JP4907107B2 - Tin plating material and method for producing the same - Google Patents
Tin plating material and method for producing the same Download PDFInfo
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- JP4907107B2 JP4907107B2 JP2005181819A JP2005181819A JP4907107B2 JP 4907107 B2 JP4907107 B2 JP 4907107B2 JP 2005181819 A JP2005181819 A JP 2005181819A JP 2005181819 A JP2005181819 A JP 2005181819A JP 4907107 B2 JP4907107 B2 JP 4907107B2
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- 239000000463 material Substances 0.000 title claims description 120
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 101
- 238000007747 plating Methods 0.000 title claims description 99
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 76
- 239000002245 particle Substances 0.000 claims description 62
- 239000002131 composite material Substances 0.000 claims description 29
- 229910002804 graphite Inorganic materials 0.000 claims description 23
- 239000010439 graphite Substances 0.000 claims description 23
- -1 aromatic carbonyl compound Chemical class 0.000 claims description 10
- 238000009713 electroplating Methods 0.000 claims description 9
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 3
- 150000008365 aromatic ketones Chemical class 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 description 92
- 229910052799 carbon Inorganic materials 0.000 description 54
- 238000000034 method Methods 0.000 description 20
- 230000003746 surface roughness Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229910018100 Ni-Sn Inorganic materials 0.000 description 2
- 229910018532 Ni—Sn Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
Description
本発明は、錫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錫めっき材およびその製造方法に関する。 The present invention relates to a tin-plated material and a method for manufacturing the same, and more particularly to a tin-plated material used as a material such as a connectable / detachable connection terminal 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錫めっきを施した錫めっき材が使用されている。特に、錫めっき材は、接触抵抗が小さく、自動車などの接続端子の材料として使用されている。 Conventionally, a tin-plated material obtained by applying tin 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, the tin plating material has a low contact resistance and is used as a material for connection terminals of automobiles and the like.
しかし、錫めっき材は、軟質で端子接続時に変形を生じ易いため、挿入時の摩擦係数が高いという問題がある。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 tin plating material is soft and easily deforms at the time of terminal connection, there is a problem that the friction coefficient at the time of insertion is 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、錫めっき後にリフロー処理を施した錫リフロー材が、自動車などの接続端子の一般的な材料として使用されている。この錫リフロー材では、軟質層である錫めっき皮膜の膜厚を薄くし、さらにリフロー処理により硬質な錫合金層を下地に形成することにより、摩擦係数の低減をしている。また、錫を主体とする金属マトリクス中に耐磨耗性または潤滑性の固体粒子を複合化させた複合材の皮膜を電気めっきにより導体素材上に形成することにより、機械的な耐摩耗性を向上させることが提案され（例えば、特許文献１〜３参照）、このような複合めっき皮膜を応用した接続端子が提案されている（例えば、特許文献４参照）。また、錫または錫／鉛と黒鉛の複合めっき皮膜を導体素材上に形成することにより、耐摩耗性に優れた導電性皮膜を形成することが提案されている（例えば、特許文献５参照）。さらに、本発明者らは、炭素粒子および芳香族カルボニル化合物を添加した錫めっき液を使用して電気めっきを行うことにより、錫層中に炭素粒子を含有する複合材からなる皮膜が素材上に形成され、同種の錫めっき材同士の摩擦係数が０．１８以下の錫めっき材を製造する方法を提案している（特願２００５−８６０７４号）。
In order to solve such a problem, a tin reflow material subjected to a reflow treatment after tin plating is used as a general material for connection terminals of automobiles and the like. In this tin reflow material, the friction coefficient is reduced by reducing the film thickness of the tin plating film, which is a soft layer, and forming a hard tin alloy layer on the base by reflow treatment. In addition, by forming a coating of composite material, which is a composite of wear-resistant or lubricious solid particles in a metal matrix mainly composed of tin, on the conductor material by electroplating, mechanical wear resistance is improved. Improvement is proposed (for example, refer to
しかし、錫リフロー材は、一般的に摩擦係数が０．２〜０．３０程度で比較的高く、上記の特許文献１〜５の方法により製造された錫めっき材の摩擦係数も比較的高く、特に、特許文献５に記載された錫と黒鉛の複合めっき材の摩擦係数（同種の錫めっき材同士の摩擦係数）は０．２程度と比較的高くなっている。
However, the tin reflow material generally has a relatively high friction coefficient of about 0.2 to 0.30, and the friction coefficient of the tin-plated material manufactured by the methods of
また、通常の接続端子では、雄端子と雌端子の嵌合時の接触面の面積を減少させて挿入力を小さくするために、一方の端子の接触面の形状を平面にし、他方の端子の接触面の形状を凸面にインデント加工しており、一般に両端子のめっき皮膜の種類が異なっている。そのため、特願２００５−８６０７４号に提案された方法によって製造された錫めっき材からなる端子であっても、その端子がインデント加工され、嵌合する相手方の端子が錫リフロー材からなる場合には、摩擦係数が０．２程度と比較的高くなる場合がある。 Also, in the normal connection terminal, in order to reduce the insertion force by reducing the area of the contact surface when the male terminal and the female terminal are fitted, the shape of the contact surface of one terminal is made flat, The shape of the contact surface is indented into a convex surface, and the types of plating films on both terminals are generally different. Therefore, even if the terminal is made of a tin-plated material manufactured by the method proposed in Japanese Patent Application No. 2005-86074, the terminal is indented and the mating counterpart terminal is made of a tin reflow material. In some cases, the friction coefficient is relatively high at about 0.2.
したがって、本発明は、このような従来の問題点に鑑み、インデント加工した場合でも、錫リフロー材などの他の種類の錫めっき材との間の摩擦係数が極めて低い錫めっき材およびその製造方法を提供することを目的とする。 Therefore, in view of such conventional problems, the present invention provides a tin-plated material having a very low coefficient of friction with other types of tin-plated materials such as a tin reflow material even when indented, and a method for producing the same. The purpose is to provide.
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、グラファイト粒子および芳香族カルボニル化合物を添加した錫めっき液を使用して電気めっきを行う際、錫めっき液中のグラファイト粒子の濃度を２０ｇ／Ｌ未満、好ましくは１〜１０ｇ／Ｌ、さらに好ましくは５〜１０ｇ／Ｌにすることにより、錫層中にグラファイト粒子が分散した複合材からなる皮膜を素材上に形成し、インデント加工した場合でも、錫リフロー材などの他の種類の錫めっき材との間の摩擦係数が極めて低い錫めっき材を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 intensive studies to solve the above problems, the present inventors have found that the concentration of graphite particles in the tin plating solution when performing electroplating using a tin plating solution to which graphite particles and an aromatic carbonyl compound are added. Is formed to be indented by forming a film made of a composite material in which graphite particles are dispersed in a tin layer on the material by making the amount less than 20 g / L, preferably 1 to 10 g / L, more preferably 5 to 10 g / L. Even in this case, it was found that a tin plating material having a very low friction coefficient with other types of tin plating materials such as a tin reflow material can be produced, and the present invention has been completed.
すなわち、本発明による錫めっき材の製造方法は、グラファイト粒子および芳香族カルボニル化合物を添加した錫めっき液を使用して電気めっきを行うことにより、錫層中にグラファイト粒子を含有する複合材からなる皮膜を素材上に形成する錫めっき材の製造方法において、錫めっき液中のグラファイト粒子の濃度を２０ｇ／Ｌ未満、好ましくは１〜１０ｇ／Ｌ、さらに好ましくは５〜１０ｇ／Ｌにすることを特徴とする。この錫めっき材の製造方法において、芳香族カルボニル化合物が、芳香族アルデヒドまたは芳香族ケトンであるのが好ましい。 That is, the manufacturing method of the tin plating material by this invention consists of a composite material which contains a graphite particle in a tin layer by performing electroplating using the tin plating liquid which added the graphite particle and the aromatic carbonyl compound. In the method for producing a tin plating material for forming a film on a material, the concentration of graphite particles in the tin plating solution is less than 20 g / L, preferably 1 to 10 g / L, more preferably 5 to 10 g / L. Features. In this method for producing a tin plating material, the aromatic carbonyl compound is preferably an aromatic aldehyde or an aromatic ketone.
また本発明による錫めっき材は、錫層中にグラファイト粒子を含有する複合材からなる皮膜が素材上に形成され、同種同士の摩擦係数が０．２０〜０．２４のリフロー処理を施した錫めっき材との間の摩擦係数が０．１６以下、好ましくは０．１３以下であることを特徴とする。この錫めっき材において、表面の算術平均粗さが０．１〜０．５μｍ、最大高さが８〜１６μｍ、十点平均粗さが７〜１２μｍ、光沢度０．８以上であり、皮膜の厚さが０．５〜３μｍ、皮膜中の炭素の含有量が１．２重量％以下であるのが好ましい。
Further, the tin plating material according to the present invention is a tin-plated tin film in which a film made of a composite material containing graphite particles is formed on the material and subjected to reflow treatment with a friction coefficient of 0.20 to 0.24 of the same kind. The coefficient of friction with the plating material is 0.16 or less, preferably 0.13 or less. In this tin-plated product, 0.1 to 0.5 [mu] m is arithmetic average roughness of the surface, the
さらに、本発明による接続端子は、雌端子とこの雌端子に嵌合する雄端子とからなり、雌端子と雄端子の少なくとも一方の少なくとも他方と接触する部分が、上記の錫めっき材からなることを特徴とする。 Furthermore, the connection terminal according to the present invention is composed of a female terminal and a male terminal fitted to the female terminal, and a portion in contact with at least one of the female terminal and at least one of the male terminals is composed of the above tin plating material. It is characterized by.
本発明によれば、インデント加工した場合でも、錫リフロー材などの他の種類の錫めっき材との間の摩擦係数が極めて低い錫めっき材を製造することができる。この錫めっき材は、自動車用などの接続端子がさらに多極化された場合にも十分に対応可能な材料として使用することができ、嵌合する相手方の端子が錫リフロー材からなる場合でも、挿入力が小さい接続端子を製造することができる。 According to the present invention, even when indented, a tin-plated material having a very low friction coefficient with other types of tin-plated materials such as a tin reflow material can be produced. This tin-plated material can be used as a material that can sufficiently handle even when the connection terminals for automobiles and the like are further multipolarized, and even when the mating counterpart terminal is made of a tin reflow material, the insertion force Can be produced.
本発明による錫めっき材の製造方法の実施の形態では、炭素粒子および芳香族カルボニル化合物を添加した錫めっき液を使用して電気めっきを行うことにより、錫層中に炭素粒子を含有する複合材からなる皮膜を素材上に形成する際に、錫めっき液中の炭素粒子の濃度を２０ｇ／Ｌ未満、好ましくは１〜１０ｇ／Ｌ、さらに好ましくは５〜１０ｇ／Ｌにする。 In an embodiment of a method for producing a tin plating material according to the present invention, a composite material containing carbon particles in a tin layer is obtained by performing electroplating using a tin plating solution to which carbon particles and an aromatic carbonyl compound are added. When forming a film composed of the above material on the material, the concentration of carbon particles in the tin plating solution is less than 20 g / L, preferably 1 to 10 g / L, and more preferably 5 to 10 g / L.
錫めっき液としては、アルカノールスルホン酸からなる錫めっき液を使用するのが好ましい。炭素粒子としては、様々な炭素粒子を使用することができるが、鱗片状や土状のグラファイト粒子を使用するのが好ましい。芳香族カルボニル化合物としては、芳香族アルデヒドまたは芳香族ケトンを使用するのが好ましい。錫めっき液に芳香族カルボニル化合物を添加することにより、錫めっき液中において炭素粒子が弱い凝集の分散状態になり、錫マトリクス中に炭素粒子が島状に分散された皮膜を形成することができる。従来の炭素粒子が複合化した皮膜では、炭素粒子を略均一に分散させるために種々の湿潤材を添加して錫マトリクス中に分散した皮膜を形成しているが、本実施の形態のように錫マトリクス中の炭素粒子の凝集状態を制御することによってさらに低い摩擦係数の皮膜を形成することができる。 As the tin plating solution, a tin plating solution made of alkanol sulfonic acid is preferably used. Various carbon particles can be used as the carbon particles, but it is preferable to use scaly or earthy graphite particles. As the aromatic carbonyl compound, an aromatic aldehyde or an aromatic ketone is preferably used. By adding an aromatic carbonyl compound to the tin plating solution, the carbon particles become weakly aggregated and dispersed in the tin plating solution, and a film in which the carbon particles are dispersed in an island shape in the tin matrix can be formed. . In a conventional film in which carbon particles are combined, various wetting materials are added to form a film dispersed in a tin matrix in order to disperse the carbon particles substantially uniformly. A film having a lower coefficient of friction can be formed by controlling the aggregation state of the carbon particles in the tin matrix.
また、めっき液中の炭素粒子の濃度は、２０ｇ／Ｌ未満であり、１〜１０ｇ／Ｌであるのが好ましく、５〜１０ｇ／Ｌであるのがさらに好ましい。１ｇ／Ｌ未満では、炭素粒子が表面構造を構築して複合化するには不十分であり、２０ｇ／Ｌ以上では、炭素粒子が複合化する量が増加して、錫マトリクス中において炭素粒子が適切な凝集状態で分散された皮膜を形成することができないからである。また、電気めっきの際の電流密度は５〜１５Ａ／ｄｍ２であるのが好ましい。５Ａ／ｄｍ２未満では生産性が悪く、１５Ａ／ｄｍ２を超えるとめっきやけが生じるからである。 Moreover, the density | concentration of the carbon particle in a plating solution is less than 20 g / L, it is preferable that it is 1-10 g / L, and it is more preferable that it is 5-10 g / L. If it is less than 1 g / L, the carbon particles are insufficient for building up a surface structure and complexing, and if it is 20 g / L or more, the amount of carbon particles that are complexed increases, and the carbon particles are contained in the tin matrix. This is because it is impossible to form a film dispersed in an appropriate aggregated state. Moreover, it is preferable that the current density in the case of electroplating is 5-15 A / dm < 2 >. If it is less than 5 A / dm 2 , the productivity is poor, and if it exceeds 15 A / dm 2 , plating burns occur.
なお、本発明による錫めっき材の実施の形態は、最表面の構造に特徴があり、下地に影響されないので、下地めっきは、素材や用途に応じてＳｎ、Ｃｕ、Ｎｉなどの様々な下地めっきから選択することができる。また、下地めっきとしてＳｎめっきを施すと、最表面の炭素粒子の凝集構造を変化させることなく、膜厚を厚くして耐摩耗性を向上させることができる。 In addition, since the embodiment of the tin plating material according to the present invention is characterized by the structure of the outermost surface and is not affected by the base, the base plating may be various base platings such as Sn, Cu, and Ni depending on the material and application. You can choose from. Further, when Sn plating is performed as the base plating, the wear resistance can be improved by increasing the film thickness without changing the aggregate structure of the carbon particles on the outermost surface.
上述した本発明による錫めっき材の製造方法の実施の形態により、適度に凝集した炭素粒子が錫層中に適度に分散した複合材からなる皮膜を素材上に形成され、同種同士の摩擦係数が０．２０〜０．２４のリフロー処理を施した錫めっき材との間の摩擦係数が０．１６以下、好ましくは０．１３以下であり、表面粗さを表すパラメータである算術平均粗さＲａが０．１〜０．５μｍ、好ましくは０．１３〜０．４８μｍ、最大高さＲｙが８〜１６μｍ、好ましくは８．９〜５．９μｍ、および十点平均粗さＲｚ７〜１２μｍ、好ましくは７．０〜１１．３μｍであり、光沢度が０．８以上、好ましくは０．８３以上であり、皮膜の厚さが０．５〜３μｍ、好ましくは０．５〜１．０μｍであり、皮膜中の炭素の含有量が０．１〜１．２重量％、好ましくは０．５〜１．１４重量％の錫めっき材を製造することができる。なお、この皮膜が最外層に形成されているのが好ましい。 According to the embodiment of the method for producing a tin-plated material according to the present invention described above, a film made of a composite material in which appropriately aggregated carbon particles are appropriately dispersed in a tin layer is formed on the material, and the friction coefficient between the same types the coefficient of friction between the tin-plated product treated by the reflow treatment of 0.20 to 0.24 are 0.16 or less, preferably 0.13 or less, arithmetic average roughness is a parameter representing the surface roughness Ra is 0.1 to 0.5 μm, preferably 0.13 to 0.48 μm, maximum height Ry is 8 to 16 μm, preferably 8.9 to 5.9 μm, and ten-point average roughness Rz 7 to 12 μm, preferably Is 7.0 to 11.3 μm, the glossiness is 0.8 or more, preferably 0.83 or more, and the film thickness is 0.5 to 3 μm, preferably 0.5 to 1.0 μm. The carbon content in the film is preferably 0.1 to 1.2% by weight. Alternatively, a tin plating material of 0.5 to 1.14% by weight can be manufactured. In addition, it is preferable that this film is formed in the outermost layer.
複合めっき材の複合めっき皮膜は、金属マトリックスと固体粒子とからなり、固体粒子の凝集状態や金属マトリックス中の固体粒子の分散状態によって表面粗さが大きく変化し、それによって複合めっき皮膜の特性が大きく変化すると考えられる。この複合めっき皮膜の表面粗さを適切な状態にすることにより、複合めっき材をインデント加工して端子として使用する場合に、凝集した固体粒子における相手方の端子との点接触および固体粒子の適度な分散による接触面の面積の減少により、摩擦係数が減少すると考えられる。 The composite plating film of the composite plating material consists of a metal matrix and solid particles, and the surface roughness varies greatly depending on the aggregation state of the solid particles and the dispersion state of the solid particles in the metal matrix. It is thought that it will change greatly. By setting the surface roughness of this composite plating film to an appropriate state, when the composite plating material is indented and used as a terminal, the agglomerated solid particles are brought into point contact with the other terminal and the solid particles are moderately It is considered that the friction coefficient decreases due to a decrease in the area of the contact surface due to dispersion.
また、固体粒子の適切な添加量は、複合めっき皮膜および固体粒子の種類により異なると考えられる。錫と炭素粒子の複合めっき材では、錫めっき液中に添加される炭素粒子の量が２０ｇ／Ｌよりも多いと、複合化される炭素粒子が大きな凝集粒子になり、特に錫めっき材をインデント加工した場合には、大きな凹凸が形成され、炭素粒子の接触点における圧力が増大する。そのため、相手方の端子が錫めっき材からなる場合、相手方の端子の錫めっき材を強く押圧して、摩擦係数が悪化すると考えられる。また、表面粗さが上記の範囲よりも粗い場合にも、特にインデント加工された場合には、大きな凹凸が形成され、炭素粒子の接触点における圧力が増加し、そのため、相手方の端子錫めっき材からなる場合、相手方の端子の錫めっき材を強く押圧して、摩擦係数が悪化するものと考えられる。 Moreover, it is thought that the appropriate addition amount of a solid particle changes with the composite plating film and the kind of solid particle. In the composite plating material of tin and carbon particles, if the amount of carbon particles added to the tin plating solution is more than 20 g / L, the composited carbon particles become large aggregate particles, and in particular the tin plating material is indented. When processed, large irregularities are formed, and the pressure at the contact point of the carbon particles increases. Therefore, when the counterpart terminal is made of a tin plating material, it is considered that the friction coefficient is deteriorated by strongly pressing the tin plating material of the counterpart terminal. In addition, even when the surface roughness is rougher than the above range, particularly when indented, large irregularities are formed, and the pressure at the contact point of the carbon particles increases. It is considered that the friction coefficient deteriorates by strongly pressing the tin plating material of the counterpart terminal.
なお、めっき皮膜の厚さが０．５μｍ未満では、錫の酸化などによって接触抵抗の経時変化が大きくなり、接続端子の重要な機能である接続信頼性に欠ける。一方、めっき皮膜の厚さが３μｍを超えると、炭素粒子の複合化が進み、上述したような炭素粒子が分散した状態を維持することができなくなる。 When the thickness of the plating film is less than 0.5 μm, the change in contact resistance with time is increased due to oxidation of tin or the like, and connection reliability, which is an important function of the connection terminal, is lacking. On the other hand, when the thickness of the plating film exceeds 3 μm, the composite of the carbon particles proceeds, and the state in which the carbon particles are dispersed as described above cannot be maintained.
以下、本発明による錫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 tin plating material and the manufacturing method thereof according to the present invention will be described in detail.
［実施例１］
まず、錫めっき液として、６０ｇ／Ｌの金属錫（金属錫塩としてアルカノールスルホン酸錫（ユケン工業製のメタスＳＭ）６００ｍＬ／Ｌを含む）と１１３ｇ／Ｌの遊離酸（遊離酸としてアルカノールスルホン酸（ユケン工業製のメタスＡＭ）１３０ｍＬ／Ｌを含む）とを含む錫めっき液を用意した。この錫めっき液に、良好な錫めっき皮膜を得るために錫めっき用の界面活性剤（ユケン工業製のメタスＬＳＡ−Ｍ）２０ｍＬ／Ｌを添加し、平均粒径３．４μｍの鱗片状グラファイト粒子（エスイーシー社製のグラファイトＳＧＰ−３）５ｇ／Ｌを添加して分散させるとともに、グラファイト粒子の凝集状態を制御するために芳香族カルボニル化合物としてベンズアルデヒド３０ｍＬ／Ｌを添加した。なお、グラファイト粒子の平均粒径は、グラファイト粒子０．５ｇを０．２重量％のヘキサメタリン酸ナトリウム溶液５０ｇに分散させ、さらに超音波により分散させた後、レーザー光散乱粒度分布測定装置を用いて測定し、累積分布で５０％の粒径を平均粒径とすることにより求めた。
[Example 1]
First, as a tin plating solution, 60 g / L of metallic tin (including 600 mL / L of tin alkanol sulfonate (Metas SM manufactured by Yuken Industry) as a metal tin salt) and 113 g / L of free acid (alkanol sulfonic acid as a free acid) (Including YUKEN INDUSTRY METASU AM) 130 mL / L) was prepared. In order to obtain a good tin plating film, 20 mL / L of a tin plating surfactant (Metas LSA-M manufactured by Yuken Industry) was added to this tin plating solution, and flaky graphite particles having an average particle size of 3.4 μm. (Graphic SGP-3 manufactured by ESC) 5 g / L was added and dispersed, and
上記の錫めっき浴中に、厚さ０．２５ｍｍのＣｕ−Ｎｉ−Ｓｎ合金材（同和鉱業製のＮＢ−１０９ＥＨ）からなる素材を入れ、陽極として錫板を使用して、液温２５℃、電流密度１０Ａ／ｄｍ２でスターラーにより３００ｒｐｍで攪拌しながら電気めっきを行い、膜厚１μｍの錫とグラファイト粒子の複合めっき皮膜が形成された錫めっき材を作製した。なお、複合めっき皮膜の膜厚は、蛍光Ｘ線膜厚測定法により４点の平均値から算出した。 In the above tin plating bath, a material made of Cu-Ni-Sn alloy material (NB-109EH manufactured by Dowa Mining Co., Ltd.) having a thickness of 0.25 mm was put, and a tin plate was used as an anode, and the liquid temperature was 25 ° C, Electroplating was performed while stirring at 300 rpm with a stirrer at a current density of 10 A / dm 2 to prepare a tin-plated material on which a composite plating film of tin and graphite particles having a thickness of 1 μm was formed. In addition, the film thickness of the composite plating film was calculated from the average value of 4 points by the fluorescent X-ray film thickness measurement method.
得られた錫めっき材を超音波洗浄して表面に付着したグラファイト粒子を除去した後、錫めっき材の複合めっき皮膜中の炭素の含有量を算出し、錫めっき材の摩擦係数を算出し、光沢度および表面粗さを測定した。 After removing the graphite particles adhering to the surface by ultrasonically cleaning the obtained tin plating material, calculating the carbon content in the composite plating film of the tin plating material, calculating the friction coefficient of the tin plating material, Glossiness and surface roughness were measured.
錫めっき皮膜中の炭素含有量は、得られた錫めっき材（素材を含む）から切り出した試験片を錫および炭素の分析用にそれぞれ用意し、試験片中の錫の含有量（Ｘ重量％）をＩＣＰ装置（ジャーレルアッシュ社製のＩＲＩＳ／ＡＲ）を用いてプラズマ分光分析法によって求めるとともに、試験片中の炭素の含有量（Ｙ重量％）を微量炭素・硫黄分析装置（堀場製作所製のＥＭＩＡ−Ｕ５１０）を用いて燃焼赤外線吸収法によって求め、Ｙ／（Ｘ＋Ｙ）として算出した。その結果、本実施例では、炭素含有量が１．１３重量％であった。 The carbon content in the tin plating film was prepared by preparing test pieces cut out from the obtained tin-plated material (including raw materials) for analysis of tin and carbon, respectively. ) Is obtained by plasma spectroscopic analysis using an ICP apparatus (IRIS / AR manufactured by Jarrel Ash), and the carbon content (Y wt%) in the test piece is determined by a trace carbon / sulfur analyzer (manufactured by Horiba, Ltd. EMIA-U510), and was calculated by the combustion infrared absorption method and calculated as Y / (X + Y). As a result, in this example, the carbon content was 1.13% by weight.
錫めっき材の摩擦係数として、得られた錫めっき材から切り出した試験片と錫リフロー材との間の摩擦係数を求めた。この摩擦係数（μ）は、得られた錫めっき材から切り出した試験片をインデント加工（Ｒ３ｍｍ）して凸形状の圧子とするとともに、平板状の錫リフロー材をベース側の評価試料とし、ロードセルを使用して、圧子を加重３Ｎで評価試料の表面に押し付けながら移動速度６０ｍｍ／分で滑らせ、水平方向にかかる力（Ｆ）を測定し、μ＝Ｆ／Ｎから算出した。その結果、本実施例では、摩擦係数は０．１１であった。なお、ベース側の評価試料として使用した錫リフロー材は、６０ｇ／Ｌの金属錫を含む硫酸第一錫と６０ｇ／Ｌの硫酸とを含む錫めっき液中に、厚さ０．２５ｍｍのＣｕ−Ｎｉ−Ｓｎ合金材（同和鉱業製のＮＢ−１０９ＥＨ）からなる素材を入れ、液温２５℃、電流密度１０Ａ／ｄｍ２で電気めっきを行って、膜厚１．０μｍのめっき皮膜を形成した後、２４０℃でリフロー処理を施すことにより作製した。このリフロー処理により作製した錫リフロー材の同種同士の摩擦係数は０．２０〜０．２４であった。 The friction coefficient between the test piece cut out from the obtained tin plating material and the tin reflow material was determined as the friction coefficient of the tin plating material. The friction coefficient (μ) is obtained by indenting (R3 mm) a test piece cut out from the obtained tin-plated material to form a convex indenter, and using a plate-shaped tin reflow material as a base-side evaluation sample. , The indenter was slid at a moving speed of 60 mm / min while pressing the indenter against the surface of the evaluation sample with a weight of 3 N, the force (F) applied in the horizontal direction was measured, and calculated from μ = F / N. As a result, in this example, the coefficient of friction was 0.11. In addition, the tin reflow material used as the evaluation sample on the base side was Cu-- having a thickness of 0.25 mm in a tin plating solution containing stannous sulfate containing 60 g / L of metallic tin and 60 g / L of sulfuric acid. After putting a material made of Ni-Sn alloy material (NB-109EH made by Dowa Mining) and performing electroplating at a liquid temperature of 25 ° C. and a current density of 10 A / dm 2 to form a plating film with a film thickness of 1.0 μm It was prepared by applying a reflow treatment at 240 ° C. The friction coefficient of the same kind of tin reflow material produced by this reflow treatment was 0.20 to 0.24.
錫めっき材の光沢度として、光沢度計（日本電色工業製のデンシトメーターＮＤ−１）を使用して視感反射濃度を測定した。その結果、本実施例では、光沢度が１．２８であった。 As the glossiness of the tin plating material, the luminous reflection density was measured using a gloss meter (Nippon Denshoku Densitometer ND-1). As a result, in this example, the glossiness was 1.28.
錫めっき材の表面粗さについては、超深度顕微鏡（ＫＹＥＮＣＥ社製のＶＫ−８５００）による測定結果から、ＪＩＳ Ｂ０６０１に基づいて表面粗さを表すパラメータである算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを算出した。その結果、本実施例では、算術平均粗さＲａが０．１１μｍ、最大高さＲｙが１０．４μｍ、十点平均粗さＲｚが８．３μｍであった。 The surface roughness of the tin-plated, ultradeep microscope from the measurement result by (KYENCE Co. VK-8500), arithmetic mean roughness Ra, the maximum height is a parameter representing the surface roughness based on JIS B0601 Ry and ten-point average roughness Rz were calculated. As a result, in the present embodiment, arithmetic mean roughness Ra of 0.11 .mu.m, a maximum height Ry of 10.4 .mu.m, the ten-point average roughness Rz was 8.3 .mu.m.
［実施例２］
電流密度を１５Ａ／ｄｍ２にした以外は実施例１と同様の方法により錫めっき材を作製し、得られた錫めっき材について、実施例１と同様の方法により、錫めっき材の複合めっき皮膜中の炭素含有量および錫めっき材の摩擦係数を算出し、光沢度および表面粗さを測定した。その結果、炭素含有量は１．１４重量％、摩擦係数は０．１０、光沢度は１．５３であり、算術平均粗さＲａは０．１３μｍ、最大高さＲｙは１５．９μｍ、十点平均粗さＲｚは１０．８μｍであった。
[Example 2]
A tin-plated material was prepared by the same method as in Example 1 except that the current density was 15 A / dm 2 , and the resulting tin-plated material was composite-plated with a tin-plated material by the same method as in Example 1. The carbon content and the friction coefficient of the tin plating material were calculated, and the glossiness and surface roughness were measured. As a result, the carbon content is 1.14 wt%, the friction coefficient is 0.10, the gloss is 1.53, arithmetic average roughness Ra is 0.13 [mu] m, maximum height Ry is 15.9Myuemu, ten The point average roughness Rz was 10.8 μm.
［比較例１］
電流密度を５Ａ／ｄｍ２にした以外は実施例１と同様の方法により錫めっき材を作製し、得られた錫めっき材について、実施例１と同様の方法により、錫めっき材の複合めっき皮膜中の炭素含有量および錫めっき材の摩擦係数を算出し、光沢度および表面粗さを測定した。その結果、炭素含有量は１．１１重量％、摩擦係数は０．２０、光沢度は０．７３であった。また、表面に炭素粒子が強く凝集しており、表面粗さが粗く、算術平均粗さＲａは０．８１μｍ、最大高さＲｙは２４．９μｍ、十点平均粗さＲｚは１９．０μｍであった。
[Comparative Example 1]
A tin-plated material was prepared by the same method as in Example 1 except that the current density was 5 A / dm 2 , and the resulting tin-plated material was combined with a tin-plated composite film by the same method as in Example 1. The carbon content and the friction coefficient of the tin plating material were calculated, and the glossiness and surface roughness were measured. As a result, the carbon content was 1.11% by weight, the friction coefficient was 0.20, and the glossiness was 0.73. The surface has strong aggregation carbon particles, rough surface roughness, arithmetic average roughness Ra is 0.81 .mu.m, the maximum height Ry is 24.9Myuemu, the ten-point average roughness Rz at 19.0μm there were.
［実施例３］
スターラーを５００ｒｐｍで回転させた以外は実施例１と同様の方法により錫めっき材を作製し、得られた錫めっき材について、実施例１と同様の方法により、錫めっき材の複合めっき皮膜中の炭素含有量および錫めっき材の摩擦係数を算出し、光沢度および表面粗さを測定した。その結果、炭素含有量は１．１３重量％、摩擦係数は０．１２、光沢度は１．１５であり、算術平均粗さＲａは０．３１μｍ、最大高さＲｙは１１．７μｍ、十点平均粗さＲｚは９．６μｍであった。
[Example 3]
A tin-plated material was produced by the same method as in Example 1 except that the stirrer was rotated at 500 rpm, and the obtained tin-plated material was subjected to the same process as in Example 1 by the same method as in Example 1 in the composite plating film of the tin-plated material. The carbon content and the coefficient of friction of the tin plating material were calculated, and the glossiness and surface roughness were measured. As a result, the carbon content is 1.13 wt%, the friction coefficient is 0.12, the gloss is 1.15, arithmetic average roughness Ra is 0.31 .mu.m, the maximum height Ry is 11.7, ten The point average roughness Rz was 9.6 μm.
［実施例４］
スターラーを５００ｒｐｍで回転させた以外は実施例２と同様の方法により錫めっき材を作製し、得られた錫めっき材について、実施例１と同様の方法により、錫めっき材の複合めっき皮膜中の炭素含有量および錫めっき材の摩擦係数を算出し、光沢度および表面粗さを測定した。その結果、炭素含有量は０．９４重量％、摩擦係数は０．０９、光沢度は１．２６であり、算術平均粗さＲａは０．１３μｍ、最大高さＲｙは１３．３μｍ、十点平均粗さＲｚは８．２μｍであった。
[Example 4]
A tin-plated material was produced by the same method as in Example 2 except that the stirrer was rotated at 500 rpm, and the obtained tin-plated material was subjected to the same process as in Example 1 by the same method as in Example 1 in the composite plating film of the tin-plated material. The carbon content and the coefficient of friction of the tin plating material were calculated, and the glossiness and surface roughness were measured. As a result, the carbon content is 0.94 wt%, the friction coefficient is 0.09, the gloss is 1.26, arithmetic average roughness Ra is 0.13 [mu] m, maximum height Ry is 13.3, ten The point average roughness Rz was 8.2 μm.
［比較例２］
スターラーを５００ｒｐｍで回転させた以外は比較例１と同様の方法により錫めっき材を作製し、得られた錫めっき材について、実施例１と同様の方法により、錫めっき材の複合めっき皮膜中の炭素含有量および錫めっき材の摩擦係数を算出し、光沢度および表面粗さを測定した。その結果、炭素含有量は０．９６重量％、摩擦係数は０．１８、光沢度は０．８５であり、算術平均粗さＲａは０．５８μｍ、最大高さＲｙは２２．７μｍ、十点平均粗さＲｚは１４．８μｍであった。
[Comparative Example 2]
A tin-plated material was produced by the same method as in Comparative Example 1 except that the stirrer was rotated at 500 rpm, and the obtained tin-plated material was subjected to the same process as in Example 1 by the same method as in Example 1 in the composite plating film of the tin-plated material. The carbon content and the coefficient of friction of the tin plating material were calculated, and the glossiness and surface roughness were measured. As a result, the carbon content is 0.96 wt%, the friction coefficient is 0.18, the gloss was 0.85, arithmetic average roughness Ra is 0.58 .mu.m, the maximum height Ry is 22.7Myuemu, ten The point average roughness Rz was 14.8 μm.
［実施例５〜７］
グラファイト粒子の添加量を１０ｇ／Ｌとした以外は、それぞれ比較例１、実施例１および実施例２と同様の方法により錫めっき材を作製し、得られた錫めっき材について、実施例１と同様の方法により、錫めっき材の複合めっき皮膜中の炭素含有量および錫めっき材の摩擦係数を算出し、光沢度および表面粗さを測定した。その結果、炭素含有量は０．９４〜１．０２重量％、摩擦係数は０．０７〜０．１０、光沢度は０．９０〜１．４４であり、算術平均粗さＲａは０．１６〜０．４６μｍ、最大高さＲｙは９．７〜１２．７μｍ、十点平均粗さＲｚは７．１〜１０．３μｍであった。
[Examples 5 to 7]
A tin plating material was produced by the same method as Comparative Example 1, Example 1 and Example 2 except that the addition amount of the graphite particles was 10 g / L. By the same method, the carbon content in the composite plating film of the tin plating material and the friction coefficient of the tin plating material were calculated, and the glossiness and surface roughness were measured. As a result, the carbon content is 0.94 to 1.02 wt%, the friction coefficient is 0.07 to 0.10, the gloss is from 0.90 to 1.44, arithmetic average roughness Ra is 0. The maximum height Ry was 9.7 to 12.7 μm, and the ten-point average roughness Rz was 7.1 to 10.3 μm.
［実施例８〜１０］
スターラーを５００ｒｐｍで回転させた以外は、それぞれ実施例５〜７と同様の方法により錫めっき材を作製し、得られた錫めっき材について、実施例１と同様の方法により、錫めっき材の複合めっき皮膜中の炭素含有量および錫めっき材の摩擦係数を算出し、光沢度および表面粗さを測定した。その結果、炭素含有量は０．９９〜１．０２重量％、摩擦係数は０．１１〜０．１３、光沢度は０．８３〜１．１６であり、算術平均粗さＲａは０．１９〜０．４８μｍ、最大高さＲｙは８．９〜１４．６μｍ、十点平均粗さＲｚは７．０〜１１．３μｍであった。
[Examples 8 to 10]
Except for rotating the stirrer at 500 rpm, a tin-plated material was prepared in the same manner as in Examples 5 to 7, and the obtained tin-plated material was combined with a tin-plated material in the same manner as in Example 1. The carbon content in the plating film and the friction coefficient of the tin plating material were calculated, and the glossiness and surface roughness were measured. As a result, the carbon content is 0.99 to 1.02 wt%, the friction coefficient is 0.11 and 0.13, the gloss is from 0.83 to 1.16, arithmetic average roughness Ra is 0. The maximum height Ry was 8.9 to 14.6 μm, and the ten-point average roughness Rz was 7.0 to 11.3 μm.
［比較例３〜５］
グラファイト粒子の添加量を２０ｇ／Ｌとした以外は、それぞれ実施例５〜７と同様の方法により錫めっき材を作製し、得られた錫めっき材について、実施例１と同様の方法により、錫めっき材の複合めっき皮膜中の炭素含有量および錫めっき材の摩擦係数を算出し、光沢度および表面粗さを測定した。その結果、炭素含有量は０．９６〜１．３８重量％、摩擦係数は０．２０〜０．３６、光沢度は０．５９〜１．３９であった。また、表面に炭素粒子が強く凝集しており算術平均粗さＲａは０．３５〜０．６２μｍ、最大高さＲｙは１０．５〜１４．８μｍ、十点平均粗さＲｚは９．０〜１１．９μｍであった。
[Comparative Examples 3 to 5]
A tin-plated material was prepared in the same manner as in Examples 5 to 7 except that the amount of graphite particles added was 20 g / L. The obtained tin-plated material was tinned in the same manner as in Example 1. The carbon content in the composite plating film of the plating material and the friction coefficient of the tin plating material were calculated, and the glossiness and surface roughness were measured. As a result, the carbon content was 0.96 to 1.38% by weight, the friction coefficient was 0.20 to 0.36, and the glossiness was 0.59 to 1.39. Further, the arithmetic average roughness Ra has strong aggregation carbon particles to the surface 0.35～0.62Myuemu, the maximum height Ry is 10.5～14.8Myuemu, the ten-point average roughness Rz 9.0 It was ˜11.9 μm.
［比較例６〜８］
グラファイト粒子の添加量を２０ｇ／Ｌとした以外は、それぞれ実施例８〜１０と同様の方法により錫めっき材を作製し、得られた錫めっき材について、実施例１と同様の方法により、錫めっき材の複合めっき皮膜中の炭素含有量および錫めっき材の摩擦係数を算出し、光沢度および表面粗さを測定した。その結果、炭素含有量は１．０２〜１．４０重量％、摩擦係数は０．１７〜０．３７、光沢度は０．５４〜１．１４であった。また、表面に炭素粒子が強く凝集しており算術平均粗さＲａは０．２４〜０．５３μｍ、最大高さＲｙは８．４〜１８．８μｍ、十点平均粗さＲｚは７．１〜１２．０μｍであった。
[Comparative Examples 6-8]
A tin-plated material was prepared in the same manner as in Examples 8 to 10 except that the amount of graphite particles added was 20 g / L. The obtained tin-plated material was tinned in the same manner as in Example 1. The carbon content in the composite plating film of the plating material and the friction coefficient of the tin plating material were calculated, and the glossiness and surface roughness were measured. As a result, the carbon content was 1.02 to 1.40% by weight, the friction coefficient was 0.17 to 0.37, and the glossiness was 0.54 to 1.14. Further, the arithmetic average roughness Ra has strong aggregation carbon particles to the surface 0.24～0.53Myuemu, the maximum height Ry is 8.4～18.8Myuemu, ten-point average roughness Rz is 7.1 It was ˜12.0 μm.
これらの実施例および比較例の結果を表１に示し、算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚ、光沢度と摩擦係数との関係を図１〜図４に示す。これらの表および図に示すように、実施例では、比較例と比べて、錫リフロー材との間の摩擦係数が極めて低いことがわかる。 The results of these examples and comparative examples shown in Table 1, showing arithmetic average roughness Ra, the maximum height Ry, the ten-point average roughness Rz, the relationship between the glossiness and the coefficient of friction in FIGS . As shown in these tables and figures, it can be seen that the friction coefficient between the example and the tin reflow material in the example is extremely low as compared with the comparative example.
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