JP5692799B2 - Sn plating material and method for producing the same - Google Patents
Sn plating material and method for producing the same Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims description 237
- 239000000463 material Substances 0.000 title claims description 183
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- 238000000034 method Methods 0.000 claims description 46
- 229910017755 Cu-Sn Inorganic materials 0.000 claims description 44
- -1 Cu-Sn compound Chemical class 0.000 claims description 44
- 229910017927 Cu—Sn Inorganic materials 0.000 claims description 44
- 239000010687 lubricating oil Substances 0.000 claims description 44
- 230000003287 optical effect Effects 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 19
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 17
- 238000009713 electroplating Methods 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000007664 blowing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 4
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000679 solder Inorganic materials 0.000 description 58
- 239000013078 crystal Substances 0.000 description 53
- 238000004070 electrodeposition Methods 0.000 description 49
- 238000003780 insertion Methods 0.000 description 8
- 230000037431 insertion Effects 0.000 description 8
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- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
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- 235000010446 mineral oil Nutrition 0.000 description 2
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- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 238000005238 degreasing Methods 0.000 description 1
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- 150000002222 fluorine compounds Chemical class 0.000 description 1
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- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
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- 238000009736 wetting Methods 0.000 description 1
Description
本発明は、Ｓｎめっき材およびその製造方法に関し、特に、挿抜可能な接続端子などの材料として使用されるＳｎめっき材およびその製造方法に関する。 The present invention relates to an Sn plating material and a method for manufacturing the same, and more particularly, to an Sn plating material used as a material such as a connection terminal that can be inserted and removed and a method for manufacturing the same.
従来、挿抜可能な接続端子の材料として、銅や銅合金などの導体素材の最外層にＳｎめっきを施したＳｎめっき材が使用されている。特に、Ｓｎめっき材は、接触抵抗が小さく、接触信頼性、耐食性、はんだ付け性、経済性などの観点から、自動車、携帯電話、パソコンなどの情報通信機器、ロボットなどの産業機器の制御基板、コネクタ、リードフレーム、リレー、スイッチなどの端子やバスバーの材料として使用されている。 Conventionally, an Sn plated material obtained by applying Sn plating to the outermost layer of a conductor material such as copper or copper alloy has been used as a material for a connection terminal that can be inserted and removed. In particular, Sn plating materials have low contact resistance, and from the viewpoints of contact reliability, corrosion resistance, solderability, economy, etc., control boards for industrial equipment such as automobiles, mobile phones, personal computers and other industrial equipment such as robots, Used as a material for terminals and bus bars of connectors, lead frames, relays, switches, etc.
一般に、このようなＳｎめっきは、電気めっきによって行われており、Ｓｎめっき材の内部応力を除去してウイスカの発生を抑制するために、電気めっきの直後にリフロー処理（Ｓｎ溶融処理）が行われている。このようにＳｎめっき後にリフロー処理を行うと、Ｓｎの一部が素材や下地成分に拡散して化合物層を形成し、この化合物層の上に柔らかい溶融凝固組織になったＳｎ層（以下「純Ｓｎ層」という）が形成される。この純Ｓｎ層は、優れた接触信頼性、耐食性およびはんだ付け性を得るために極めて重要な役割を果たす。 In general, such Sn plating is performed by electroplating, and a reflow process (Sn melting process) is performed immediately after electroplating in order to remove internal stress of the Sn plating material and suppress the generation of whiskers. It has been broken. When the reflow treatment is performed after Sn plating in this way, a part of Sn diffuses into the material and the base component to form a compound layer, and a Sn layer (hereinafter referred to as “pure”) having a soft molten and solidified structure on this compound layer. Sn layer ") is formed. This pure Sn layer plays an extremely important role in order to obtain excellent contact reliability, corrosion resistance and solderability.
しかし、純Ｓｎ層は軟質で変形し易いため、リフロー処理を施したＳｎめっき材を挿抜可能な接続端子などの材料として使用すると、接続端子の挿入時に表面が削れて摩擦係数が高くなって挿入力が高くなるという問題がある。また、自動車などの接続端子では、端子の多極化が進んでおり、端子の数に比例して組立て時の挿入力が上昇し、作業負荷が問題になっている。 However, since the pure Sn layer is soft and easily deformed, if the Sn-plated material subjected to reflow processing is used as a material such as a connection terminal that can be inserted and removed, the surface is scraped when the connection terminal is inserted and the friction coefficient is increased. There is a problem that power becomes high. In connection terminals of automobiles and the like, the number of terminals is increasing, and the insertion force at the time of assembly increases in proportion to the number of terminals, and the work load becomes a problem.
このような問題を解消するため、リフロー処理を施したＳｎめっき材では、軟質層である純Ｓｎ層の膜厚を薄くして、リフロー処理により硬質なＣｕ−Ｓｎ化合物層などの化合物層を下地に形成することによって、摩擦係数の低減を図っている。しかし、純Ｓｎ層を薄くすると、素材や下地の成分が経時変化により最表面に速く拡散して耐熱性や接触信頼性が低下する。そのため、Ｃｕ−Ｓｎ化合物層の下層に拡散抑制層としてＮｉ層を挿入する方法が提案されている（例えば、特許文献１参照）。 In order to solve such problems, in the Sn plating material subjected to reflow treatment, the film thickness of the pure Sn layer, which is a soft layer, is reduced, and a compound layer such as a hard Cu—Sn compound layer is ground by reflow treatment. Thus, the friction coefficient is reduced. However, when the pure Sn layer is thinned, the material and the base component diffuse quickly to the outermost surface due to changes over time, and heat resistance and contact reliability are lowered. Therefore, a method of inserting a Ni layer as a diffusion suppressing layer under the Cu—Sn compound layer has been proposed (see, for example, Patent Document 1).
また、素材の表面に算術平均粗さＲａが０．１５μｍ以上の凹凸を形成して、凸部においてＣｕ−Ｓｎ化合物層を露出させることによって、挿入力を低くする方法も提案されている（例えば、特許文献２参照）。 In addition, a method of reducing the insertion force by forming irregularities having an arithmetic average roughness Ra of 0.15 μm or more on the surface of the material and exposing the Cu—Sn compound layer at the convex portions (for example, , See Patent Document 2).
また、Ｓｎを含む鋼合金の基材を加熱して酸化処理し、水素イオン濃度を所定の範囲に調整したフッ素化合物溶液に浸した後に、下地用金属をめっきすることにより直径１０〜１００μｍの基材の複数の凹部を形成し、接触用金属をめっきし、潤滑物質を塗布して、充分な耐摩耗性のコンタクトを得る方法も提案されている（例えば、特許文献３参照）。 In addition, a base material having a diameter of 10 to 100 μm is obtained by plating a base metal after heating and oxidizing a base material of a steel alloy containing Sn and immersing it in a fluorine compound solution whose hydrogen ion concentration is adjusted to a predetermined range. There has also been proposed a method in which a plurality of concave portions of a material is formed, a contact metal is plated, and a lubricant is applied to obtain a contact with sufficient wear resistance (see, for example, Patent Document 3).
さらに、Ｓｎめっき上にシラン化合物の皮膜を形成することによって、挿入力を低減する方法も提案されている（例えば、特許文献４参照）。 Furthermore, a method of reducing insertion force by forming a silane compound film on Sn plating has been proposed (see, for example, Patent Document 4).
しかし、特許文献１のように、Ｎｉ層を挿入する方法では、Ｎｉめっきの工程の分だけ工程数が多くなり、めっきラインの管理コストやイニシャルコストが増大する。また、純Ｓｎ層を０．２μｍ以下の薄い層にすると、挿入力を低くすることができるものの、Ｃｕ−Ｓｎ化合物層が露出する部分が生じて、はんだ付け性や耐食性が劣化する。 However, as in Patent Document 1, in the method of inserting the Ni layer, the number of steps increases by the Ni plating step, and the management cost and initial cost of the plating line increase. Further, when the pure Sn layer is a thin layer having a thickness of 0.2 μm or less, the insertion force can be lowered, but a portion where the Cu—Sn compound layer is exposed is generated, and solderability and corrosion resistance are deteriorated.
また、特許文献２のように、素材の表面に算術平均粗さＲａが０．１５μｍ以上の凹凸を形成してＣｕ−Ｓｎ化合物層を露出させる方法では、Ｃｕ−Ｓｎ化合物層の露出により、特許文献１と同様にはんだ付け性や耐食性が劣化する。 In addition, as disclosed in Patent Document 2, in the method of forming irregularities having an arithmetic average roughness Ra of 0.15 μm or more on the surface of the material and exposing the Cu—Sn compound layer, the exposure of the Cu—Sn compound layer causes a patent. Similar to Reference 1, solderability and corrosion resistance deteriorate.
また、特許文献３のように、Ｓｎを含む銅合金の基材の表面に凹凸を形成する方法では、基材の種類がＳｎを含む銅合金に限定され、また、素材の処理に多大なコストがかかり、素材の処理により生産性が低くなる。 Further, as in Patent Document 3, in the method of forming irregularities on the surface of a copper alloy substrate containing Sn, the type of the substrate is limited to the copper alloy containing Sn, and the material processing costs are enormous. And the processing of the material reduces the productivity.
さらに、特許文献４のように、プレス加工時に使用されないシラン化合物のような潤滑材を使用すると、プレス加工により連続的に成形するにつれて、プレス機の油として指定した油以外の物質が混入することになり、プレス成形品の形状や金型の管理面の負荷が増大してコストがかかる。 In addition, when a lubricant such as a silane compound that is not used during press processing is used as in Patent Document 4, substances other than the oil designated as the oil for the press machine are mixed as it is continuously formed by press processing. As a result, the load on the shape of the press-formed product and the control surface of the mold increases and costs increase.
したがって、本発明は、このような従来の問題点に鑑み、摩擦係数が低く、耐食性、はんだ濡れ性および接触信頼性に優れたＳｎめっき材およびそのＳｎめっき材を低コストで製造する方法を提供することを目的とする。 Therefore, the present invention provides a Sn plating material having a low coefficient of friction, excellent corrosion resistance, solder wettability, and contact reliability, and a method for producing the Sn plating material at a low cost in view of such conventional problems. The purpose is to do.
本発明者らは、上記課題を解決するために鋭意研究した結果、０．２ｇ／Ｌ以上のＳｎ酸化物を含むＳｎめっき浴を使用して電気めっきにより素材上にＳｎめっき層を形成し、Ｓｎめっき層の表面を乾燥させた後、Ｓｎめっき層の表面を加熱してＳｎを溶融させた後に冷却することにより、摩擦係数が低く、耐食性、はんだ濡れ性および接触信頼性に優れたＳｎめっき材を低コストで製造することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors formed a Sn plating layer on the material by electroplating using a Sn plating bath containing Sn oxide of 0.2 g / L or more, Sn plating layer with low friction coefficient, corrosion resistance, solder wettability and excellent contact reliability by drying Sn plating layer surface, heating Sn plating layer surface to melt Sn and then cooling The present inventors have found that a material can be manufactured at a low cost and have completed the present invention.
すなわち、本発明によるＳｎめっき材の製造方法は、０．２ｇ／Ｌ以上のＳｎ酸化物を含むＳｎめっき浴を使用して電気めっきにより素材上にＳｎめっき層を形成し、Ｓｎめっき層の表面を乾燥させた後、Ｓｎめっき層の表面を加熱してＳｎを溶融させた後に冷却することを特徴とする。 That is, the manufacturing method of the Sn plating material by this invention forms an Sn plating layer on a raw material by electroplating using the Sn plating bath containing 0.2 g / L or more of Sn oxide, The surface of Sn plating layer After drying, the surface of the Sn plating layer is heated to melt Sn, and then cooled.
このＳｎめっき材の製造方法において、Ｓｎめっき浴が硫酸錫を含み、Ｓｎ酸化物がＳｎめっき浴を大気と接触させることによって生成されるのが好ましい。また、電気めっきにより形成されたＳｎめっき層の厚さが０．５μｍ以上であるのが好ましく、電気めっきにより形成されたＳｎめっき層の厚さに対する結晶粒度の比（結晶粒度／厚さ）が１．５以下であるのが好ましい。また、素材が銅または銅合金からなるのが好ましい。 In this method for producing a Sn plating material, it is preferable that the Sn plating bath contains tin sulfate and the Sn oxide is generated by bringing the Sn plating bath into contact with the atmosphere. The thickness of the Sn plating layer formed by electroplating is preferably 0.5 μm or more, and the ratio of the crystal grain size to the thickness of the Sn plating layer formed by electroplating (crystal grain size / thickness) is It is preferably 1.5 or less. Moreover, it is preferable that a raw material consists of copper or a copper alloy.
また、上記のＳｎめっき材の製造方法において、Ｓｎめっき層の表面を加熱してＳｎを溶融させた後に冷却することにより、Ｓｎめっき層から最表面の純Ｓｎ層とその下層の化合物層を形成することができる。この場合、純Ｓｎ層の厚さが０．２μｍ以上であり、化合物層の厚さが０．４μｍ以上であるのが好ましい。また、素材が銅または銅合金からなり、化合物層がＣｕ−Ｓｎ化合物層であるのが好ましい。 Moreover, in the manufacturing method of said Sn plating material, the surface of Sn plating layer is heated, and after melting Sn, it cools, and the outermost pure Sn layer and the compound layer of the lower layer are formed from Sn plating layer can do. In this case, the thickness of the pure Sn layer is preferably 0.2 μm or more, and the thickness of the compound layer is preferably 0.4 μm or more. Moreover, it is preferable that a raw material consists of copper or a copper alloy, and a compound layer is a Cu-Sn compound layer.
さらに、上記のＳｎめっき材の製造方法において、Ｓｎめっき層の表面を加熱してＳｎを溶融させた後に冷却したＳｎめっき材の表面の１５７５μｍ２の領域に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数が５０個以上であるのが好ましい。また、Ｓｎめっき層の表面の光学濃度が１．０以下であるのが好ましい。さらに、Ｓｎめっき層を加熱してＳｎを溶融させた後に冷却した後に、Ｓｎめっき層の表面に潤滑油を塗布するのが好ましい。この場合、Ｓｎめっき層の表面に塗布された潤滑油の量がＳｎめっき層の表面の面積（表面の粗さを考慮せずに平面としたときの面積）に対して２０ｍｇ／ｄｍ２以上であるのが好ましい。 Further, in the above-described method for manufacturing a Sn-plated material, 1575Myuemu region formed area 10 [mu] m 2 or less at a depth of 2 of the surface of the cooled Sn-plated material after heating the surface of the Sn-plated layer is melted Sn It is preferable that the number of minute recesses of 0.1 μm or more is 50 or more. Moreover, it is preferable that the optical density of the surface of Sn plating layer is 1.0 or less. Furthermore, it is preferable to apply a lubricating oil to the surface of the Sn plating layer after cooling the Sn plating layer by heating and melting Sn. In this case, the amount of the lubricating oil applied to the surface of the Sn plating layer is 20 mg / dm 2 or more with respect to the surface area of the Sn plating layer (the area when the surface is flat without considering the surface roughness). Preferably there is.
また、本発明によるＳｎめっき材は、素材上に形成されたＳｎめっき層の表面の１５７５μｍ２の領域に面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部が５０個以上形成されていることを特徴とする。 Moreover, Sn-plated material according to the present invention, the depth 0.1μm or more micro-recesses in the area of 10 [mu] m 2 or less in the region of 1575Myuemu 2 of the surface of the Sn-plated layer formed on the material is formed 50 or more It is characterized by.
このＳｎめっき材において、素材が銅または銅合金からなるのが好ましい。また、Ｓｎめっき層が、最表面側の純Ｓｎ層と、この純Ｓｎ層と素材との間に形成された化合物層とからなるのが好ましい。この場合、純Ｓｎ層の厚さが０．２μｍ以上であり、化合物層の厚さが０．４μｍ以上であるのが好ましい。また、素材が銅または銅合金からなり、化合物層がＣｕ−Ｓｎ化合物層であるのが好ましい。また、Ｓｎめっき材の光学濃度が１．０以下であるのが好ましい。 In this Sn plated material, the material is preferably made of copper or a copper alloy. Moreover, it is preferable that the Sn plating layer is composed of a pure Sn layer on the outermost surface side and a compound layer formed between the pure Sn layer and the material. In this case, the thickness of the pure Sn layer is preferably 0.2 μm or more, and the thickness of the compound layer is preferably 0.4 μm or more. Moreover, it is preferable that a raw material consists of copper or a copper alloy, and a compound layer is a Cu-Sn compound layer. Moreover, it is preferable that the optical density of Sn plating material is 1.0 or less.
また、上記のＳｎめっき材において、微小凹部が形成されたＳｎめっき層の表面に潤滑油が塗布されているのが好ましい。この場合、Ｓｎめっき材の摩擦係数が０．２５以下であるのが好ましい。Ｓｎめっき層の表面に塗布された潤滑油の量がＳｎめっき層の表面の面積（表面を平面としたときの面積）に対して２０ｍｇ／ｄｍ２以上であるのが好ましい。 Further, in the above Sn plating material, it is preferable that a lubricating oil is applied to the surface of the Sn plating layer in which the minute recesses are formed. In this case, it is preferable that the friction coefficient of the Sn plating material is 0.25 or less. The amount of lubricating oil applied to the surface of the Sn plating layer is preferably 20 mg / dm 2 or more with respect to the surface area of the Sn plating layer (area when the surface is a flat surface).
本発明によれば、摩擦係数が低く、耐食性、はんだ濡れ性および接触信頼性に優れたＳｎめっき材を低コストで製造することができる。 According to the present invention, a Sn plating material having a low friction coefficient and excellent corrosion resistance, solder wettability, and contact reliability can be produced at low cost.
本発明によるＳｎめっき材の製造方法の実施の形態では、０．２ｇ／Ｌ以上のＳｎ酸化物を含むＳｎめっき浴を使用して電気めっきにより銅や銅合金などからなる素材上にＳｎめっき層を形成し、Ｓｎめっき層の表面を乾燥させた後、Ｓｎめっき層の表面を加熱してＳｎを溶融させた後に冷却する。 In the embodiment of the method for producing a Sn plating material according to the present invention, a Sn plating layer is formed on a material made of copper, a copper alloy, or the like by electroplating using a Sn plating bath containing Sn oxide of 0.2 g / L or more. After drying the surface of the Sn plating layer, the surface of the Sn plating layer is heated to melt Sn, and then cooled.
このＳｎめっき材の製造方法において、電気めっきにより素材上にＳｎめっき層を形成した後に、Ｓｎめっき層の表面を乾燥させるのは、表面が濡れたままでは、表面が酸化し難く、Ｓｎめっき層の表面を加熱してＳｎを溶融させる際にＳｎめっき層が均一に溶けて広がり易くなって、Ｓｎめっき層の表面に微小凹部を形成し難くなるからである。 In this manufacturing method of the Sn plating material, after forming the Sn plating layer on the material by electroplating, the surface of the Sn plating layer is dried because the surface is difficult to oxidize when the surface is wet. This is because when the surface is heated to melt Sn, the Sn plating layer is uniformly melted and spreads easily, and it becomes difficult to form minute recesses on the surface of the Sn plating layer.
また、Ｓｎめっき浴は、０．２ｇ／Ｌ以上のＳｎ酸化物を含み、１ｇ／Ｌ以上のＳｎ酸化物を含むのが好ましい。Ｓｎめっき浴がＳｎ酸化物を含むと、電気めっきの際にＳｎ酸化物がＳｎ結晶の内部、表面および粒界に巻き込まれて、Ｓｎめっき層の表面を加熱してＳｎを溶融させる際にＳｎめっき層が均一に溶けて広がるのを抑制すると考えられ、また、Ｓｎめっき浴中のＳｎ酸化物の量が０．２ｇ／Ｌより少ないと、Ｓｎを溶融させる際にＳｎめっき層が均一に溶けて広がり易くなってＳｎめっき層の表面に微小凹部を形成し難くなるからである。また、Ｓｎめっき浴が硫酸錫を含み、Ｓｎめっき浴に空気を吹き込んだり、Ｓｎめっき浴を攪拌または循環させて大気と接触させることによって、Ｓｎ酸化物がＳｎめっき浴中に生成されるのが好ましい。 The Sn plating bath preferably contains 0.2 g / L or more of Sn oxide, and preferably contains 1 g / L or more of Sn oxide. When the Sn plating bath contains Sn oxide, Sn oxide is caught in the inside, surface and grain boundary of the Sn crystal during electroplating, and Sn is melted by heating the surface of the Sn plating layer to melt Sn. It is considered that the plating layer is prevented from melting and spreading uniformly, and when the amount of Sn oxide in the Sn plating bath is less than 0.2 g / L, the Sn plating layer is uniformly melted when melting Sn. This is because it becomes easy to spread and it becomes difficult to form minute recesses on the surface of the Sn plating layer. Further, the Sn plating bath contains tin sulfate, and Sn oxide is produced in the Sn plating bath by blowing air into the Sn plating bath or by stirring or circulating the Sn plating bath and contacting with the atmosphere. preferable.
また、電気めっきの際の電流密度を３〜１２Ａ／ｄｍ２にするのが好ましく、電気めっきにより形成されるＳｎめっき層の厚さが０．５μｍ以上であるのが好ましく、０．８μｍ以上であるのがさらに好ましい。また、電気めっきにより形成されるＳｎめっき層の結晶粒度が１．７μｍ以下であるのが好ましく、１．５μｍ以下であるのがさらに好ましい。さらに、Ｓｎめっき層の厚さに対する結晶粒度の比（結晶粒度／厚さ）が１．５以下であるのが好ましく、１．１以下であるのがさらに好ましい。結晶粒度／厚さが１．５より大きいと、粒界が減少してＳｎめっき層の表面に微小凹部を形成し難くなるからである。 The current density during electroplating is preferably 3 to 12 A / dm 2. The thickness of the Sn plating layer formed by electroplating is preferably 0.5 μm or more, and is 0.8 μm or more. More preferably. Further, the grain size of the Sn plating layer formed by electroplating is preferably 1.7 μm or less, and more preferably 1.5 μm or less. Furthermore, the ratio of crystal grain size to the thickness of the Sn plating layer (crystal grain size / thickness) is preferably 1.5 or less, and more preferably 1.1 or less. This is because if the crystal grain size / thickness is larger than 1.5, the grain boundary is reduced, and it becomes difficult to form minute recesses on the surface of the Sn plating layer.
また、Ｓｎめっき層の表面を加熱してＳｎを溶融させた後に冷却することにより、Ｓｎめっき層から最表面の純Ｓｎ層とその下層の化合物層（素材が銅または銅合金の場合にはＣｕ−Ｓｎ化合物層）を形成することができる。この場合、純Ｓｎ層の厚さが０．２〜１．５μｍであるのが好ましく、０．４〜１．５μｍであるのがさらに好ましい。純Ｓｎ層の厚さが０．２μｍより薄いとＳｎめっきとしての特性を発揮できず、１．５μｍより厚いとコストが高くなるからである。また、化合物層の厚さが０．４〜１．５μｍであるのが好ましく、０．６〜１．５μｍであるのがさらに好ましい。化合物層の厚さが０．４μｍより薄いと純Ｓｎ層の下に硬質の化合物層を形成して挿入力を低下させる効果を十分に得ることができず、１．５μｍより厚いと曲げ加工時にＳｎめっき材が割れ易くなるからである。 In addition, by heating the surface of the Sn plating layer to melt Sn and then cooling it, the outermost pure Sn layer and the lower compound layer (Cu when the material is copper or copper alloy) are cooled from the Sn plating layer. -Sn compound layer) can be formed. In this case, the thickness of the pure Sn layer is preferably 0.2 to 1.5 μm, and more preferably 0.4 to 1.5 μm. This is because if the thickness of the pure Sn layer is thinner than 0.2 μm, the characteristics as Sn plating cannot be exhibited, and if it is thicker than 1.5 μm, the cost increases. Moreover, it is preferable that the thickness of a compound layer is 0.4-1.5 micrometers, and it is still more preferable that it is 0.6-1.5 micrometers. If the thickness of the compound layer is less than 0.4 μm, the effect of reducing the insertion force by forming a hard compound layer under the pure Sn layer cannot be obtained sufficiently. This is because the Sn plating material is easily broken.
また、Ｓｎめっき層の表面を加熱してＳｎを溶融させた後に冷却したＳｎめっき材の表面の１５７５μｍ２の領域に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数が５０個以上であるのが好ましい。深さが０．１μｍより浅い微小凹部や、微小凹部の数が５０個未満では、Ｓｎめっき層の表面に潤滑油を十分に保持することができないからである。 Further, the number of cooled Sn 1575Myuemu 2 regions in the formed area 10 [mu] m 2 depth 0.1μm or more micro-recess below the surface of the plated material was melted and Sn by heating the surface of the Sn plated layer The number is preferably 50 or more. This is because the lubricating oil cannot be sufficiently retained on the surface of the Sn plating layer if the depth is less than 0.1 μm or the number of the minute recesses is less than 50.
また、Ｓｎめっき層の表面の光学濃度が１．０以下であるのが好ましい。光学濃度が１．０より高いと、Ｓｎめっき層の表面に潤滑油を十分に保持して摩擦係数を低下させる効果を発揮することができないからである。 Moreover, it is preferable that the optical density of the surface of Sn plating layer is 1.0 or less. This is because if the optical density is higher than 1.0, the effect of reducing the friction coefficient by sufficiently retaining the lubricating oil on the surface of the Sn plating layer cannot be exhibited.
また、Ｓｎめっき層の表面を加熱してＳｎを溶融させた後に冷却した後に、Ｓｎめっき層の表面に潤滑油を塗布するのが好ましい。このように微小凹部が形成されたＳｎめっき層の表面に潤滑油を塗布すると、微小凹部によって潤滑油が保持されて、Ｓｎめっき材の摩擦係数を大幅に低くすることができ、Ｓｎめっき材を挿抜可能な接続端子の材料として使用した場合に挿入力を飛躍的に低減することができるからである。この場合、Ｓｎめっき層の表面に塗布された潤滑油の量がＳｎめっき層の表面の面積に対して２０ｍｇ／ｄｍ２以上であるのが好ましい。潤滑油の量が２０ｍｇ／ｄｍ２未満であると、潤滑油が不足して摩擦係数を低下させる効果を発揮することができないからである。 Moreover, it is preferable to apply the lubricating oil to the surface of the Sn plating layer after cooling the surface of the Sn plating layer by heating it and then melting Sn. When lubricating oil is applied to the surface of the Sn plating layer in which the minute recesses are formed in this way, the lubricating oil is held by the minute recesses, and the friction coefficient of the Sn plating material can be greatly reduced. This is because the insertion force can be drastically reduced when used as a material for a connectable connection terminal. In this case, the amount of lubricating oil applied to the surface of the Sn plating layer is preferably 20 mg / dm 2 or more with respect to the surface area of the Sn plating layer. This is because if the amount of the lubricating oil is less than 20 mg / dm 2 , the lubricating oil is insufficient and the effect of reducing the friction coefficient cannot be exhibited.
また、本発明によるＳｎめっき材は、銅や銅合金などからなる素材上に形成されたＳｎめっき層の表面の１５７５μｍ２の領域に面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部が５０個以上形成されている。 Moreover, Sn-plated material according to the present invention, the depth 0.1μm or more micro-recesses in the area of 10 [mu] m 2 or less in the region of 1575Myuemu 2 of the surface of the copper or copper alloy Sn-plated layer formed on the material consisting of a 50 More than one is formed.
このＳｎめっき材において、Ｓｎめっき層が、最表面側の純Ｓｎ層と、この純Ｓｎ層と素材との間に形成された化合物層（素材が銅または銅合金の場合にはＣｕ−Ｓｎ化合物層）とからなるのが好ましい。この場合、純Ｓｎ層の厚さが０．２μｍ以上であり、化合物層の厚さが０．４μｍ以上であるのが好ましい。 In this Sn plating material, the Sn plating layer is composed of a pure Sn layer on the outermost surface side, and a compound layer formed between the pure Sn layer and the material (Cu—Sn compound when the material is copper or a copper alloy). Layer). In this case, the thickness of the pure Sn layer is preferably 0.2 μm or more, and the thickness of the compound layer is preferably 0.4 μm or more.
また、上記のＳｎめっき材において、Ｓｎめっき材の光学濃度が１．０以下であるのが好ましい。また、微小凹部が形成されたＳｎめっき層の表面に潤滑油が塗布されているのが好ましい。この場合、Ｓｎめっき材の摩擦係数が０．２５以下であるのが好ましい。また、Ｓｎめっき層の表面に塗布された潤滑油の量がＳｎめっき層の表面の面積に対して２０ｍｇ／ｄｍ２以上であるのが好ましい。 Moreover, in said Sn plating material, it is preferable that the optical density of Sn plating material is 1.0 or less. Moreover, it is preferable that lubricating oil is apply | coated to the surface of Sn plating layer in which the micro recessed part was formed. In this case, it is preferable that the friction coefficient of the Sn plating material is 0.25 or less. Moreover, it is preferable that the amount of the lubricating oil applied to the surface of the Sn plating layer is 20 mg / dm 2 or more with respect to the surface area of the Sn plating layer.
なお、潤滑油として、パラフィン系鉱油、ナフテン系鉱油、合成油などの基油に各種の添加物が添加された潤滑油を使用することができるが、端子やバスバーをプレス成形する際に使用するプレス油を使用するのが管理面から好ましい。 As lubricating oil, lubricating oil in which various additives are added to base oil such as paraffinic mineral oil, naphthenic mineral oil, synthetic oil can be used, but it is used when press molding terminals and bus bars. Use of press oil is preferable from the viewpoint of management.
以下、本発明によるＳｎめっき材およびその製造方法の実施例について詳細に説明する。 Hereinafter, examples of the Sn plating material and the manufacturing method thereof according to the present invention will be described in detail.
［実施例１］
まず、素材（被めっき材）として、（ミツトヨ株式会社製のビッカース硬度計により荷重０．５ｋｇｆで測定した）ビッカース硬さが１０５で長さ１００ｍｍ×幅６０ｍｍ×厚さ０．４ｍｍの純銅板（無酸素銅Ｃ１０２０）を用意し、前処理として、電解脱脂を行った後に水洗し、その後、酸洗した後に水洗した。
[Example 1]
First, as a material (material to be plated), a pure copper plate having a Vickers hardness of 105 (measured with a load of 0.5 kgf using a Vickers hardness meter manufactured by Mitutoyo Corporation) and having a length of 100 mm × width of 60 mm × thickness of 0.4 mm ( Oxygen-free copper C1020) was prepared, and as a pretreatment, it was washed with water after electrolytic degreasing, and then washed with water after pickling.
また、硫酸Ｓｎ（ＳｎＳＯ４）６０ｇ／Ｌと硫酸（Ｈ２ＳＯ４）７５ｇ／Ｌとクレゾールスルホン酸３０ｇ／Ｌとβナフトール１ｇ／Ｌを含有する１Ｌの水溶液に空気を１Ｌ／分の流量で１５０分間吹き込んで酸化Ｓｎ１ｇ／Ｌを生成させてめっき浴を作製した。なお、電子線マイクロアナライザ（ＥＰＭＡ）によって、生成した物質がＳｎと酸素（Ｏ）で構成される物質であることを確認した。また、めっき浴中の酸化Ｓｎの生成量は、空気の吹き込み量（Ｌ／分）と吹き込み時間（分）を調整して酸化Ｓｎを生成させた後に、ろ紙（ＡＤＶＡＮＴＥＣ社製のＧＡ−１００（保留粒子径１．０ｍｍ））によりろ過して液中の固体分を採取し、扇風機で２４時間乾燥させて重量を測定することによって定量した。 In addition, air is supplied at a flow rate of 1 L / min to 1 L of an aqueous solution containing Sn (SnSO 4 ) 60 g / L, 75 g / L sulfuric acid (H 2 SO 4 ), 30 g / L cresolsulfonic acid, and 1 g / L β-naphthol. It was blown for 150 minutes to produce oxidized Sn 1 g / L to prepare a plating bath. In addition, it confirmed that the produced | generated substance was a substance comprised by Sn and oxygen (O) by the electron beam microanalyzer (EPMA). Further, the amount of oxidized Sn in the plating bath is adjusted by adjusting the air blowing amount (L / min) and blowing time (min) to generate oxidized Sn, and then filter paper (GA-100 manufactured by ADVANTEC Co., Ltd.). The solid content in the liquid was collected by filtration through a retained particle size of 1.0 mm)), dried by a fan for 24 hours, and quantified by measuring the weight.
次に、前処理済の素材とＳｎ板を４０ｍｍ離間させて１Ｌビーカーに配置し、作製しためっき浴１Ｌをビーカーに入れ、ビーカー中のスターラーを３００ｒｐｍで回転させてめっき浴を攪拌し、液温２０℃に制御し、素材およびＳｎ板をそれぞれ陰極および陽極として、電流密度７Ａ／ｄｍ２で４３秒間通電して、素材の両面のそれぞれ長さ５０ｍｍ×幅６０ｍｍの領域にＳｎめっき層を形成した。 Next, the pre-processed material and the Sn plate are spaced apart by 40 mm and placed in a 1 L beaker, the prepared plating bath 1 L is placed in the beaker, the stirrer in the beaker is rotated at 300 rpm, the plating bath is stirred, and the liquid temperature The temperature was controlled at 20 ° C., and the material and the Sn plate were used as a cathode and an anode, respectively, and current was applied at a current density of 7 A / dm 2 for 43 seconds to form Sn plating layers on both sides of the material with a length of 50 mm × width of 60 mm. .
このように素材上にＳｎめっき層を形成したＳｎめっき材を水洗し、Ｓｎめっき材の表面をドライヤーで５０℃に加熱して１分間乾燥させた後、１分以内にＳｎめっき材のリフロー処理を行った。このリフロー処理（Ｓｎ溶融処理）は、近赤外線ヒーター（ハイベック社製）によって大気雰囲気においてＳｎめっき材を加熱して、Ｓｎめっき層の表面が溶融した後、１０秒以内に温度２０℃の水槽内に浸漬して冷却した。 The Sn plating material in which the Sn plating layer is formed on the material is washed with water, the surface of the Sn plating material is heated to 50 ° C. with a dryer and dried for 1 minute, and then the reflow treatment of the Sn plating material is performed within 1 minute. Went. This reflow process (Sn melting process) is carried out in a water tank at a temperature of 20 ° C. within 10 seconds after the surface of the Sn plating layer is melted by heating the Sn plating material in the air atmosphere by a near infrared heater (manufactured by Hibeck). It was immersed in and cooled.
このようにリフロー処理を行ったＳｎめっき材の表面に、プレスや切断加工などの塑性加工に使用する潤滑油（ＪＸ日鉱日石エネルギー株式会社製のユニプレスＰＡ５）５０ｍｇ／ｄｍ２を塗布した。なお、潤滑油の塗布量は、電子天秤を用いて測定した。 Lubricating oil (Unipress PA5 manufactured by JX Nippon Mining & Energy Corporation) 50 mg / dm 2 used for plastic processing such as pressing and cutting was applied to the surface of the Sn plating material that had been subjected to reflow treatment in this way. The amount of lubricant applied was measured using an electronic balance.
このようにリフロー処理を行った後に潤滑油を塗布したＳｎめっき材の製造条件を表１に示す。 Table 1 shows the manufacturing conditions of the Sn plating material to which the lubricating oil is applied after the reflow treatment as described above.
リフロー処理前のＳｎめっき材について、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。 About the Sn plating material before a reflow process, the thickness (electrodeposition thickness) of Sn plating layer was measured, the crystal grain size of electrodeposition Sn was calculated | required, and the electrodeposition crystal grain size / electrodeposition thickness was computed.
Ｓｎめっき層の厚さ（電析厚さ）は、蛍光Ｘ線膜厚計（セイコーインスツル株式会社製）を用いて測定し、電析Ｓｎの結晶粒度は、電子線マイクロアナライザ（ＥＰＭＡ）により得られる二次電子像（ＳＥＩ）を用いてＳｎめっき層の表面を倍率５０００倍に拡大して切断法（ＪＩＳ Ｈ０５０１）によって求めた。その結果、電析厚さは１．０μｍ、電析結晶粒度は０．９μｍであり、電析結晶粒度／電析厚さは０．９であった。これらの結果を表２に示す。 The thickness (electrodeposition thickness) of the Sn plating layer was measured using a fluorescent X-ray film thickness meter (manufactured by Seiko Instruments Inc.), and the crystal grain size of electrodeposited Sn was measured by an electron beam microanalyzer (EPMA). Using the obtained secondary electron image (SEI), the surface of the Sn plating layer was magnified 5000 times and determined by a cutting method (JIS H0501). As a result, the deposited thickness was 1.0 μm, the deposited crystal grain size was 0.9 μm, and the deposited crystal grain size / deposited thickness was 0.9. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。 In addition, for the Sn-plated material after the reflow treatment, the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface was measured, the optical density was measured, the thickness of the pure Sn layer and Cu -The thickness of the Sn compound layer was measured.
微小凹部の面積については、電子線マイクロアナライザ（ＥＰＭＡ）により得られる二次電子像（ＳＥＩ）を用いて表面を倍率３０００倍に拡大して、表面に形成された凹部の面積が１０μｍ２以下であるか否かを判定した。また、微小凹部の深さは、原子間力顕微鏡（ＡＦＭ）（日本電子株式会社製のＪＳＰＭ５４００）を用いて計測し、微小凹部の数は、電子線マイクロアナライザ（ＥＰＭＡ）により得られる二次電子像（ＳＥＩ）を用いて表面を倍率３０００倍に拡大して３５μｍ×４５μｍ（＝１５７５μｍ２）の領域で計測した。その結果、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数は２００個であった。 About the area of a micro recessed part, the surface is expanded 3000 times using the secondary electron image (SEI) obtained by an electron beam microanalyzer (EPMA), and the area of the recessed part formed in the surface is 10 micrometers 2 or less. It was determined whether there was. The depth of the minute recesses is measured using an atomic force microscope (AFM) (JSPM5400 manufactured by JEOL Ltd.), and the number of minute recesses is secondary electrons obtained by an electron beam microanalyzer (EPMA). Using the image (SEI), the surface was magnified 3000 times and measured in an area of 35 μm × 45 μm (= 1575 μm 2 ). As a result, the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface was 200.
表面の光学濃度は、反射濃度計（マクベス社製のＲＤ９１８）を用いて測定した。この光学濃度の数値が低い程、表面の光沢度が低いことを意味している。その結果、表面の光学濃度は０．５であった。 The optical density of the surface was measured using a reflection densitometer (RD918 manufactured by Macbeth). A lower numerical value of this optical density means that the glossiness of the surface is lower. As a result, the optical density of the surface was 0.5.
純Ｓｎ層の厚さは、電解式膜厚計（中央製作所製のＴＨ１１）を用いて測定した。また、Ｃｕ−Ｓｎ化合物層の厚さは、純Ｓｎ層と同様に電解式膜厚計を用いて測定し、純Ｓｎ層の厚さの測定後に再測定を行って計測表示される値をＣｕ−Ｓｎ化合物層の厚さとした。その結果、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。なお、集束イオンビーム（ＦＩＢ）を用いてめっき断面を露出させ、走査イオン顕微鏡（ＳＩＭ）で断面観察を行ったところ、純Ｓｎ層およびＣｕ−Ｓｎ化合物層の厚さはいずれも電解式膜厚計で測定した厚さと同じであった。 The thickness of the pure Sn layer was measured using an electrolytic film thickness meter (TH11 manufactured by Chuo Seisakusho). Further, the thickness of the Cu—Sn compound layer is measured using an electrolytic film thickness meter in the same manner as the pure Sn layer, and the value displayed by measuring again after the measurement of the thickness of the pure Sn layer is expressed as Cu. -The thickness of the Sn compound layer. As a result, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. In addition, when the plating cross section was exposed using a focused ion beam (FIB) and the cross section was observed with a scanning ion microscope (SIM), the thicknesses of the pure Sn layer and the Cu—Sn compound layer were both electrolytic film thicknesses. It was the same as the thickness measured by the meter.
これらの結果を表３に示す。なお、表３において、リフロー処理後のＳｎめっき材の表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数が０〜９個の場合を×、１０〜４９個の場合を△、５０〜９９個の場合を○、１００個以上の場合を◎で示している。 These results are shown in Table 3. In Table 3, the case where the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface of the Sn plating material after the reflow treatment is 0 to 9 ×, 10 to 49 The case is indicated by Δ, the case of 50 to 99 is indicated by ○, and the case of 100 or more is indicated by ◎.
また、潤滑油塗布後のＳｎめっき材について、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。 Moreover, about the Sn plating material after lubrication oil application | coating, the friction coefficient of the surface was calculated, solder wettability was evaluated, and contact reliability was evaluated.
雄端子と雌端子の嵌合時の挿入力は、端子接圧が一定の場合に表面の摩擦係数と相関があることから、摩擦係数を測定して挿入力を評価した。摩擦係数（μ）は、リフロー処理後のＳｎめっき材から切り出した平板状の試験片に潤滑油を塗布して雄端子とし、Ｃｕ−１．０質量％Ｎｉ−０．９質量％Ｓｎ−０．０５質量％Ｐのからなるビッカース硬さ１８０の銅合金板に厚さ１．０μｍのＳｎめっき層を形成た後にリフロー処理して厚さ０．６μｍの純Ｓｎ層の下層に厚さ０．８μｍのＣｕ−Ｓｎ層が形成されたリフローＳｎめっき材（微小凹部数０個）を卓上プレス機によりインデント加工（Ｒ=１．５ｍｍ）して（潤滑油を塗布しない）雌端子とし、電気接点シミュレータとステージコントローラとロードセルとロードセルアンプを組み合わせた装置（株式会社山崎精機研究所製）を使用して、ステージに固定した平板状の雄端子にインデント加工した雌端子を負荷荷重３００ｇｆ、摺動速度６０ｍｍ／分で７ｍｍ滑らせ、摺動距離１ｍｍから５ｍｍまでの４ｍｍの区間でロードセルアンプによって検出された摺動時の力の平均値（Ｆ）を負荷荷重（Ｎ）で除して、μ＝Ｆ／Ｎから算出した。その結果、摩擦係数は０．１５であった。 Since the insertion force when the male terminal and the female terminal are fitted has a correlation with the friction coefficient of the surface when the terminal contact pressure is constant, the insertion force was evaluated by measuring the friction coefficient. The coefficient of friction (μ) is Cu-1.0 mass% Ni-0.9 mass% Sn-0 by applying lubricating oil to a flat test piece cut out from the Sn-plated material after the reflow treatment to form a male terminal. A Sn plating layer having a thickness of 1.0 μm is formed on a Vickers hardness 180 copper alloy plate made of 0.05 mass% P, and then subjected to a reflow treatment, and a thickness of 0.05 μm is formed below the pure Sn layer having a thickness of 0.6 μm. Reflow Sn plating material (with 0 micro-recesses) with a Cu-Sn layer of 8 μm is indented (R = 1.5 mm) with a desktop press machine to make female terminals (without applying lubricating oil), and electrical contacts Using a device (manufactured by Yamazaki Seiki Laboratory Co., Ltd.) that combines a simulator, a stage controller, a load cell, and a load cell amplifier, a flat male terminal fixed to the stage is indented into a female terminal with a load of 300 gf, The sliding force average value (F) detected by the load cell amplifier in a section of 4 mm from a sliding distance of 1 mm to 5 mm is divided by the load load (N) by sliding 7 mm at a moving speed of 60 mm / min. Calculated from μ = F / N. As a result, the friction coefficient was 0.15.
はんだ濡れ性の評価は、潤滑油塗布後のＳｎめっき材から幅１０ｍｍ、長さ６０ｍｍの試験片をプレスで打ち抜いて、ソルダーチェッカ（株式会社レスカ製のＳＡＴ−５２００）を用いて、８５℃で相対湿度８５％の環境下に２４時間放置した後に、非活性フラックスを塗布し、２６０℃に保持したＰｂフリーはんだ（Ｓｎ−３質量％Ａｇ−０．５質量％Ｃｕ）槽に浸漬速度４ｍｍ／ｓで長さ４ｍｍの部分を１０秒間浸漬して、めっき面を外観観察することにより、試験片のはんだに浸漬した表面積に対するはんだで濡れた部分の面積（はんだ濡れ率）を求めることによって行った。その結果、はんだ濡れ率は９５％であり、はんだ濡れ性は良好であった。 Evaluation of solder wettability is performed by punching out a test piece having a width of 10 mm and a length of 60 mm from the Sn plating material after applying the lubricating oil with a press, and using a solder checker (SAT-5200 manufactured by Reska Co., Ltd.) at 85 ° C. After leaving in an environment with a relative humidity of 85% for 24 hours, an inactive flux was applied and immersed in a Pb-free solder (Sn-3 mass% Ag-0.5 mass% Cu) bath at a rate of 4 mm / This was done by immersing a portion of 4 mm in length for 10 seconds and observing the appearance of the plated surface to obtain the area of the portion wetted with solder (solder wetting ratio) relative to the surface area immersed in the solder of the test piece. . As a result, the solder wettability was 95% and the solder wettability was good.
接触信頼性の評価は、潤滑油塗布後のＳｎめっき材から切り出した試験片を大気雰囲気下において１２０℃の恒温槽内に１２０時間保持した後に恒温槽から取り出し、２０℃の測定室において試験片の表面の接触抵抗値を（高温放置後の接触抵抗値）測定することによって行った。接触抵抗値の測定は、マイクロオームメータ（株式会社山崎精機研究所製）を使用して、開放電圧２０ｍＶ、電流１０ｍＡ、直径０．５ｍｍのＵ型金線プローブ、最大荷重１００ｇｆ、摺動有り（１ｍｍ／１００ｇｆ）の条件で５回測定して、（最大荷重１００ｇｆが加えられたときの）平均値を求めた。その結果、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。 The contact reliability was evaluated by holding a test piece cut out from the Sn-plated material after application of the lubricating oil in a constant temperature bath at 120 ° C. for 120 hours in the air atmosphere and then taking it out from the constant temperature bath and then testing the test piece in a 20 ° C. measurement chamber. The contact resistance value of the surface of (contact resistance value after being left at high temperature) was measured. The contact resistance value was measured using a micro-ohm meter (manufactured by Yamazaki Seiki Laboratory Co., Ltd.), an open-circuit voltage of 20 mV, a current of 10 mA, a U-shaped wire probe with a diameter of 0.5 mm, a maximum load of 100 gf, and sliding ( Measurement was performed 5 times under the condition of 1 mm / 100 gf) to obtain an average value (when a maximum load of 100 gf was applied). As a result, the contact resistance value after leaving at high temperature was 1.0 mΩ, and the contact reliability was good.
これらの結果を表４に示す。なお、表４において、はんだ濡れ率が９０％以上ではんだ濡れ性が良好な場合を○、はんだ濡れ率が９０％未満ではんだ濡れ性が良好でない場合を×で示し、高温放置後の接触抵抗値が２ｍΩ以下で接触信頼性が良好な場合を○、高温放置後の接触抵抗値が２ｍΩより高く接触信頼性が良好でない場合を×で示している。 These results are shown in Table 4. In Table 4, the case where the solder wettability is 90% or more and the solder wettability is good is indicated by ◯, the case where the solder wettability is less than 90% and the solder wettability is not good is indicated by x, and the contact resistance after being left at high temperature The case where the value is 2 mΩ or less and the contact reliability is good is indicated by ○, and the case where the contact resistance value after standing at high temperature is higher than 2 mΩ and the contact reliability is not good is indicated by ×.
［実施例２］
Ｓｎめっき層を形成する際の通電時間を３４秒間としてＳｎめっき層を薄くした以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Example 2]
An Sn plating material was produced in the same manner as in Example 1 except that the energization time for forming the Sn plating layer was 34 seconds and the Sn plating layer was thinned. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは０．８μｍ、電析結晶粒度は０．８μｍであり、電析結晶粒度／電析厚さは１．０であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the deposited thickness was 0.8 μm, the deposited crystal grain size was 0.8 μm, and the deposited crystal grain size / deposited thickness was 1.0. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は２２０個、表面の光学濃度は０．５、純Ｓｎ層の厚さは０．４μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．６μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 220, the optical density of the surface was 0.5, the thickness of the pure Sn layer was 0.4 μm, and the thickness of the Cu—Sn compound layer was 0.6 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．１４、はんだ濡れ率は９０％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．２ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.14, the solder wettability was 90%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.2 mΩ, and the contact reliability was good. These results are shown in Table 4.
［実施例３］
Ｓｎめっき層を形成する際の通電時間を６４秒間としてＳｎめっき層を厚くした以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Example 3]
An Sn plating material was produced in the same manner as in Example 1 except that the energization time for forming the Sn plating layer was 64 seconds and the Sn plating layer was thickened. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．５μｍ、電析結晶粒度は１．５μｍであり、電析結晶粒度／電析厚さは１．０であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the deposited thickness was 1.5 μm, the deposited crystal grain size was 1.5 μm, and the deposited crystal grain size / deposited thickness was 1.0. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は１２０個、表面の光学濃度は０．７、純Ｓｎ層の厚さは１．０μｍ、Ｃｕ−Ｓｎ化合物層の厚さは１．０μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 120, the optical density of the surface was 0.7, the thickness of the pure Sn layer was 1.0 μm, and the thickness of the Cu—Sn compound layer was 1.0 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．１９、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は０．９ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.19, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 0.9 mΩ, and the contact reliability was good. These results are shown in Table 4.
［実施例４］
潤滑油の塗布量を２０ｍｇ／ｄｍ２と少なくした以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Example 4]
An Sn plating material was produced in the same manner as in Example 1 except that the amount of the lubricating oil applied was reduced to 20 mg / dm 2 . Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は０．９μｍであり、電析結晶粒度／電析厚さは０．９であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the deposited thickness was 1.0 μm, the deposited crystal grain size was 0.9 μm, and the deposited crystal grain size / deposited thickness was 0.9. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は２００個、表面の光学濃度は０．５、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 200, the optical density of the surface was 0.5, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．１９、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.19, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
［実施例５］
潤滑油の塗布量を３００ｍｇ／ｄｍ２と多くした以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Example 5]
An Sn plating material was produced by the same method as in Example 1 except that the amount of the lubricating oil applied was increased to 300 mg / dm 2 . Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は０．９μｍであり、電析結晶粒度／電析厚さは０．９であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the deposited thickness was 1.0 μm, the deposited crystal grain size was 0.9 μm, and the deposited crystal grain size / deposited thickness was 0.9. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は２００個、表面の光学濃度は０．５、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 200, the optical density of the surface was 0.5, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．１４、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.14, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
［実施例６］
空気の吹き込み時間を３０分間としてめっき浴中の酸化Ｓｎの生成量を０．２ｇ／Ｌと少なくした以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Example 6]
An Sn plating material was produced in the same manner as in Example 1 except that the air blowing time was 30 minutes and the amount of Sn oxide produced in the plating bath was reduced to 0.2 g / L. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は１．１μｍであり、電析結晶粒度／電析厚さは１．１であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the electrodeposition thickness was 1.0 μm, the electrodeposition crystal grain size was 1.1 μm, and the electrodeposition crystal grain size / electrodeposition thickness was 1.1. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は８０個、表面の光学濃度は０．８、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 80, the optical density of the surface was 0.8, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．２４、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.24, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
［実施例７］
空気の吹き込み時間を６００分間としてめっき浴中の酸化Ｓｎの生成量を４ｇ／Ｌと多くした以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Example 7]
An Sn plating material was produced in the same manner as in Example 1 except that the air blowing time was 600 minutes and the amount of Sn oxide produced in the plating bath was increased to 4 g / L. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は０．９μｍであり、電析結晶粒度／電析厚さは０．９であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the deposited thickness was 1.0 μm, the deposited crystal grain size was 0.9 μm, and the deposited crystal grain size / deposited thickness was 0.9. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は２４０個、表面の光学濃度は０．４、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 240, the optical density of the surface was 0.4, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．１５、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.15, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
［実施例８］
Ｓｎめっき層を形成する際の電流密度を３Ａ／ｄｍ２と低くし且つ通電時間を１００秒間と長くした以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Example 8]
An Sn plating material was produced in the same manner as in Example 1 except that the current density when forming the Sn plating layer was reduced to 3 A / dm 2 and the energization time was increased to 100 seconds. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は１．３μｍであり、電析結晶粒度／電析厚さは１．３であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the deposited thickness was 1.0 μm, the deposited crystal grain size was 1.3 μm, and the deposited crystal grain size / deposited thickness was 1.3. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は６０個、表面の光学濃度は０．８、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 60, the optical density of the surface was 0.8, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．２４、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.24, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
［実施例９］
Ｓｎめっき層を形成する際の電流密度を１２Ａ／ｄｍ２と高くし且つ通電時間を２５秒間と短くした以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Example 9]
An Sn plating material was produced in the same manner as in Example 1 except that the current density when forming the Sn plating layer was increased to 12 A / dm 2 and the energization time was shortened to 25 seconds. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は０．８μｍであり、電析結晶粒度／電析厚さは０．８であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the electrodeposition thickness was 1.0 μm, the electrodeposition crystal grain size was 0.8 μm, and the electrodeposition crystal grain size / electrodeposition thickness was 0.8. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は２６０個、表面の光学濃度は０．４、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 260, the optical density of the surface was 0.4, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．１４、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.14, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
［比較例１］
めっき浴中に酸化Ｓｎを生成させず、Ｓｎめっき層を形成する際の電流密度を２Ａ／ｄｍ２と低くし且つ通電時間を１５０秒間と長くし、リフロー処理前にＳｎめっき材の表面を乾燥しないで表面が濡れたまま１分以内にリフロー処理を行い、潤滑油を塗布しなかった以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Comparative Example 1]
Sn oxide is not generated in the plating bath, the current density when forming the Sn plating layer is reduced to 2 A / dm 2 and the energization time is increased to 150 seconds, and the surface of the Sn plating material is dried before the reflow treatment. An Sn plated material was prepared in the same manner as in Example 1 except that the reflow treatment was performed within 1 minute while the surface was wet and no lubricating oil was applied. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は１．８μｍであり、電析結晶粒度／電析厚さは１．８であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the electrodeposition thickness was 1.0 μm, the electrodeposition crystal grain size was 1.8 μm, and the electrodeposition crystal grain size / electrodeposition thickness was 1.8. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は０個、表面の光学濃度は１．４、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 0, the surface optical density was 1.4, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．３６、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 For the Sn-plated material after the reflow treatment, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.36, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
［比較例２］
めっき浴中に酸化Ｓｎを生成させず、Ｓｎめっき層を形成する際の電流密度を２Ａ／ｄｍ２と低くし且つ通電時間を１５０秒間と長くし、リフロー処理前にＳｎめっき材の表面を乾燥しないで表面が濡れたまま１分以内にリフロー処理を行った以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Comparative Example 2]
Sn oxide is not generated in the plating bath, the current density when forming the Sn plating layer is reduced to 2 A / dm 2 and the energization time is increased to 150 seconds, and the surface of the Sn plating material is dried before the reflow treatment. The Sn plating material was produced by the method similar to Example 1 except having performed the reflow process within 1 minute, without the surface getting wet. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は１．８μｍであり、電析結晶粒度／電析厚さは１．８であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the electrodeposition thickness was 1.0 μm, the electrodeposition crystal grain size was 1.8 μm, and the electrodeposition crystal grain size / electrodeposition thickness was 1.8. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は０個、表面の光学濃度は１．４、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 0, the surface optical density was 1.4, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．２８、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.28, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
［比較例３］
潤滑油を塗布しなかった以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Comparative Example 3]
An Sn plated material was produced in the same manner as in Example 1 except that the lubricating oil was not applied. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は０．９μｍであり、電析結晶粒度／電析厚さは０．９であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the deposited thickness was 1.0 μm, the deposited crystal grain size was 0.9 μm, and the deposited crystal grain size / deposited thickness was 0.9. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は２００個、表面の光学濃度は０．５、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 200, the optical density of the surface was 0.5, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．３６、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 For the Sn-plated material after the reflow treatment, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.36, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
［比較例４］
Ｓｎめっき層を形成する際の通電時間を１７秒間としてＳｎめっき層を非常に薄くした以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Comparative Example 4]
An Sn plating material was produced in the same manner as in Example 1 except that the energization time for forming the Sn plating layer was 17 seconds and the Sn plating layer was very thin. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは０．４μｍ、電析結晶粒度は０．４μｍであり、電析結晶粒度／電析厚さは１．０であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the deposited thickness was 0.4 μm, the deposited crystal grain size was 0.4 μm, and the deposited crystal grain size / deposited thickness was 1.0. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は０個、表面の光学濃度は１．２、純Ｓｎ層の厚さは０．１μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．５μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 0, the surface optical density was 1.2, the thickness of the pure Sn layer was 0.1 μm, and the thickness of the Cu—Sn compound layer was 0.5 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．２２、はんだ濡れ率は７０％ではんだ濡れ性が悪く、高温放置後の接触抵抗値は５．５ｍΩで接触信頼性が良好でなかった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.22, the solder wettability was 70%, the solder wettability was poor, the contact resistance value after standing at high temperature was 5.5 mΩ, and the contact reliability was not good. These results are shown in Table 4.
［比較例５］
リフロー処理前にＳｎめっき材の表面を乾燥しないで表面が濡れたまま１分以内にリフロー処理を行った以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Comparative Example 5]
An Sn plating material was produced in the same manner as in Example 1 except that the surface of the Sn plating material was not dried before the reflow treatment and the reflow treatment was performed within 1 minute while the surface was wet. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は０．９μｍであり、電析結晶粒度／電析厚さは０．９であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the deposited thickness was 1.0 μm, the deposited crystal grain size was 0.9 μm, and the deposited crystal grain size / deposited thickness was 0.9. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は１０個、表面の光学濃度は１．２、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 10, the optical density of the surface was 1.2, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．２７、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.27, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
［比較例６］
空気を吹き込まないでめっき浴中に酸化Ｓｎを生成させなかった以外は、実施例１と同様の方法により、Ｓｎめっき材を作製した。このＳｎめっき材の製造条件を表１に示す。
[Comparative Example 6]
An Sn plating material was produced in the same manner as in Example 1 except that no oxidized Sn was generated in the plating bath without blowing air. Table 1 shows the production conditions of the Sn plating material.
また、リフロー処理前のＳｎめっき材について、実施例１と同様の方法により、Ｓｎめっき層の厚さ（電析厚さ）を測定し、電析Ｓｎの結晶粒度を求め、電析結晶粒度／電析厚さを算出した。その結果、電析厚さは１．０μｍ、電析結晶粒度は１．４μｍであり、電析結晶粒度／電析厚さは１．４であった。これらの結果を表２に示す。 Further, with respect to the Sn plating material before the reflow treatment, the thickness (electrodeposition thickness) of the Sn plating layer was measured by the same method as in Example 1 to obtain the crystal grain size of the electrodeposited Sn. The electrodeposition thickness was calculated. As a result, the deposited thickness was 1.0 μm, the deposited crystal grain size was 1.4 μm, and the deposited crystal grain size / deposited thickness was 1.4. These results are shown in Table 2.
また、リフロー処理後のＳｎめっき材について、実施例１と同様の方法により、表面に形成された面積１０μｍ２以下で深さ０．１μｍ以上の微小凹部の数を計測し、光学濃度を測定し、純Ｓｎ層の厚さおよびＣｕ−Ｓｎ化合物層の厚さを測定した。その結果、微小凹部の数は３０個、表面の光学濃度は１．１、純Ｓｎ層の厚さは０．６μｍ、Ｃｕ−Ｓｎ化合物層の厚さは０．８μｍであった。これらの結果を表３に示す。 Further, for the Sn-plated material after the reflow treatment, the optical density was measured by measuring the number of minute recesses having an area of 10 μm 2 or less and a depth of 0.1 μm or more formed on the surface in the same manner as in Example 1. The thickness of the pure Sn layer and the thickness of the Cu—Sn compound layer were measured. As a result, the number of minute recesses was 30, the surface optical density was 1.1, the thickness of the pure Sn layer was 0.6 μm, and the thickness of the Cu—Sn compound layer was 0.8 μm. These results are shown in Table 3.
また、潤滑油塗布後のＳｎめっき材について、実施例１と同様の方法により、表面の摩擦係数を算出し、はんだ濡れ性を評価し、接触信頼性を評価した。その結果、摩擦係数は０．２７、はんだ濡れ率は９５％ではんだ濡れ性が良好であり、高温放置後の接触抵抗値は１．０ｍΩで接触信頼性が良好であった。これらの結果を表４に示す。 Further, for the Sn plated material after applying the lubricating oil, the surface friction coefficient was calculated by the same method as in Example 1, the solder wettability was evaluated, and the contact reliability was evaluated. As a result, the coefficient of friction was 0.27, the solder wettability was 95%, and the solder wettability was good. The contact resistance value after standing at high temperature was 1.0 mΩ, and the contact reliability was good. These results are shown in Table 4.
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