JP2010090400A - Electroconductive material and method for manufacturing the same - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000007747 plating Methods 0.000 claims abstract description 44
- 238000011282 treatment Methods 0.000 claims abstract description 32
- 238000005422 blasting Methods 0.000 claims abstract description 28
- 239000004020 conductor Substances 0.000 claims description 62
- 239000010949 copper Substances 0.000 claims description 35
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 12
- 229910017755 Cu-Sn Inorganic materials 0.000 claims description 12
- 229910017927 Cu—Sn Inorganic materials 0.000 claims description 12
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 238000004458 analytical method Methods 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 112
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000523 sample Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
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- 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 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
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- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
本発明は、自動車用コネクタ端子、バスバー、電気・電子部品の端子等に用いられる耐熱性に優れた導電材及び該導電材の製造方法に関する。 The present invention relates to a conductive material having excellent heat resistance used for connector terminals for automobiles, bus bars, terminals of electric / electronic parts, and the like, and a method for producing the conductive material.
プリント回路基板（以下、「ＰＣＢ」と称することもある）等のスルーホールに挿入される端子、又は表面実装される端子は、錫（Ｓｎ）被覆された銅又は銅合金の条材からプレスで成形されたものが一般的であり、Ｓｎ−Ｐｂ系はんだで基板に取り付けられていた。また、部品の小型化等により端子の細線化も進み、プレス時に露出した端面の面積比率が高まっている。更に、Ｐｂフリー化に伴いＰｂを含まないはんだ（以下、「Ｐｂフリーはんだ」と称することもある）でのはんだ付けが要求されている。Ｐｂを含まないはんだでは、Ｓｎ−Ａｇ−Ｃｕ系等が有名であるが、Ｓｎ−Ｐｂ系はんだに比べて融点が高く、はんだ付け性が低下するため端子を基板へ取り付けることが困難になっている。 A terminal inserted into a through hole such as a printed circuit board (hereinafter also referred to as “PCB”) or a surface-mounted terminal is pressed from a strip of copper or copper alloy coated with tin (Sn). What was shape | molded was common and was attached to the board | substrate with the Sn-Pb type solder. In addition, due to the miniaturization of parts and the like, the terminals are becoming thinner, and the area ratio of the end face exposed during pressing is increasing. Furthermore, with Pb-free, soldering with solder that does not contain Pb (hereinafter also referred to as “Pb-free solder”) is required. Sn-Ag-Cu-based solders are well known as solders that do not contain Pb. However, since the melting point is higher than that of Sn-Pb-based solders and solderability is reduced, it is difficult to attach terminals to a substrate. Yes.
また、Ｐｂフリー化に対する別のアプローチとして、端子の先端をバネ状にプレス成形し、直接スルーホールに固定する技術も開発されている。端子の耐熱性を確保するために、プレス加工後に厚い（３μｍ超の）Ｓｎめっきを施す場合が多いが、元々非常に高い接圧で設計された端子のため、スルーホール挿入時の挿入力が大きすぎるという問題がある。
また、挿入力低減のために、Ｓｎ層の厚さを単純に薄くすることが考えられるが、その場合には経時変化により表面に厚い酸化物が形成されやすく、基板や別コネクタとの接続部において耐熱性に問題が生じるおそれがある。
As another approach to Pb-free, a technique has been developed in which the tip of the terminal is pressed into a spring shape and directly fixed to the through hole. In order to ensure the heat resistance of the terminals, thick (> 3 μm) Sn plating is often applied after pressing, but since the terminals were originally designed with a very high contact pressure, the insertion force when inserting through-holes There is a problem that it is too big.
In order to reduce the insertion force, it is conceivable to simply reduce the thickness of the Sn layer. In that case, a thick oxide is likely to be formed on the surface due to changes over time, and the connection portion with the substrate or another connector There is a risk of problems in heat resistance.
ＰＣＢに挿入される端子には、コスト、耐熱性、耐食性、はんだ付け性の観点から、Ｓｎめっきが広く利用されている（特許文献１参照）。
しかし、Ｓｎ被覆方法が光沢Ｓｎめっきの場合、ウィスカ及び耐熱性の問題がある。Ｓｎめっき後にリフロー処理を行えばウィスカを大幅に低減できるが、自動車のエンジンルーム等の厳しい熱環境においては十分な耐熱性を有していない。
したがって耐熱性に優れた低コストの導電材の提供が強く求められているのが現状である。
For the terminals inserted into the PCB, Sn plating is widely used from the viewpoint of cost, heat resistance, corrosion resistance, and solderability (see Patent Document 1).
However, when the Sn coating method is bright Sn plating, there are whisker and heat resistance problems. If reflow treatment is performed after Sn plating, whiskers can be greatly reduced, but they do not have sufficient heat resistance in a severe thermal environment such as an engine room of an automobile.
Therefore, at present, there is a strong demand for providing a low-cost conductive material having excellent heat resistance.
本発明は、従来における前記問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、１６０℃の大気中で長時間保持した後の接触抵抗の上昇が少ない耐熱性に優れた導電材及び該導電材を効率よく製造する方法を提供することを目的とする。 An object of the present invention is to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide a conductive material excellent in heat resistance with little increase in contact resistance after being kept in the atmosphere at 160 ° C. for a long time, and a method for efficiently producing the conductive material.
前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ 素材上に少なくともＳｎ層を形成するＳｎ層形成工程と、
前記Ｓｎ層をウエットブラスト処理するウエットブラスト処理工程と、を含むことを特徴とする導電材の製造方法である。
＜２＞ Ｓｎ層がめっきにより形成される前記＜１＞に記載の導電材の製造方法である。
＜３＞ Ｓｎ層形成工程において、素材側から順にＮｉ層、Ｃｕ層、及びＳｎ層をめっきにより形成する前記＜２＞に記載の導電材の製造方法である。
＜４＞ Ｓｎ層形成工程とウエットブラスト処理工程の間において、該Ｓｎ層形成工程により形成された層にリフロー処理を行うリフロー処理工程を含む前記＜１＞から＜３＞のいずれかに記載の導電材の製造方法である。
＜５＞ Ｓｎ層形成工程、ウエットブラスト処理工程、及びリフロー処理工程の少なくともいずれかが、リールトゥリールのラインで行われる前記＜４＞に記載の導電材の製造方法である。
＜６＞ 前記＜１＞から＜５＞のいずれかに記載の導電材の製造方法により製造されたことを特徴とする導電材である。
＜７＞ 最表面がＳｎ層であり、該Ｓｎ層がＥＳＣＡ分析により金属の水酸化物を含有する前記＜６＞に記載の導電材である。
＜８＞ 素材側から順にＮｉ層、Ｃｕ層、及びＳｎ層を有する前記＜６＞から＜７＞のいずれかに記載の導電材である。
＜９＞ 素材側から順にＮｉ層、Ｃｕ−Ｓｎ合金層、及びＳｎ層、又は素材側から順にＮｉ層、Ｃｕ層、Ｃｕ−Ｓｎ合金層、及びＳｎ層を有する前記＜６＞から＜７＞のいずれかに記載の導電材である。
＜１０＞ Ｓｎ層の厚みが、０.３μｍ〜３μｍである前記＜６＞から＜９＞のいずれかに記載の導電材である。
＜１１＞ Ｎｉ層の厚みが０.０５μｍ〜２μｍであり、Ｃｕ層の厚みが０.０５μｍ〜１μｍである前記＜６＞から＜１０＞のいずれかに記載の導電材である。
＜１２＞ Ｃｕ−Ｓｎ層の厚みが０．１μｍ〜２．０μｍである前記＜９＞から＜１１＞のいずれかに記載の導電材である。
＜１３＞ Ｓｎ層が、リフロー処理による溶融組織を有する前記＜６＞から＜１２＞のいずれかに記載の導電材である。
＜１４＞ 素材が、銅又は銅合金である前記＜６＞から＜１３＞のいずれかに記載の導電材である。
＜１５＞ 素材の最表面にＳｎ層が形成され、該Ｓｎ層がＥＳＣＡ分析により金属の水酸化物を含有することを特徴とする導電材である。
Means for solving the problems are as follows. That is,
<1> a Sn layer forming step of forming at least a Sn layer on the material;
And a wet blasting process for wet blasting the Sn layer.
<2> The method for producing a conductive material according to <1>, wherein the Sn layer is formed by plating.
<3> The method for producing a conductive material according to <2>, wherein in the Sn layer forming step, the Ni layer, the Cu layer, and the Sn layer are formed in order from the material side by plating.
<4> The method according to any one of <1> to <3>, further including a reflow treatment step of performing a reflow treatment on the layer formed by the Sn layer formation step between the Sn layer formation step and the wet blast treatment step. It is a manufacturing method of an electrically-conductive material.
<5> The method for producing a conductive material according to <4>, wherein at least one of the Sn layer forming step, the wet blasting step, and the reflow processing step is performed on a reel-to-reel line.
<6> A conductive material produced by the method for producing a conductive material according to any one of <1> to <5>.
<7> The conductive material according to <6>, wherein the outermost surface is a Sn layer, and the Sn layer contains a metal hydroxide by ESCA analysis.
<8> The conductive material according to any one of <6> to <7>, including a Ni layer, a Cu layer, and a Sn layer in order from the material side.
<9> From the above <6> to <7> having a Ni layer, a Cu—Sn alloy layer, and a Sn layer sequentially from the material side, or a Ni layer, a Cu layer, a Cu—Sn alloy layer, and a Sn layer sequentially from the material side The conductive material according to any one of the above.
<10> The conductive material according to any one of <6> to <9>, wherein the Sn layer has a thickness of 0.3 μm to 3 μm.
<11> The conductive material according to any one of <6> to <10>, wherein the Ni layer has a thickness of 0.05 μm to 2 μm and the Cu layer has a thickness of 0.05 μm to 1 μm.
<12> The conductive material according to any one of <9> to <11>, wherein the Cu—Sn layer has a thickness of 0.1 μm to 2.0 μm.
<13> The conductive material according to any one of <6> to <12>, wherein the Sn layer has a molten structure by reflow treatment.
<14> The conductive material according to any one of <6> to <13>, wherein the material is copper or a copper alloy.
<15> A conductive material characterized in that a Sn layer is formed on the outermost surface of the material, and the Sn layer contains a metal hydroxide by ESCA analysis.
本発明によると、従来における諸問題を解決でき、１６０℃の大気中で長時間保持した後の接触抵抗の上昇が少ない耐熱性に優れた導電材及び該導電材を効率よく製造する方法を提供することができる。 According to the present invention, it is possible to solve conventional problems and provide a conductive material having excellent heat resistance with little increase in contact resistance after being kept in the atmosphere at 160 ° C. for a long time, and a method for efficiently producing the conductive material. can do.
（導電材及び導電材の製造方法）
本発明の導電材の製造方法は、Ｓｎ層形成工程（「めっき工程」と称することもある）と、ウエットブラスト処理工程とを含み、リフロー処理工程、更に必要に応じてその他の工程を含んでなる。前記Ｓｎ層形成工程は湿式又は乾式でＳｎ層（皮膜）を形成する工程である。また、Ｓｎ層は、電気めっき、無電解めっき、溶融めっき等のめっきで形成されることが好ましい。
本発明の導電材は、本発明の導電材の製造方法により製造される。
以下、本発明の導電材の製造方法及び導電材について詳細に説明する。
(Conductive material and conductive material manufacturing method)
The method for producing a conductive material of the present invention includes a Sn layer forming step (sometimes referred to as a “plating step”) and a wet blasting step, a reflow processing step, and further including other steps as necessary. Become. The Sn layer forming step is a step of forming an Sn layer (film) by a wet method or a dry method. The Sn layer is preferably formed by electroplating, electroless plating, hot dipping, or the like.
The conductive material of the present invention is manufactured by the method for manufacturing a conductive material of the present invention.
Hereinafter, the method for producing a conductive material and the conductive material of the present invention will be described in detail.
本発明の導電材の製造方法としては、例えば銅又は銅合金の条又は所望のコネクタやリードフレーム等の電気・電子部品の形状に成形された連鎖条としての素材上に、下地層を形成することが好ましい。
前記下地層としては、素材側からＮｉ層とＣｕ層で形成された層であることが好ましい。
前記下地層上にＳｎ層を形成し、好ましくはリフロー処理を行い、その後ウエットブラスト処理を行う。
前記ウエットブラスト処理を行う場合には、素材上に下地層を設けずＳｎ層のみを設けてもよい。
また、前記下地層及びＳｎ層はめっきにより形成することが好ましい。
As the method for producing a conductive material of the present invention, for example, a base layer is formed on a material as a strip or a strip formed of copper or a copper alloy or a desired connector or lead frame. It is preferable.
The underlayer is preferably a layer formed of a Ni layer and a Cu layer from the material side.
An Sn layer is formed on the underlayer, and preferably a reflow process is performed, followed by a wet blast process.
When the wet blasting is performed, only the Sn layer may be provided on the material without providing the base layer.
The underlayer and Sn layer are preferably formed by plating.
本発明の導電材の製造方法においては、図１に示すように、Ｓｎ層形成工程（めっき工程）、ウエットブラスト処理工程、及びリフロー処理工程の少なくともいずれかが、リールトゥリールのラインで行われることが好ましい。
銅又は銅合金からなる素材の条を巻き取った材料リールから、まず素材の条を巻き出し、必要に応じてあらかじめ下地層を形成したのち、電気Ｓｎめっき等によりＳｎ層を形成し、次いでリフロー処理を行い、その後ウエットブラスト処理を行って、製品リールに巻き取る方法を行えば、効率的である。なお、各工程ごとに、必要に応じて電解脱脂、酸洗、洗浄、乾燥を行うことが好ましい。
より具体的には、リールトゥリールのラインでめっき工程を行う場合には、素材の条材を連続的にめっき槽に供給し電気めっき後に連続的に巻き取ることができる。例えば、素材の条材をめっき槽の側面から水平方向にめっき槽内へ供給し、めっき後、対向する側面からめっき槽外へ水平方向に巻き取る。
下地層の形成工程、リフロー処理工程、及びウエットブラスト処理工程も同様に連続的に行うことができ、これら工程を連続して行えばリールトゥリールのラインですべての工程を一回で連続して行うことができる。
In the method for producing a conductive material of the present invention, as shown in FIG. 1, at least one of an Sn layer forming step (plating step), a wet blasting step, and a reflow processing step is performed on a reel-to-reel line. It is preferable.
First, the material strip is unwound from the material reel wound with the material strip made of copper or copper alloy, and after forming the base layer in advance as necessary, the Sn layer is formed by electric Sn plating or the like, and then reflowed It is efficient to carry out the process, and then perform a method of winding the product reel by wet blasting. In addition, it is preferable to perform electrolytic degreasing, pickling, washing, and drying as necessary for each step.
More specifically, when the plating process is performed on a reel-to-reel line, the strip material can be continuously supplied to the plating tank and continuously wound after electroplating. For example, the strip material is supplied into the plating tank from the side surface of the plating tank in the horizontal direction, and after the plating, it is wound up from the opposite side surface to the outside of the plating tank in the horizontal direction.
The underlayer formation process, reflow process process, and wet blast process process can be performed continuously as well, and if these processes are performed continuously, all the processes can be performed at once in a reel-to-reel line. It can be carried out.
−Ｓｎ層形成工程（めっき工程）−
前記Ｓｎ層形成工程は、素材上に少なくともＳｎ層を電気めっき等により形成する工程である。
前記素材としては、特に制限はなく、目的に応じて適宜選択することができ、例えば銅、銅合金、ステンレス、アルミニウム、などが挙げられる。これらの中でも、銅、銅合金が特に好ましい。
前記素材は、条又は所望の形状に成形された連鎖条の形態であることが好ましい。
-Sn layer formation process (plating process)-
The Sn layer forming step is a step of forming at least a Sn layer on the material by electroplating or the like.
There is no restriction | limiting in particular as said raw material, According to the objective, it can select suitably, For example, copper, copper alloy, stainless steel, aluminum, etc. are mentioned. Among these, copper and copper alloys are particularly preferable.
The material is preferably in the form of a strip or a chain strip formed into a desired shape.
前記Ｓｎ層形成工程においては、素材上にＳｎ層を直接形成してもよいが、素材側から順にＣｕ層、Ｓｎ層を形成してもよく、また素材側から順にＮｉ層、Ｃｕ層、及びＳｎ層を電気めっきにより形成することが好ましい。前記電気めっきは、厚さの制御に優れ、コスト的にも有利である点で好適である。
前記Ｎｉめっきは、複塩浴、普通浴、回転浴、高硫酸塩浴、ワット浴、全塩化物浴、硫酸塩−塩化物浴、全硫酸塩浴、高質浴、ストライクニッケル浴、スルファミン酸ニッケル浴、ほうふっ化ニッケル浴などの浴で行うことが好ましい。
Ｃｕめっきは、硫酸銅浴、ほうふっ化銅浴、シアン化銅浴、ピロリン酸銅浴などの浴で行うことが好ましい。
Ｓｎめっきは、アルカリ性浴、硫酸浴、塩酸浴、スルフォン酸浴、シアン性浴、ピロリン酸浴、ほうふっ化浴などの浴で行うことが好ましい。
なお、各めっき浴ともに光沢剤を添加してもしなくてもよい。
また、Ｓｎ層形成は無電解めっきや溶融めっき、あるいは蒸着やスパッタリング等で形成してもよいが、層の形成コストから電気めっきが好ましい。
In the Sn layer forming step, the Sn layer may be formed directly on the material, but the Cu layer and the Sn layer may be formed in order from the material side, and the Ni layer, the Cu layer, and The Sn layer is preferably formed by electroplating. The electroplating is preferable in that it is excellent in thickness control and advantageous in cost.
The Ni plating includes double salt bath, normal bath, rotating bath, high sulfate bath, watt bath, total chloride bath, sulfate-chloride bath, total sulfate bath, high quality bath, strike nickel bath, sulfamic acid. It is preferable to use a bath such as a nickel bath or a nickel borofluoride bath.
Cu plating is preferably performed in a copper sulfate bath, a copper borofluoride bath, a copper cyanide bath, a copper pyrophosphate bath, or the like.
The Sn plating is preferably performed in a bath such as an alkaline bath, a sulfuric acid bath, a hydrochloric acid bath, a sulfonic acid bath, a cyanic bath, a pyrophosphoric acid bath, or a fluorinated bath.
Note that a brightener may or may not be added to each plating bath.
The Sn layer may be formed by electroless plating, hot dipping, vapor deposition, sputtering, or the like, but electroplating is preferred from the cost of forming the layer.
−ウエットブラスト処理工程−
前記ウエットブラスト処理工程は、前記Ｓｎ層形成工程で形成された最表面層であるＳｎ層をウエットブラスト処理する工程である。
前記ウエットブラストとは、粒子を利用した加工方法の１種であり、粒子（研磨材）と液体を混ぜ合せたスラリー液を投射ガン部において、圧縮空気の力を使って高速加速し、対象物に吹き付けて加工を行う方法である。
前記粒子（研磨材）としては、例えばアルミナ、ガラス、樹脂、ジルコニア、銅、チタン、ステンレス、シリカなど液と反応しない物質が挙げられる。粒子の形状としては多角状、球状のものが挙げられ、中心粒径は１μｍ〜１０００μｍ程度までのものが挙げられる。前記液体としては、水が挙げられる。圧縮空気圧力は０．０５ＭＰａ〜０．５ＭＰａ程度、スラリー濃度(粒子と液体の容積比)は３％〜４０％程度で実施する。
-Wet blasting process-
The wet blasting process is a process of performing a wet blasting process on the Sn layer that is the outermost surface layer formed in the Sn layer forming process.
The wet blasting is a kind of processing method using particles, and a slurry liquid obtained by mixing particles (abrasive material) and liquid is accelerated at high speed using the force of compressed air in the projection gun unit, It is a method of spraying and processing.
Examples of the particles (abrasive) include substances that do not react with the liquid, such as alumina, glass, resin, zirconia, copper, titanium, stainless steel, and silica. Examples of the shape of the particles include polygonal and spherical shapes, and those having a center particle size of about 1 μm to 1000 μm. An example of the liquid is water. The compressed air pressure is about 0.05 MPa to 0.5 MPa, and the slurry concentration (volume ratio of particles to liquid) is about 3% to 40%.
−リフロー処理工程−
前記リフロー処理工程は、前記Ｓｎ層形成工程と前記ウエットブラスト処理工程の間において、該Ｓｎ層形成工程により形成された層にリフロー処理を行う工程である。
めっき後にＳｎ層を加熱溶融させるリフロー処理を行う理由としては、耐ウィスカ性を向上させるためである。なお、耐ウィスカ性を必要としない場合は、リフロー処理を行わなくても構わない。
前記リフロー処理は、２５０℃〜９００℃の温度中に０.１秒〜１８０秒滞留させた後、１２０秒以内に水冷、空冷等により１００℃以下に冷却する方法であることが好ましい。
前記リフロー処理としては、例えばバーナー方式、熱風循環方式、赤外線方式、ジュール熱方式などが挙げられる。
本発明においては、Ｓｎ層がリフロー処理による溶融組織を有することが、上記の通りウィスカ対策の点で好ましい。
-Reflow treatment process-
The reflow treatment step is a step of performing a reflow treatment on the layer formed by the Sn layer formation step between the Sn layer formation step and the wet blast treatment step.
The reason for performing the reflow process for heating and melting the Sn layer after plating is to improve the whisker resistance. In addition, when the whisker resistance is not required, the reflow process may not be performed.
The reflow treatment is preferably a method in which the sample is kept at a temperature of 250 ° C. to 900 ° C. for 0.1 seconds to 180 seconds and then cooled to 100 ° C. or less by water cooling, air cooling, or the like within 120 seconds.
Examples of the reflow process include a burner method, a hot air circulation method, an infrared method, and a Joule heat method.
In the present invention, it is preferable that the Sn layer has a molten structure by reflow treatment in terms of measures against whisker as described above.
本発明の導電材は、本発明の前記導電材の製造方法により製造される。
前記導電材は、その最表面がＳｎ層であり、該Ｓｎ層がＥＳＣＡ分析（Ｘ線光電子分光分析）で金属の水酸化物を含有する。この金属の水酸化物の効果は完全に解明されていないが、金属水酸化物はウエットブラスト処理を実施することにより形成され、Ｓｎ表面に皮膜効果を発揮し、熱拡散を抑制していると推定される。
ここで、前記ＥＳＣＡ分析は、例えば定性分析(表面から数十ｎｍの深さまでの分析)、状態分析(表面から数十ｎｍの深さまでの分析)、深さ方向の分析(深さはＳｉＯ２換算)などにより行うことができる。
The electrically conductive material of this invention is manufactured by the manufacturing method of the said electrically conductive material of this invention.
The outermost surface of the conductive material is a Sn layer, and the Sn layer contains a metal hydroxide by ESCA analysis (X-ray photoelectron spectroscopy). Although the effect of this metal hydroxide has not been fully elucidated, the metal hydroxide is formed by carrying out wet blasting, exhibits a film effect on the Sn surface, and suppresses thermal diffusion. Presumed.
Here, the ESCA analysis includes, for example, qualitative analysis (analysis from the surface to a depth of several tens of nm), state analysis (analysis from the surface to a depth of several tens of nm), and analysis in the depth direction (depth is SiO 2 Conversion).
前記導電材は、素材側からＮｉ層、Ｃｕ層、Ｓｎ層、もしくはリフロー処理を行ったものについては素材側からＮｉ層、Ｃｕ−Ｓｎ合金層、Ｓｎ層、又は場合によってはＮｉ層とＣｕ−Ｓｎ層間にＣｕ層を有することが好ましい。
前記Ｓｎ層の厚みは、０.３μｍ〜３μｍであることが好ましく、０．５μｍ〜２．５μｍがより好ましく、０．８μｍ〜２μｍが更に好ましい。前記厚みが、０.３μｍ未満であると、経時変化によりはんだ付け性が十分ではないことがあり、３μｍを超えると、挿入力及びＳｎ層の削れが顕著になる他、コスト面でも不利となることがある。
The conductive material is Ni layer, Cu layer, Sn layer from the material side, or the Ni layer, Cu-Sn alloy layer, Sn layer, or in some cases Ni layer and Cu- It is preferable to have a Cu layer between Sn layers.
The thickness of the Sn layer is preferably 0.3 μm to 3 μm, more preferably 0.5 μm to 2.5 μm, and still more preferably 0.8 μm to 2 μm. If the thickness is less than 0.3 μm, the solderability may not be sufficient due to changes over time. If the thickness exceeds 3 μm, the insertion force and the Sn layer are severed, and the cost is disadvantageous. Sometimes.
前記Ｎｉ層は素材の銅又は銅合金のＣｕの拡散を効果的に抑制し、更には銅合金中の添加元素の拡散を効果的に抑制し（例えばＺｎやＰ）、接触抵抗やはんだ付け性、更には皮膜の耐熱密着性の低下を効果的に防止する。
前記Ｎｉ層の厚みは、０.０５μｍ〜２μｍであることが好ましい。前記厚みが、０.０５μｍ未満であると、前記元素の拡散を抑制する効果が得られないことがあり、２μｍを超えると、曲げ加工性が低下することがある。
The Ni layer effectively suppresses the diffusion of copper of the material copper or Cu of the copper alloy, and also effectively suppresses the diffusion of additive elements in the copper alloy (for example, Zn or P), and the contact resistance and solderability. In addition, it effectively prevents a decrease in the heat-resistant adhesion of the film.
The thickness of the Ni layer is preferably 0.05 μm to 2 μm. If the thickness is less than 0.05 μm, the effect of suppressing the diffusion of the element may not be obtained, and if it exceeds 2 μm, the bending workability may be deteriorated.
前記Ｃｕ層は、表面に被覆したＳｎ層と熱処理（リフロー処理等）によりＣｕ−Ｓｎの合金層を形成することが好ましい。Ｃｕ−Ｓｎ層についてもＮｉ層と同じくＣｕ又はＮｉの拡散、更には銅合金中の添加元素の拡散を効果的に抑制する。
前記Ｃｕ層の厚みは、０.０５μｍ〜１μｍであることが、耐食性向上、及び耐熱性向上を図る目的から好ましい。
更には、Ｃｕ−Ｓｎ層については０．１μｍ〜２μｍであることが、前記Ｎｉめっきの下限、上限を規定した同じ理由から好ましい。
The Cu layer is preferably formed by forming a Cu—Sn alloy layer by a Sn layer coated on the surface and heat treatment (reflow treatment or the like). Similarly to the Ni layer, the Cu—Sn layer also effectively suppresses the diffusion of Cu or Ni, and further the diffusion of the additive element in the copper alloy.
The thickness of the Cu layer is preferably 0.05 μm to 1 μm for the purpose of improving corrosion resistance and heat resistance.
Furthermore, about Cu-Sn layer, it is preferable that it is 0.1 micrometer-2 micrometers from the same reason which prescribed | regulated the minimum and the upper limit of said Ni plating.
−用途−
本発明の導電材は、１６０℃の大気中で長時間保持した後の接触抵抗の上昇が少ない耐熱性に優れたものであるので、例えば自動車用コネクタ端子、バスバー、電気・電子部品の端子等に好適に用いられる。
-Use-
Since the conductive material of the present invention is excellent in heat resistance with little increase in contact resistance after being kept in the atmosphere at 160 ° C. for a long time, for example, connector terminals for automobiles, bus bars, terminals of electric / electronic parts, etc. Is preferably used.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。
以下の例において、Ｎｉ層、Ｃｕ層、Ｃｕ−Ｓｎ合金層、及びＳｎ層の厚みは、以下のようにして測定した。
Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the following examples, the thicknesses of the Ni layer, Cu layer, Cu—Sn alloy layer, and Sn layer were measured as follows.
＜厚み測定＞
Ｎｉ層とＳｎ層の厚みは、蛍光Ｘ線膜厚測定器（セイコーインスツル社製、ＳＦＴ３３００）で測定した。
Ｃｕ層の厚みは、ＦＩＢ(集束イオンビーム)を用いて試料をエッチングしてその断面を露出させ、ＳＩＭ(走査イオン顕微鏡)を用いてその断面（エッチング面）観察することでＣｕ層の厚さを測定した。
Ｃｕ−Ｓｎ合金層の厚みは、表面Ｓｎめっきを薬液で剥離した後、電解式膜厚計（中央製作所製、ＴＨＩＣＫＮＥＳＳ ＴＥＳＴＥＲ ＴＨ１１）で測定した。
各層の厚さは、それぞれサンプルの両端１ｍｍ〜９ｍｍの範囲で２ｍｍおきに５点測定し、その平均値を求めた。
<Thickness measurement>
The thicknesses of the Ni layer and the Sn layer were measured with a fluorescent X-ray film thickness measuring instrument (manufactured by Seiko Instruments Inc., SFT3300).
The thickness of the Cu layer is determined by etching the sample using FIB (focused ion beam) to expose the cross section, and observing the cross section (etched surface) using SIM (scanning ion microscope). Was measured.
The thickness of the Cu—Sn alloy layer was measured with an electrolytic film thickness meter (manufactured by Chuo Seisakusho, THICKNESS TESTER TH11) after the surface Sn plating was peeled off with a chemical solution.
The thickness of each layer was measured at 5 points every 2 mm in the range of 1 mm to 9 mm at both ends of the sample, and the average value was obtained.
（実施例１）
素材として、Ｃｕ−１．０質量％Ｎｉ−０．９質量％Ｓｎ−０．０５質量％Ｐ、ビッカース硬さ（ＨＶ）１７０、厚さ０.２５ｍｍ、幅５０ｍｍの銅合金条を使用した。
リールトゥリールの連続めっきラインで、素材の表面及び端面を電解脱脂と酸洗で活性化した後、Ｓｎ層の被覆を行った。Ｓｎ層の被覆方法は、厚さの制御に優れ、コスト的にも有利な電気めっきを用いた。
なお、Ｓｎめっきは硫酸錫浴で行い、光沢剤を添加し、光沢めっきを行った。
Ｓｎめっきは、素材の両面からそれぞれ５０ｍｍの間隔で対向してＳｎ板の陽極を配置し、液温２０℃、見かけの陰極電流密度５.７Ａ／ｄｍ２で行い、厚み１μｍのＳｎ層を形成した。
Ｓｎ層を被覆後、バーナー炉でリフロー処理を行った。リフロー処理は、炉内温度４００〜６００℃、炉内滞留時間０.１〜２０秒で表面を溶融させた後、水冷と空冷を併用して１０秒以内に１００℃以下へ冷却した。
次に、以下の条件でウエットブラスト（ＷＢ）処理を行った。なお、ＷＢ処理によりＳｎ層が約０．１μｍ削られた。
−ウエットブラスト（ＷＢ）処理条件−
（１）装置：Ｘ軸ロボット式ウエットブラスト装置（ＷＦＢ−２−２Ｃ、マコー株式会社製）
（２）研磨材：アルミナ
（３）研磨材粒度：＃３２０（約４０μｍ）
（４）研磨材濃度：１８ｖｏｌ％
（５）ライン（ガン）スピード１０ｍ／ｍｉｎ、パス回数１回、ブラストエアー圧０．２５ＭＰａ
以上により、実施例１の導電材を作製した。
Example 1
As a raw material, a copper alloy strip having Cu-1.0 mass% Ni-0.9 mass% Sn-0.05 mass% P, Vickers hardness (HV) 170, thickness 0.25 mm, and width 50 mm was used.
In the reel-to-reel continuous plating line, the surface and the end face of the material were activated by electrolytic degreasing and pickling, and then the Sn layer was coated. As a method for coating the Sn layer, electroplating, which is excellent in thickness control and advantageous in terms of cost, was used.
Sn plating was performed in a tin sulfate bath, a brightener was added, and bright plating was performed.
Sn plating is carried out at a liquid temperature of 20 ° C. and an apparent cathode current density of 5.7 A / dm 2 to form a Sn layer with a thickness of 1 μm, facing each other at 50 mm intervals from both sides of the material. did.
After coating the Sn layer, reflow treatment was performed in a burner furnace. In the reflow treatment, the surface was melted at a furnace temperature of 400 to 600 ° C. and a furnace residence time of 0.1 to 20 seconds, and then cooled to 100 ° C. or less within 10 seconds using both water cooling and air cooling.
Next, wet blasting (WB) treatment was performed under the following conditions. Note that the Sn layer was scraped by about 0.1 μm by the WB treatment.
-Wet blasting (WB) processing conditions-
(1) Apparatus: X-axis robot type wet blasting apparatus (WFB-2-2C, manufactured by Macau Corporation)
(2) Abrasive: Alumina (3) Abrasive grain size: # 320 (about 40 μm)
(4) Abrasive concentration: 18 vol%
(5) Line (gun) speed 10 m / min, number of passes once, blast air pressure 0.25 MPa
Thus, the conductive material of Example 1 was produced.
（比較例１）
実施例１において、ウエットブラスト（ＷＢ）処理を行わなかった以外は、実施例１と同様にして、比較例１の導電材を作製した。
(Comparative Example 1)
A conductive material of Comparative Example 1 was produced in the same manner as in Example 1 except that the wet blasting (WB) treatment was not performed in Example 1.
（比較例２〜５）
比較例１において、表１に示す４通りのウエットブラスト（ＷＢ）処理をめっき工程の前に素材表面に行った以外は、比較例１と同様にして、比較例２〜５の導電材を作製した。
(Comparative Examples 2 to 5)
In Comparative Example 1, the conductive materials of Comparative Examples 2 to 5 were prepared in the same manner as Comparative Example 1 except that the four wet blasting (WB) treatments shown in Table 1 were performed on the material surface before the plating step. did.
（実施例２〜３及び比較例６）
実施例１において、ウエットブラスト（ＷＢ）処理条件を表１に示すように変えた以外は、実施例１と同様にして、実施例２〜３及び比較例６の導電材を作製した。
(Examples 2-3 and Comparative Example 6)
In Example 1, except that the wet blasting (WB) treatment conditions were changed as shown in Table 1, conductive materials of Examples 2 to 3 and Comparative Example 6 were produced in the same manner as Example 1.
（実施例４）
素材として、Ｃｕ−１．０質量％Ｎｉ−０．９質量％Ｓｎ−０．０５質量％Ｐ、ビッカース硬さ（ＨＶ）１７０、厚さ０.２ｍｍ、幅５０ｍｍの銅合金条を使用した。
リールトゥリールの連続めっきラインで、素材の表面及び端面を電解脱脂と酸洗で活性化した後、Ｎｉ及びＣｕからなる下地層と、Ｓｎ層の被覆を行った。各層の被覆方法は、厚さの制御に優れ、コスト的にも有利な電気めっきを用いた。下地層は全面均一に被覆するよう調整した。
Ｎｉめっきはスルファミン酸Ｎｉ浴、Ｃｕめっきは硫酸銅浴、Ｓｎめっきは硫酸錫浴で行った。Ｓｎめっき以外は無光沢めっきを行い、Ｓｎめっきは光沢剤を添加し、光沢めっきで行った。
Ｎｉめっきは、素材の両面からそれぞれ５０ｍｍの間隔で対向してＮｉ板の陽極を配置し、液温４０〜５０℃、見かけの陰極電流密度８Ａ／ｄｍ２で行い、厚み０．４μｍのＮｉ層を形成した。
Ｃｕめっきは、素材の両面からそれぞれ５０ｍｍの間隔で対向してＣｕ板の陽極を配置し、液温２５〜３５℃、見かけの陰極電流密度５Ａ／ｄｍ２で行い、厚み０．４μｍのＣｕ層を形成した。
Ｓｎめっきは、下地層を形成した素材の両面からそれぞれ５０ｍｍの間隔で対向してＳｎ板の陽極を配置し、液温２０℃、見かけの陰極電流密度５.７Ａ／ｄｍ２で行い、厚み０．７μｍのＳｎ層を形成した。
Ｓｎ層を被覆後、バーナー炉でリフロー処理を行った。リフロー処理は、炉内温度４００〜６００℃、炉内滞留時間０.１〜２０秒で表面を溶融させた後、水冷と空冷を併用して１０秒以内に１００℃以下へ冷却した。
次に、以下の条件でウエットブラスト（ＷＢ）処理を行った。なお、ＷＢ処理によりＳｎ層が約０．１μｍ削られた。
−ウエットブラスト（ＷＢ）処理条件−
（１）装置：Ｘ軸ロボット式ウエットブラスト装置（ＷＦＢ−２−２Ｃ、マコー株式会社製）
（２）研磨材：アルミナ
（３）研磨材粒度：＃３２０（約４０μｍ）
（４）研磨材濃度：１８ｖｏｌ％
（５）ライン（ガン）スピード１０ｍ／ｍｉｎ、パス回数１回、ブラストエアー圧０．２５ＭＰａ
以上により、実施例４の導電材を作製した
Example 4
A copper alloy strip having Cu-1.0 mass% Ni-0.9 mass% Sn-0.05 mass% P, Vickers hardness (HV) 170, thickness 0.2 mm, width 50 mm was used as a material.
In the reel-to-reel continuous plating line, the surface and end face of the material were activated by electrolytic degreasing and pickling, and then the underlayer made of Ni and Cu and the Sn layer were coated. As a coating method for each layer, electroplating that is excellent in thickness control and advantageous in cost was used. The underlayer was adjusted so as to cover the entire surface uniformly.
Ni plating was performed using a sulfamic acid Ni bath, Cu plating was performed using a copper sulfate bath, and Sn plating was performed using a tin sulfate bath. Except for Sn plating, matte plating was performed, and Sn plating was performed by bright plating with a brightener added.
Ni plating is carried out at a liquid temperature of 40 to 50 ° C., an apparent cathode current density of 8 A / dm 2 , and an Ni layer having a thickness of 0.4 μm. Formed.
Cu plating is carried out at a liquid temperature of 25 to 35 ° C. and an apparent cathode current density of 5 A / dm 2 , with a Cu layer having a thickness of 0.4 μm. Formed.
Sn plating is carried out at a liquid temperature of 20 ° C. and an apparent cathode current density of 5.7 A / dm 2 with a thickness of 0 mm, with the anodes of Sn plates facing each other at an interval of 50 mm from both surfaces of the material on which the base layer is formed. A 7 μm Sn layer was formed.
After coating the Sn layer, reflow treatment was performed in a burner furnace. In the reflow treatment, the surface was melted at a furnace temperature of 400 to 600 ° C. and a furnace residence time of 0.1 to 20 seconds, and then cooled to 100 ° C. or less within 10 seconds using both water cooling and air cooling.
Next, wet blasting (WB) treatment was performed under the following conditions. Note that the Sn layer was scraped by about 0.1 μm by the WB treatment.
-Wet blasting (WB) processing conditions-
(1) Apparatus: X-axis robot type wet blasting apparatus (WFB-2-2C, manufactured by Macau Corporation)
(2) Abrasive: Alumina (3) Abrasive grain size: # 320 (about 40 μm)
(4) Abrasive concentration: 18 vol%
(5) Line (gun) speed 10 m / min, number of passes once, blast air pressure 0.25 MPa
Thus, the conductive material of Example 4 was produced.
（実施例５〜７及び比較例７）
実施例４において、ウエットブラスト（ＷＢ）処理条件を表１に示すように変えた以外は、実施例４と同様にして、実施例５〜７及び比較例７の導電材を作製した。
(Examples 5 to 7 and Comparative Example 7)
In Example 4, conductive materials of Examples 5 to 7 and Comparative Example 7 were produced in the same manner as Example 4 except that the wet blasting (WB) treatment conditions were changed as shown in Table 1.
次に、実施例及び比較例の導電材について、以下のようにして、耐熱性、及び表面粗さを評価した。結果を表２に示す。 Next, the heat resistance and surface roughness of the conductive materials of Examples and Comparative Examples were evaluated as follows. The results are shown in Table 2.
＜耐熱性の評価＞
耐熱性は１６０℃の大気雰囲気中で２４時間、４８時間、９６時間、２５０時間、及び５００時間保持した後の室温での接触抵抗値で評価した。
接触抵抗値は、マイクロオームメーター（株式会社山崎精機研究所製、ＹＭＲ−３）を使用し、開放電圧２０ｍＶ、電流１０ｍＡ、０.５φｍｍのＵ型金線プローブ、最大荷重１００ｇｆ、摺動無しの条件で、試験数Ｎ＝３で測定し、その平均値を求めた。
<Evaluation of heat resistance>
The heat resistance was evaluated by a contact resistance value at room temperature after being kept in an air atmosphere at 160 ° C. for 24 hours, 48 hours, 96 hours, 250 hours, and 500 hours.
The contact resistance value uses a micro ohm meter (YMR-3, manufactured by Yamazaki Seiki Laboratory Co., Ltd.), open-circuit voltage 20 mV, current 10 mA, 0.5 φmm U-shaped wire probe, maximum load 100 gf, no sliding Under the conditions, the number of tests was N = 3, and the average value was obtained.
＜表面粗さＲａの測定＞
接触式表面粗さ計（株式会社小坂研究所製、サーフコーダＳＥ４０００）を用いて、表面粗さＲａを測定した。
<Measurement of surface roughness Ra>
The surface roughness Ra was measured using a contact-type surface roughness meter (manufactured by Kosaka Laboratory Ltd., Surfcoder SE4000).
＜Ｓｎ層の表面分析＞
次に、比較例６、実施例１、及び実施例４の導電材について、最表面のＳｎ層のＥＳＣＡ（光電子分光装置、アルバック・ファイ株式会社製、ＥＳＣＡ５８００）による表面分析を行った。結果を表３に示す。
<Surface analysis of Sn layer>
Next, for the conductive materials of Comparative Example 6, Example 1, and Example 4, surface analysis was performed by ESCA (ESC 5800, photoelectron spectrometer, ULVAC-PHI Co., Ltd.) of the outermost Sn layer. The results are shown in Table 3.
本発明の導電材の製造方法により製造された導電材は、１６０℃の大気中で長時間保持した後の接触抵抗の上昇が少ない耐熱性に優れたものであるので、例えば自動車用コネクタ端子、バスバー、電気・電子部品の端子等に適用できる。 Since the conductive material manufactured by the method for manufacturing a conductive material of the present invention is excellent in heat resistance with little increase in contact resistance after being kept in the atmosphere at 160 ° C. for a long time, for example, an automobile connector terminal, Applicable to bus bars, terminals for electrical / electronic components, etc.
Claims (15)
前記Ｓｎ層をウエットブラスト処理するウエットブラスト処理工程と、を含むことを特徴とする導電材の製造方法。 A Sn layer forming step of forming at least a Sn layer on the material;
A wet blasting process for wet blasting the Sn layer.
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| JP2010202903A (en) * | 2009-03-02 | 2010-09-16 | Dowa Metaltech Kk | Sn-COATED COPPER OR COPPER ALLOY, AND METHOD OF MANUFACTURING THE SAME |
| JP2010215979A (en) * | 2009-03-17 | 2010-09-30 | Dowa Metaltech Kk | Sn-COATED COPPER OR COPPER ALLOY, AND MANUFACTURING METHOD THEREFOR |
| JP2016056422A (en) * | 2014-09-11 | 2016-04-21 | 株式会社オートネットワーク技術研究所 | Member for terminal and method for manufacturing the same, and terminal for connector |
| JP2016156064A (en) * | 2015-02-25 | 2016-09-01 | Ｄｏｗａメタルテック株式会社 | Sn PLATED MATERIAL AND MANUFACTURING METHOD THEREOF |
| JPWO2018074256A1 (en) * | 2016-10-17 | 2019-08-08 | 古河電気工業株式会社 | Conductive strip |
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| JP2010215979A (en) * | 2009-03-17 | 2010-09-30 | Dowa Metaltech Kk | Sn-COATED COPPER OR COPPER ALLOY, AND MANUFACTURING METHOD THEREFOR |
| JP2016056422A (en) * | 2014-09-11 | 2016-04-21 | 株式会社オートネットワーク技術研究所 | Member for terminal and method for manufacturing the same, and terminal for connector |
| JP2016156064A (en) * | 2015-02-25 | 2016-09-01 | Ｄｏｗａメタルテック株式会社 | Sn PLATED MATERIAL AND MANUFACTURING METHOD THEREOF |
| JPWO2018074256A1 (en) * | 2016-10-17 | 2019-08-08 | 古河電気工業株式会社 | Conductive strip |
| JP7060514B2 (en) | 2016-10-17 | 2022-04-26 | 古河電気工業株式会社 | Conductive strip |
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