JP2015183216A - ELECTRONIC COMPONENT HAVING Ag-Sn ALLOY PLATING FILM, AND MANUFACTURING METHOD OF Ag-Sn PLATING SOLUTION AND THE ELECTRONIC COMPONENT - Google Patents
ELECTRONIC COMPONENT HAVING Ag-Sn ALLOY PLATING FILM, AND MANUFACTURING METHOD OF Ag-Sn PLATING SOLUTION AND THE ELECTRONIC COMPONENT Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 133
- 229910017980 Ag—Sn Inorganic materials 0.000 title claims abstract description 73
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 69
- 239000000956 alloy Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims description 12
- 230000007423 decrease Effects 0.000 claims description 9
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 abstract description 19
- 239000004332 silver Substances 0.000 abstract description 19
- 238000005299 abrasion Methods 0.000 abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 17
- 239000010410 layer Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910001128 Sn alloy Inorganic materials 0.000 description 4
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- -1 and further Chemical compound 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000010974 bronze Substances 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- MBBUQUXJJUSCJN-UHFFFAOYSA-N [K].[Ag]C#N Chemical compound [K].[Ag]C#N MBBUQUXJJUSCJN-UHFFFAOYSA-N 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 2
- 229940098221 silver cyanide Drugs 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 description 1
- CLEJZSNZYFJMKD-UHFFFAOYSA-N 3h-1,3-oxazole-2-thione Chemical compound SC1=NC=CO1 CLEJZSNZYFJMKD-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 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 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- TZMGLOFLKLBEFW-UHFFFAOYSA-M silver;sulfamate Chemical compound [Ag+].NS([O-])(=O)=O TZMGLOFLKLBEFW-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本発明は、Ag−Sn合金めっき膜を有する電子部品、前記Ag−Sn合金めっき膜を形成するためのAg−Snめっき液、及び前記電子部品の製造方法に関する。詳しくは、コネクタ、接点等として好適な電子部品に関する。 The present invention relates to an electronic component having an Ag—Sn alloy plating film, an Ag—Sn plating solution for forming the Ag—Sn alloy plating film, and a method for manufacturing the electronic component. In detail, it is related with an electronic component suitable as a connector, a contact, etc.
電子機器用接続部品であるコネクタやスイッチには、黄銅やリン青銅の表面に銅やニッケルの下地めっきを施し、さらにその上に銀めっきを施した材料が多く使用される。銀は電気および熱の良導体であるために、銀は上記のようにコネクタやスイッチまたはリードフレームなどのめっきとして用いられる。
前記銀めっきとして、電気自動車用のコネクタ、接点として硬質であり、高温耐性のあるAg(合金)めっきが求められている。
For connectors and switches that are connection parts for electronic devices, a material is often used in which a base plate of copper or nickel is applied to the surface of brass or phosphor bronze, and further, silver is applied thereon. Since silver is a good conductor of electricity and heat, silver is used as a plating for connectors, switches or lead frames as described above.
As the silver plating, there is a demand for Ag (alloy) plating that is hard as a connector for electric vehicles and a contact and has high temperature resistance.
硬質のAg系めっき材として、Ag−Sbが報告されているが、熱処理によって硬度が低下しやすく、また、Sbは毒性があり、作業上好ましくない。
また、大電流を印加することができ、低い摩擦係数と、高い耐熱性とが両立されためっき部材及びコネクタ用めっき端子の製造方法として、銅又は銅合金よりなる母材の表面に接触させてニッケル下地めっき層を形成し、最下層および最表層を銀めっき層としてスズめっき層と銀めっき層とを交互に積層した積層構造をニッケル下地めっき層に接触させて形成した後に、加熱を行い、母材の表面を被覆する銀−スズ合金層と、銀−スズ合金層を被覆し、最表面に露出する銀被覆層とを形成する方法が開示されている(特許文献1)。しかし、この方法は工程数が多く、かつ加熱が必要なため、コストが高くなるなどの問題があった。
銀−スズ合金めっき液としては、ピロリン酸スズ錯体と銀イオンを含むピロリン酸系めつき液にアンチモン0.2乃至1.0g/を含有せしめたことを特徴とする、銀―スズ合金めつき液(特許文献2)等が開示されているが、Snが経時的に析出するため、めっき浴の安定性に問題があった。
Ag-Sb has been reported as a hard Ag-based plating material, but the hardness is easily lowered by heat treatment, and Sb is toxic, which is not preferable for work.
Moreover, as a manufacturing method of the plating member which can apply a large current, and the low friction coefficient and high heat resistance are compatible, and the plating terminal for connectors, it is made to contact the surface of the base material which consists of copper or a copper alloy. After forming a nickel base plating layer, and forming a laminated structure in which tin plating layers and silver plating layers are alternately laminated with the lowermost layer and the outermost layer as silver plating layers in contact with the nickel base plating layer, heating is performed, A method of forming a silver-tin alloy layer that covers the surface of a base material and a silver coating layer that covers the silver-tin alloy layer and is exposed on the outermost surface is disclosed (Patent Document 1). However, this method has a problem that the number of steps is large and heating is required, resulting in an increase in cost.
As a silver-tin alloy plating solution, a silver-tin alloy plating solution characterized in that 0.2 to 1.0 g / monium of antimony is contained in a pyrophosphate plating solution containing a tin pyrophosphate complex and silver ions. Although a liquid (patent document 2) etc. is disclosed, since Sn precipitates with time, there was a problem in the stability of the plating bath.
本発明は、硬度が高く、また熱処理後も硬度が下がらないAg−Snめっき膜を有する電子部品を提供することを目的とする。更には、電気抵抗率が銀と比較してほぼ同等であり、耐摩耗性にも優れるAg−Snめっき膜を有する電子部品を低コストで提供することを目的とする。 An object of the present invention is to provide an electronic component having an Ag—Sn plating film that has high hardness and does not decrease in hardness after heat treatment. It is another object of the present invention to provide an electronic component having an Ag—Sn plating film having an electrical resistivity substantially equal to that of silver and having excellent wear resistance at low cost.
本発明者らは鋭意検討を行った結果、以下の電子部品により上記課題が解決されることを見い出し、本発明に至った。
即ち、本発明は以下の通りである。
(1)銅素材、もしくは銅めっき膜上に直接、もしくは下地Niめっき膜を介してAg−Sn合金めっき膜を有する電子部品であり、前記Ag−Sn合金めっき膜の膜厚が0.1〜100μmであり、Sn品位が10〜30質量%でかつ、Ag−Sn合金めっき膜の硬度が、マイクロビッカース硬さでHv150以上でかつ、熱処理(200℃×1hr.)による硬度低下が、熱処理前の硬度の20%以下であることを特徴とする電子部品。
(2)前記電子部品がコネクタもしくは接点であることを特徴とする前記(1)記載の電子部品。
(3)前記(1)又は(2)に記載のAg−Sn合金めっき膜を形成するAg−Sn合金めっき液であって、少なくとも銀イオン濃度5〜40g/L、シアンイオン濃度10〜60g/Lであり、かつ、カルボキシル基を含む酸のSn塩をSnイオン濃度5〜40g/Lになるように含有することを特徴とするAg−Sn合金めっき液。
(4)銅素材、もしくは銅めっき膜上に直接、もしくは下地Niめっき膜を介して、前記(3)に記載のAg−Sn合金めっき液を用いて、Ag−Sn合金めっき膜を形成することを特徴とする電子部品の製造方法。
As a result of intensive studies, the present inventors have found that the above-described problems can be solved by the following electronic components, and have reached the present invention.
That is, the present invention is as follows.
(1) An electronic component having an Ag—Sn alloy plating film directly on a copper material or a copper plating film or via a base Ni plating film, and the film thickness of the Ag—Sn alloy plating film is 0.1 to 0.1 100 μm, Sn grade is 10 to 30% by mass, Ag-Sn alloy plating film has a micro Vickers hardness of Hv150 or more, and a decrease in hardness due to heat treatment (200 ° C. × 1 hr.) Before heat treatment An electronic component having a hardness of 20% or less.
(2) The electronic component according to (1), wherein the electronic component is a connector or a contact.
(3) An Ag—Sn alloy plating solution for forming the Ag—Sn alloy plating film according to (1) or (2), wherein at least a silver ion concentration is 5 to 40 g / L, and a cyan ion concentration is 10 to 60 g / L. An Ag—Sn alloy plating solution containing an Sn salt of an acid containing L and a carboxyl group so as to have a Sn ion concentration of 5 to 40 g / L.
(4) Forming an Ag-Sn alloy plating film on the copper material or the copper plating film directly or via the underlying Ni plating film using the Ag-Sn alloy plating solution described in (3) above. A method of manufacturing an electronic component characterized by the above.
本発明によると、硬度が高く、熱処理による脆弱化が抑制され、耐摩耗性があり、また、電気抵抗率も銀とほぼ同等である電子部品が得られる。電気自動車用コネクタ、接点として好適な硬質で高温耐性のあるAg−Snめっき膜を有する電子部品が得られる。また、電子部品を作製する工程が少なく、加熱も必要としないため、低コストで前記電子部品が得られる。 According to the present invention, it is possible to obtain an electronic component that has high hardness, suppresses brittleness due to heat treatment, has wear resistance, and has an electrical resistivity substantially equal to that of silver. An electronic component having a hard, high-temperature-resistant Ag-Sn plating film suitable as a connector for electric vehicles and contacts can be obtained. Moreover, since there are few processes for producing an electronic component and heating is not required, the electronic component can be obtained at low cost.
本発明の電子部品は、銅素材、もしくは銅めっき膜上に直接、もしくは下地Niめっき膜を介してAg−Sn合金めっき膜を有する電子部品であり、前記Ag−Sn合金めっき膜の膜厚が0.1〜100μm、Sn品位が10〜30質量%、Ag−Sn合金めっき膜の硬度が、マイクロビッカース硬さでHv150以上、かつ、熱処理(200℃×1hr.)による硬度低下が、熱処理前の硬度の20%以下である。 The electronic component of the present invention is an electronic component having an Ag-Sn alloy plating film directly on a copper material or a copper plating film or through a base Ni plating film, and the film thickness of the Ag-Sn alloy plating film is 0.1 to 100 μm, Sn grade is 10 to 30% by mass, Ag-Sn alloy plating film has a micro Vickers hardness of Hv150 or more, and a hardness decrease due to heat treatment (200 ° C. × 1 hr.) The hardness is 20% or less.
前記銅素材としては、銅もしくは銅合金が挙げられる。銅合金としては、銅を主成分とし、Ni,Si,Fe,Zn,Sn,Mg,P,Cr,Mn,Zr,Ti,Sb等の元素の1種または2種以上を含有する合金、例えばCu−Fe−Zn−P系銅合金等を挙げることができる。尚、前記銅を主成分とする銅合金とは、銅を50質量%以上含有する銅合金を言う。 Examples of the copper material include copper and copper alloys. As a copper alloy, an alloy containing copper as a main component and containing one or more elements such as Ni, Si, Fe, Zn, Sn, Mg, P, Cr, Mn, Zr, Ti, and Sb, for example, Cu-Fe-Zn-P based copper alloys and the like can be mentioned. In addition, the copper alloy which has the said copper as a main component says the copper alloy containing 50 mass% or more of copper.
また、前記銅めっき膜は、従来公知の銅めっき液を用いて、公知の方法によって形成されるもので良い。前記めっき膜が形成される基材としては、鉄系合金等が挙げられる。好ましく用いられる鉄系合金としては、ステンレス鋼(SUS)、42アロイ等が挙げられる。
銅めっき膜の厚さは0.1〜10μmが好ましい。
The copper plating film may be formed by a known method using a conventionally known copper plating solution. Examples of the substrate on which the plating film is formed include iron-based alloys. Examples of iron-based alloys preferably used include stainless steel (SUS) and 42 alloy.
The thickness of the copper plating film is preferably 0.1 to 10 μm.
前記下地Niめっき膜は、従来公知のNiめっき液を用いて、公知の方法により形成することができるが、下地Niめっき層を形成するめっき液としては、スルファミン浴が好ましい。
下地Niめっき膜を設けることにより、銅素材又は銅めっき膜の銅成分がAg−Sn合金めっき層に拡散するのを抑制することができ、好ましい。
下地Niめっき膜の厚さは、0.1〜10μmが好ましい。
The base Ni plating film can be formed by a known method using a conventionally known Ni plating solution, and a sulfamine bath is preferable as the plating solution for forming the base Ni plating layer.
By providing the base Ni plating film, it is possible to suppress the copper material or the copper component of the copper plating film from diffusing into the Ag—Sn alloy plating layer, which is preferable.
The thickness of the underlying Ni plating film is preferably 0.1 to 10 μm.
Ag−Sn合金めっき膜は、膜厚が0.1〜100μmである。前記膜厚が0.1〜100μmであると、所定の耐摩耗性、硬度等に優れた電子部品を低コストで得ることができる。
前記膜厚が0.1μm未満であると、摩耗により短時間で電気信頼性が低下し、好ましくない。また、前記膜厚が100μmを超えると製造コストが高くなり、好ましくない。
上記めっき膜の膜厚は、蛍光X線膜厚計により測定することができる。
The Ag—Sn alloy plating film has a thickness of 0.1 to 100 μm. When the film thickness is 0.1 to 100 μm, it is possible to obtain an electronic component excellent in predetermined wear resistance, hardness, and the like at a low cost.
If the film thickness is less than 0.1 μm, the electrical reliability decreases in a short time due to wear, which is not preferable. On the other hand, if the film thickness exceeds 100 μm, the production cost increases, which is not preferable.
The film thickness of the plating film can be measured with a fluorescent X-ray film thickness meter.
前記Ag−Sn合金めっき膜は、Sn品位が10〜30質量%であることが必要である。
Sn品位が10質量%未満であると、銀めっきの硬度が低く、好ましくない。
Sn品位が30質量%を超えると、電気抵抗が上がり、好ましくない。
上記Ag−Sn合金めっき膜のSn品位は、ICP−AESで銀とSnの定量分析を行い算出することができる。
The Ag—Sn alloy plating film needs to have an Sn quality of 10 to 30% by mass.
If the Sn quality is less than 10% by mass, the hardness of the silver plating is low, which is not preferable.
If the Sn quality exceeds 30% by mass, the electrical resistance increases, which is not preferable.
The Sn quality of the Ag—Sn alloy plating film can be calculated by quantitative analysis of silver and Sn by ICP-AES.
前記Ag−Sn合金めっき膜は、マイクロビッカース硬さがHv150以上でかつ、熱処理(200℃×1hr.)による硬度低下が、熱処理前の硬度の20%以下である。
Ag−Sn合金めっき膜が上記の特性を有することにより、該Ag−Sn合金めっき膜を有する本発明の電子部品は、硬度が要求されるコネクタ、電子部品接点として好ましく用いることができる。
マイクロビッカース硬さの試験は、被膜に測定端子を刺して、その硬さを評価する。
即ち、上記マイクロビッカース硬さは、マイクロビッカース硬さ試験機を用いて、荷重10gで、形成したAg−Sn合金めっき膜を測定した値である(JIS Z 2244、ビッカース硬さ試験−試験方法準拠)。
熱処理(200℃×1hr.)するための加熱方法としては、特に限定されるものではなく、例えば、ホットプレートまたは熱風循環式オーブンなどを用いて行うことができる。
The Ag—Sn alloy plating film has a micro Vickers hardness of Hv150 or more, and a hardness decrease due to heat treatment (200 ° C. × 1 hr.) Is 20% or less of the hardness before heat treatment.
Since the Ag—Sn alloy plating film has the above characteristics, the electronic component of the present invention having the Ag—Sn alloy plating film can be preferably used as a connector or an electronic component contact that requires hardness.
In the micro Vickers hardness test, a measurement terminal is pierced in the coating and the hardness is evaluated.
That is, the micro Vickers hardness is a value obtained by measuring the formed Ag-Sn alloy plating film with a load of 10 g using a micro Vickers hardness tester (JIS Z 2244, Vickers hardness test-compliant with test method) ).
The heating method for heat treatment (200 ° C. × 1 hr.) Is not particularly limited, and can be performed using, for example, a hot plate or a hot air circulation oven.
前記Ag−Sn合金めっき膜は、少なくとも銀イオン濃度5〜40g/L、シアンイオン濃度10〜60g/Lであり、かつ、カルボキシル基を含む酸のSn塩をSnイオン濃度5〜40g/Lとなるように含有するめっき液を用いて形成することができる。 The Ag—Sn alloy plating film has at least a silver ion concentration of 5 to 40 g / L, a cyan ion concentration of 10 to 60 g / L, and an Sn salt of an acid containing a carboxyl group as an Sn ion concentration of 5 to 40 g / L. It can form using the plating solution containing so.
カルボキシル基を含む酸のSn塩を5〜40g/Lとなるように加えることで、液の安定性が向上し、Sn品位が10〜30質量%であるAg−Sn合金が再現性よくめっき出来る。
カルボキシル基を含む酸とのSn塩の含有量が、Snイオン濃度で5g/L未満であると、Ag−Sn合金めっき膜中のSn品位が低くなり、当該合金めっき膜の硬度が低下し、好ましくない。
40g/Lを超えると、めっき液の安定性が低下して、Ag−Sn合金めっき膜の組成のばらつきが大きくなり、また、Ag−Sn合金めっき膜中のSn品位が高くなることで、電気抵抗率が高くなり、好ましくない。
By adding an Sn salt of an acid containing a carboxyl group so as to be 5 to 40 g / L, the stability of the liquid is improved, and an Ag—Sn alloy having an Sn quality of 10 to 30% by mass can be plated with good reproducibility. .
When the content of the Sn salt with the acid containing a carboxyl group is less than 5 g / L in terms of Sn ion concentration, the Sn quality in the Ag-Sn alloy plating film is lowered, and the hardness of the alloy plating film is reduced, It is not preferable.
If it exceeds 40 g / L, the stability of the plating solution is lowered, the dispersion of the composition of the Ag—Sn alloy plating film is increased, and the Sn quality in the Ag—Sn alloy plating film is increased. Resistivity increases and is not preferable.
前記カルボキシル基を含む酸としては、例えば、酢酸、蓚酸、マロン酸、コハク酸、グリコール酸、酒石酸、クエン酸、グルコン酸、エチレンジアミンテトラ酢酸、ニトリロトリ酢酸、ジエチレントリアミンペンタ酢酸、トリエチレンテトラミンヘキサ酢酸等が挙げられる。蓚酸、酒石酸、クエン酸、エチレンジアミンテトラ酢酸、ニトリロトリ酢酸等が好ましい。 Examples of the acid containing a carboxyl group include acetic acid, succinic acid, malonic acid, succinic acid, glycolic acid, tartaric acid, citric acid, gluconic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, and triethylenetetraminehexaacetic acid. Can be mentioned. Succinic acid, tartaric acid, citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid and the like are preferable.
また、銀イオン濃度は5〜40g/Lであることが好ましい。銀イオン濃度が5g/L未満であると、Ag−Sn合金めっき膜のSn品位が高くなり、30質量%を超える場合があり、銀イオン濃度が40g/Lを超えるとAg−Sn合金めっき膜のSn品位が10質量%未満となる場合がある。 The silver ion concentration is preferably 5 to 40 g / L. If the silver ion concentration is less than 5 g / L, the Sn quality of the Ag-Sn alloy plating film may be high, and may exceed 30 mass%. If the silver ion concentration exceeds 40 g / L, the Ag-Sn alloy plating film The Sn quality may be less than 10% by mass.
シアンイオン濃度は10〜60g/Lであることが好ましい。シアンイオン濃度が10g/L未満であると、Ag−Sn合金めっき膜のSn品位が10質量%未満となる場合があり、シアンイオン濃度が60g/Lを超えると、Ag−Sn合金めっき膜のSn品位が高くなり、30質量%を超える場合がある。
Sn品位が10〜30質量%であるAg−Snめっき膜を得るには、上記各成分のバランスが重要である。
The cyan ion concentration is preferably 10 to 60 g / L. If the cyan ion concentration is less than 10 g / L, the Sn quality of the Ag—Sn alloy plating film may be less than 10% by mass. If the cyan ion concentration exceeds 60 g / L, the Ag—Sn alloy plating film Sn quality becomes high and may exceed 30 mass%.
In order to obtain an Ag—Sn plating film having an Sn quality of 10 to 30% by mass, the balance of the above components is important.
Ag−Sn合金めっき液に用いられる、銀イオン源となる銀化合物としては、シアン化銀カリウム、塩化銀、臭化銀、フッ化銀、硝酸銀、スルファミン酸銀、シアン化銀などを用いることが出来る。水に対する安定性の点からは、シアン化銀カリウムが好ましい。
シアンイオン源となるシアン化合物としては、シアン化カリウム、シアン化ナトリウム等が挙げられる。銀イオン源となる銀化合物としてシアン化銀、シアン化銀カリウム等を用いた場合、これらもシアンイオン源となる。
As a silver compound used as a silver ion source used in the Ag—Sn alloy plating solution, it is possible to use silver cyanide potassium, silver chloride, silver bromide, silver fluoride, silver nitrate, silver sulfamate, silver cyanide or the like. I can do it. From the viewpoint of stability to water, potassium silver cyanide is preferred.
Examples of the cyanide compound serving as a cyan ion source include potassium cyanide and sodium cyanide. When silver cyanide, silver cyanide potassium, or the like is used as the silver compound that becomes the silver ion source, these also become the cyan ion source.
前記Ag−Sn合金めっき液には、銀めっきを光沢化するため、セレン、アンチモン等の金属を微量添加しても良い。また、同じ目的で硫黄系の有機物、例えばメルカプトベンゾチアゾール、メルカプトオキサゾールを添加しても良い。
浴中のSnの酸化を防止するため、有機芳香族系の酸化防止剤、例えばジヒドロキシナフタレン、ヒドロキシキノリンを添加しても良い。
A small amount of metal such as selenium or antimony may be added to the Ag—Sn alloy plating solution to brighten the silver plating. For the same purpose, sulfur-based organic substances such as mercaptobenzothiazole and mercaptooxazole may be added.
In order to prevent oxidation of Sn in the bath, an organic aromatic antioxidant such as dihydroxynaphthalene or hydroxyquinoline may be added.
本発明におけるAg−Sn合金めっき膜は、前記Ag−Sn合金めっき液を用いためっきにより得ることができる。めっきを行う際は、電流密度1A/dm2以上で電気めっきし、Ag−Sn合金めっき皮膜を析出させることが好ましく、さらに好ましくは2〜20A/dm2の範囲で行うのがより好ましい。1A/dm2未満の電流密度ではSnと銀を共析させることが困難であり、20A/dm2以上の条件でめっきを行うとヤケなどにより、硬度が低下する恐れがある。また、めっき浴温度は10〜40℃、電解時間は5秒〜20分が好ましい。 The Ag—Sn alloy plating film in the present invention can be obtained by plating using the Ag—Sn alloy plating solution. When performing plating, it is preferable to perform electroplating at a current density of 1 A / dm 2 or more to precipitate an Ag—Sn alloy plating film, and more preferably in the range of 2 to 20 A / dm 2 . If the current density is less than 1 A / dm 2, it is difficult to co-deposit Sn and silver, and if plating is performed under the condition of 20 A / dm 2 or more, there is a risk that the hardness may decrease due to burns or the like. The plating bath temperature is preferably 10 to 40 ° C., and the electrolysis time is preferably 5 seconds to 20 minutes.
また、前記Ag−Sn合金めっき液を用いて得られるAg−Sn合金めっき膜は、前記したように、硬度が高く、熱処理後の硬度の低下20%以下であるが、更に電気抵抗率が銀と比較してほぼ同等となり、耐摩耗性にも優れる。
電気抵抗率としては、30μΩ・cm以下が好ましく、前記Ag−Sn合金めっき液により、9〜30μΩ・cmのAg−Sn合金めっき膜が得られる。
Further, as described above, the Ag—Sn alloy plating film obtained using the Ag—Sn alloy plating solution has a high hardness and a decrease in hardness of 20% or less after the heat treatment. Compared to, the wear resistance is excellent.
The electrical resistivity is preferably 30 μΩ · cm or less, and an Ag—Sn alloy plating film of 9 to 30 μΩ · cm can be obtained by the Ag—Sn alloy plating solution.
前記Ag−Sn合金めっきの前にAgストライクめっきを行ってもよい。Agストライクめっきを行うことにより、Ag−Sn合金めっき膜の密着性が良くなる。 Ag strike plating may be performed before the Ag—Sn alloy plating. By performing the Ag strike plating, the adhesion of the Ag—Sn alloy plating film is improved.
本発明の電子部品は、銅素材、又は銅めっき膜上に、直接もしくは下地Niめっき膜を介して、前記Ag−Sn合金めっき液を用いて、Ag−Sn合金めっき膜を形成することにより製造することができる。
本発明の電子部品は、上述のように硬質であり、加熱による硬さの低下がなく、耐摩耗性に優れ、接触抵抗は上昇しないので、電子機器用接続部品であるコネクタやスイッチに好適に用いることができる。特に、電気自動車に用いられているスイッチの可動接点及び/又は固定接点として好適に用いることができる。
The electronic component of the present invention is manufactured by forming an Ag-Sn alloy plating film on a copper material or a copper plating film, directly or via a base Ni plating film, using the Ag-Sn alloy plating solution. can do.
Since the electronic component of the present invention is hard as described above, there is no decrease in hardness due to heating, excellent wear resistance, and contact resistance does not increase, so it is suitable for connectors and switches that are connecting components for electronic devices. Can be used. In particular, it can be suitably used as a movable contact and / or a fixed contact of a switch used in an electric vehicle.
次に、実施例に基づいて本発明をさらに詳細に説明するが、本発明はこれに制限されるものではない。 Next, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
[実施例1〜15、比較例1〜9]
リン青銅基板(C5191,25mm×20mm×0.2mmt)に、銀ストライクめっきを0.05μm行った後、実施例1〜13、または比較例1〜9のAg−Sn合金めっき浴によるAg−Sn合金めっき行なっためっき基板を実施例1〜13、比較例1〜9の供試材とした。Ag−Sn合金めっきは、電流密度2A/dm2、浴温25℃で行った。
また、リン青銅基板(C5191,25mm×20mm×0.2mmt)に、スルファミン酸浴によるニッケルめっきを3μm、銀ストライクめっきを0.05μm行った後、実施例1と同じAg−Sn合金めっき浴によるAg−Sn合金めっきを行なっためっき基板を実施例14の供試材とした。
ステンレス合金(SUS304,25mm×20mm×0.2mmt)に、シアン銅浴による銅めっきを2μm、銀ストライクめっきを0.05μm行った後、実施例1と同じAg−Sn合金めっき浴によるAg−Sn合金めっきを行なっためっき基板を実施例15の供試材とした。
[Examples 1-15, Comparative Examples 1-9]
After performing silver strike plating 0.05 μm on a phosphor bronze substrate (C5191, 25 mm × 20 mm × 0.2 mmt), Ag—Sn by the Ag—Sn alloy plating bath of Examples 1 to 13 or Comparative Examples 1 to 9 The plated substrates subjected to alloy plating were used as test materials of Examples 1 to 13 and Comparative Examples 1 to 9. Ag—Sn alloy plating was performed at a current density of 2 A / dm 2 and a bath temperature of 25 ° C.
In addition, after the phosphor bronze substrate (C5191, 25 mm × 20 mm × 0.2 mmt) was subjected to nickel plating with a sulfamic acid bath at 3 μm and silver strike plating at 0.05 μm, the same Ag—Sn alloy plating bath as in Example 1 was used. A plated substrate subjected to Ag—Sn alloy plating was used as a test material of Example 14.
Stainless steel (SUS304, 25 mm × 20 mm × 0.2 mmt) was subjected to copper plating with a cyan copper bath at 2 μm and silver strike plating at 0.05 μm, and then Ag—Sn with the same Ag—Sn alloy plating bath as in Example 1. A plated substrate subjected to alloy plating was used as a test material of Example 15.
上記供試材のAg−Snめっき膜中のSn品位は、ICP−AESで銀とSnの定量分析を行い算出した。 The Sn quality in the Ag-Sn plating film of the above specimen was calculated by performing quantitative analysis of silver and Sn with ICP-AES.
上記供試材のAg−Snめっき膜の硬度は、マイクロビッカース硬さ試験機(マツザワ製 MMT−X7)で測定した。
また、めっき膜を、ホットプレートを用い、大気中で200℃×1hrの熱処理を行った後、硬度を同様にマイクロビッカース硬さ試験機(マツザワ製 MMT−X7)で測定した。
The hardness of the Ag—Sn plating film of the test material was measured with a micro Vickers hardness tester (MMT-X7 manufactured by Matsuzawa).
Further, the plated film was heat-treated at 200 ° C. for 1 hour in the air using a hot plate, and the hardness was similarly measured with a micro Vickers hardness tester (MMT-X7 manufactured by Matsuzawa).
上記供試材の電気抵抗率を、抵抗率測定器 (エヌピイエス製Model Σ-5+)を用い、直流4探針法(荷重400g)で測定した。 The electrical resistivity of the test material was measured by a direct current 4-probe method (load 400 g) using a resistivity meter (Model Σ-5 + manufactured by NPIS).
上記供試材の初期の接触抵抗、及び以下の条件で摺動摩耗試験を行った後の接触抵抗を測定した。
接触抵抗測定条件:
装置:山崎式接点シミュレータCRS−1
条件:接点荷重10g(Auプローブ)、摺動距離1mm
摺動摩耗試験条件:
装置:山崎精機研究所製CRS−G2050−JNS
条件:〔荷重〕1.6N、〔摺動範囲〕0.2mm、〔摺動速度〕1mm/s、
〔回数〕5万回
評価基準:
○:<10mΩ
△:10〜100mΩ
×:>100mΩ
The initial contact resistance of the test material and the contact resistance after performing a sliding wear test under the following conditions were measured.
Contact resistance measurement conditions:
Equipment: Yamazaki contact simulator CRS-1
Conditions: Contact load 10g (Au probe), sliding distance 1mm
Sliding wear test conditions:
Equipment: CRS-G2050-JNS manufactured by Yamazaki Seiki Laboratory
Conditions: [Load] 1.6 N, [Sliding range] 0.2 mm, [Sliding speed] 1 mm / s,
[Number of times] 50,000 times Evaluation criteria:
○: <10mΩ
Δ: 10 to 100 mΩ
×:> 100mΩ
また、熱処理しためっき基板に対し、耐摩耗試験を行った。耐摩耗試験はJISH8682記載の方法に準拠し、スガ摩耗試験機(NUS−IS03)を用い、荷重500gf(削れ面積 12mm×31mm)、#1500エメリー研磨紙、200往復の条件で実施した。
評価基準:
○:耐摩耗試験でのめっき被膜削れ量が15mg未満
△:耐摩耗試験でのめっき被膜削れ量が15mg以上30g未満
×:耐摩耗試験でのめっき被膜削れ量が30mg以上
In addition, an abrasion resistance test was performed on the heat-treated plated substrate. The abrasion resistance test was performed in accordance with the method described in JISH8682, using a Suga abrasion tester (NUS-IS03) under a load of 500 gf (scraped area: 12 mm × 31 mm), # 1500 emery abrasive paper, 200 reciprocating conditions.
Evaluation criteria:
○: Abrasion of the plating film in the abrasion resistance test is less than 15 mg. Δ: Abrasion of the plating film in the abrasion resistance test is 15 mg or more and less than 30 g. ×: Abrasion of the plating film in the abrasion resistance test is 30 mg or more
実施例1〜13、比較例1〜7で調製したAg−Sn合金めっき浴を、容量50mlのガラス製スクリュー管瓶に30ml分取した後、密栓して温度50℃に保持した乾燥器中に放置し、めっき浴の安定性を評価した。
評価基準:
○:1ヶ月以上沈殿の発生がみられなかった。
△:1週間から1ヶ月の間で沈殿の発生がみられた。
×:1週間以下で沈殿の発生がみられた。
30 ml of the Ag-Sn alloy plating bath prepared in Examples 1 to 13 and Comparative Examples 1 to 7 was dispensed into a glass screw tube bottle with a capacity of 50 ml, and then sealed in a dryer maintained at a temperature of 50 ° C. It was allowed to stand and the stability of the plating bath was evaluated.
Evaluation criteria:
○: No precipitation was observed for more than 1 month.
Δ: Precipitation was observed between 1 week and 1 month.
X: Precipitation was observed in 1 week or less.
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