及び１２０では２．２μｍより厚いＣｕ下地めっきを施したため、リフロー後のＣｕ相の厚みが２．０μｍを超え、Ｃｕ−Ｓｎ合金相の平均粗さが０．３μｍを超えた。このため比較例８８、９６、１０４、１１２及び１２０の接触抵抗値は他の試料の接触抵抗値より著しく高い。
Example 2
The influence of the thickness of each plating phase on the characteristics will be described by comparing the invention example and the comparative example with respect to claim 2 or 3. Table 7 is data showing the influence of the thickness of the Ni phase, Cu—Sn alloy phase and Sn phase in the case of Cu / Ni undercoat. Reflow Sn plating is performed on the copper alloys A to E after sequentially performing Ni base plating and Cu base plating under the conditions of b. However, in Comparative Examples 45, 53, 61, 69 and 77, the heating time for reflow is increased. The dynamic friction coefficients of Comparative Examples 44, 52, 60, 68 and 76 in which the thickness of the Sn phase exceeds 2.0 μm are higher than the dynamic friction coefficients of the other samples. Comparative Examples 45, 53, 61, 69 and 77 in which the thickness of the Cu-Sn alloy phase exceeded 2.0 μm and Comparative Examples 47, 55, 63, 71 and in which the thickness of the Ni phase after reflowing was less than 0.1 μm The contact resistance value of 79 tends to be higher than the contact resistance values of other samples. In Comparative Examples 48, 56, 64, 72, and 80 in which the thickness of the Ni phase after reflow exceeded 2.0 μm, the Ra of the Cu—Sn alloy phase exceeded 0.3 μm. For this reason, the contact resistances of Comparative Examples 48, 56, 64, 72, and 80 are significantly higher than those of other samples.
Next, Table 8 is data showing the influence of the thickness of the Cu phase, the Cu—Sn alloy phase, and the Sn phase in the case of Cu undercoat. The copper alloys A to E are subjected to reflow Sn plating after performing Cu underplating under the condition of b. However, in Comparative Examples 85, 93, 101, 109, and 117, the heating time for reflow is increased. The dynamic friction coefficients of Comparative Examples 84, 92, 100, 108 and 116 in which the thickness of the Sn phase exceeds 2.0 μm are higher than the dynamic friction coefficients of the other samples. The contact resistance values of Comparative Examples 85, 93, 101, 109 and 117 in which the thickness of the Cu—Sn alloy phase exceeds 2.0 μm tend to be higher than the contact resistance values of other samples. In Comparative Examples 88, 96, 104, 112, and 120, since the Cu base plating thicker than 2.2 μm was applied, the thickness of the Cu phase after reflow exceeded 2.0 μm, and the average roughness of the Cu—Sn alloy phase was 0.00. It exceeded 3 μm. For this reason, the contact resistance values of Comparative Examples 88, 96, 104, 112 and 120 are significantly higher than the contact resistance values of the other samples.
Claims (8)
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