JPS6312956B2 - - Google Patents
Info
- Publication number
- JPS6312956B2 JPS6312956B2 JP8124280A JP8124280A JPS6312956B2 JP S6312956 B2 JPS6312956 B2 JP S6312956B2 JP 8124280 A JP8124280 A JP 8124280A JP 8124280 A JP8124280 A JP 8124280A JP S6312956 B2 JPS6312956 B2 JP S6312956B2
- Authority
- JP
- Japan
- Prior art keywords
- gold
- plating
- tin
- bath
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000007747 plating Methods 0.000 claims description 68
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 37
- 239000010931 gold Substances 0.000 claims description 36
- 229910052737 gold Inorganic materials 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910001020 Au alloy Inorganic materials 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 239000003353 gold alloy Substances 0.000 claims description 5
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000005219 brazing Methods 0.000 description 8
- NRTDAKURTMLAFN-UHFFFAOYSA-N potassium;gold(3+);tetracyanide Chemical compound [K+].[Au+3].N#[C-].N#[C-].N#[C-].N#[C-] NRTDAKURTMLAFN-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 6
- 229910001128 Sn alloy Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000001119 stannous chloride Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 108010010803 Gelatin Proteins 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- 108010080698 Peptones Proteins 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000012493 hydrazine sulfate Substances 0.000 description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- 235000019319 peptone Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- 150000004992 toluidines Chemical class 0.000 description 2
- 239000010938 white gold Substances 0.000 description 2
- 229910000832 white gold Inorganic materials 0.000 description 2
- 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
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004283 Sodium sorbate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- -1 benzylidene acetate Chemical compound 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006023 eutectic alloy Substances 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- JVPLOXQKFGYFMN-UHFFFAOYSA-N gold tin Chemical compound [Sn].[Au] JVPLOXQKFGYFMN-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- KHZALYIIDCJNTD-UHFFFAOYSA-N rhodium titanium Chemical compound [Ti].[Rh] KHZALYIIDCJNTD-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- LROWVYNUWKVTCU-STWYSWDKSA-M sodium sorbate Chemical compound [Na+].C\C=C\C=C\C([O-])=O LROWVYNUWKVTCU-STWYSWDKSA-M 0.000 description 1
- 235000019250 sodium sorbate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Contacts (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】
本発明は、安定な金とスズおよび第３元素から
なる合金メツキ浴に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stable alloy plating bath consisting of gold, tin and a third element.
金とスズの合金は古くから使用されており、そ
の用途は多岐にわたつている。その例としてはス
ズの強い白色化力を利用したホワイトゴールド又
は、重量比で金80％、スズ20％の共晶合金を用い
たろう材が挙げられる。 Gold and tin alloys have been used for a long time and have a wide variety of uses. Examples include white gold, which utilizes the strong whitening power of tin, and brazing filler metal, which uses a eutectic alloy of 80% gold and 20% tin by weight.
金とスズの合金は、一般には治金法によつて製
造されるが、この方法は必要な形状にするまでの
工程が複雑であるため、単価が相当高くなるとい
う欠点があつた。 Gold and tin alloys are generally manufactured using metallurgical methods, but this method has the disadvantage that the process to form the desired shape is complicated, resulting in a considerably high unit price.
これに対して、金とスズの合金をメツキで析出
させる試みはいくつかなされているが、光沢を得
ることは困難であり、また、第一スズイオンは第
二スズイオンに酸化されやすいため、メツキ液と
しては不安定であるという欠点があつた。 On the other hand, several attempts have been made to deposit gold and tin alloys by plating, but it is difficult to obtain gloss, and stannous ions are easily oxidized to stannic ions, so the plating solution However, it had the disadvantage of being unstable.
本発明の目的は、かかる上記の欠点を解消し、
析出物の光沢性および第一スズイオンの安定性を
改善することにあり、さらに機械的特性を改善し
た金とスズを含む多元合金メツキ浴を提供するも
のである。 The purpose of the present invention is to eliminate the above-mentioned drawbacks,
The object of the present invention is to improve the brightness of the precipitate and the stability of stannous ions, and to provide a multi-component alloy plating bath containing gold and tin that has improved mechanical properties.
本発明の金合金浴は、金合金の電着に適した水
性浴において、シアン化金カリウムとして添加し
た金が20〜50ｇ／と、鉄（Fe）、コバルト
（Co）、ニツケル（Ni）、銅（Cu）のうちの少な
くとも１種の金属が0.5〜10ｇ／と、第一スズ
が120〜150ｇ／と、前記金属を錯化する少なく
とも一種類の化合物が600〜750ｇ／と、光沢剤
が１〜３ｇ／と、前記第一スズの酸化防止剤の
少なくとも１種が10〜50ｇ／とが添加され、PH
が４〜６であることを特徴とする。 The gold alloy bath of the present invention is an aqueous bath suitable for electrodeposition of a gold alloy, and contains 20 to 50 g of gold added as gold potassium cyanide, iron (Fe), cobalt (Co), nickel (Ni), 0.5 to 10 g of at least one metal among copper (Cu), 120 to 150 g of stannous, 600 to 750 g of at least one compound that complexes the metal, and a brightening agent. 1 to 3 g/, and 10 to 50 g/ of at least one of the stannous antioxidants are added, and the PH
is 4 to 6.
本発明のメツキ浴の構成は次のとおりである。
シアン化金カリウムとして添加される金の量は、
20〜50ｇ／である。金の量が20ｇ／未満で
は、メツキ浴の安定性、光沢性に乏しく、優秀な
析出物を得る電着速度が遅い。また、50ｇ／よ
り多い場合はメツキ浴中の金濃度が高すぎ、メツ
キキによるすくい出し等による損失のため経済的
ではない。 The structure of the plating bath of the present invention is as follows.
The amount of gold added as gold potassium cyanide is
It is 20-50g/. If the amount of gold is less than 20 g/g, the stability and gloss of the plating bath will be poor, and the rate of electrodeposition to obtain an excellent deposit will be slow. Moreover, if the amount exceeds 50 g/g, the gold concentration in the plating bath will be too high and it will be uneconomical due to loss due to scooping out by plating.
第一スズイオンは120ｇ／〜150ｇ／であ
る。第一スズイオンが120ｇ／未満ではスズの
析出および第二スズイオンへの酸化による消耗量
が大きくなつて不安定であり、150ｇ／より多
い場合は錯化が困難である。特に、スズの量が
120ｇ／をこえると液が安定になるため、大電
流を流すシヤワーメツキが可能になる。 The stannous ion is 120g/~150g/. If the amount of stannous ions is less than 120 g, the amount of consumption due to precipitation of tin and oxidation to stannic ions becomes large, resulting in instability; if the amount is more than 150 g, it is difficult to form a complex. In particular, the amount of tin
When the amount exceeds 120 g, the liquid becomes stable, allowing shower plating with a large current.
金とスズの合金の機械的強度を上げるために添
加される元素は、周期律表のａ族、ａ族、
ａ族、ａ族、ａ族、ａ族の金属およびｂ
族、ｂ族、ｂ族のものが考えられる。これら
の元素は、金とスズの合金中に析出して機械的強
度を著しく向上させることができる。さらに２種
以上の添加をすればその効果は相乗的に現われ
る。 Elements added to increase the mechanical strength of gold and tin alloys are group a, group a of the periodic table,
metals of group a, group a, group a, group a and b
Possible examples include those of the group B, group b, and group b. These elements can precipitate into gold and tin alloys to significantly improve mechanical strength. Furthermore, if two or more types are added, the effects will appear synergistically.
前記の元素は、例えばチタン、ニオブ、モリブ
デン、レニウム、鉄、コバルト、ニツケル、ロジ
ウム、パラジウム、銅、銀、ケイ素、リンなどで
あり、これらはそれぞれ水溶液に適した化合物の
形で添加されることが考えられる。 The aforementioned elements are, for example, titanium, niobium, molybdenum, rhenium, iron, cobalt, nickel, rhodium, palladium, copper, silver, silicon, phosphorus, etc., each of which may be added in the form of a suitable compound to the aqueous solution. is possible.
これらの金属のうち、添加しやすさ、錯化しや
すさ、値段、機械的強度からみて、鉄、ニツケ
ル、コバルト、銅が適当であり、その金属イオン
の量は0.5〜10ｇ／である。0.5ｇ／未満では
機械的強度が出ず、10ｇ／より多い場合は錯化
が困難で不安定なメツキ浴となる。 Among these metals, iron, nickel, cobalt, and copper are suitable in terms of ease of addition, ease of complexation, price, and mechanical strength, and the amount of metal ions is 0.5 to 10 g/. If it is less than 0.5 g/l, mechanical strength will not be achieved, and if it is more than 10 g/l, complexation will be difficult and the plating bath will be unstable.
上記の金属を錯化する化合物の量は600〜750
ｇ／である。600ｇ／より少ないと錯化され
る金属の量特にスズの量が少なくなつて析出速度
が著しく遅くなり、またメツキ浴のPHの緩衝作用
がなくなつてメツキ浴が不安定になる。また750
ｇ／より多いときには、浴の粘性が高くなるた
め実用的ではない。また錯化化合物としては上記
金属をわずかでも錯化させるものであればよい
が、リンゴ酸、クエン酸、グルコン酸、マロン
酸、マレイン酸などの有機カルボン酸がより好ま
しい。これは、有機カルボン酸は緩衝作用が強
く、またシアン化金カリウムを酸性側でも安定に
存在させることができるためである。 The amount of compounds complexing the above metals is 600-750
g/. If the amount is less than 600 g, the amount of metal to be complexed, especially the amount of tin, will be small and the precipitation rate will be extremely slow, and the pH buffering effect of the plating bath will be lost, making the plating bath unstable. 750 again
When the amount is more than g/g, it is not practical because the viscosity of the bath becomes high. The complexing compound may be one that complexes the above-mentioned metal even slightly, but organic carboxylic acids such as malic acid, citric acid, gluconic acid, malonic acid, and maleic acid are more preferable. This is because organic carboxylic acids have a strong buffering effect, and gold potassium cyanide can be stably present even on the acidic side.
析出する合金組成は、浴中の各金属イオンの濃
度、錯化合物濃度、PH、浴温および陰極電流密度
に依存する。浴が安定な範囲では、濃度の高い成
分が析出しやすく、金金属イオン量が大きいほど
析出速度は遅い。錯化合物濃度は多い方が析出合
金組成が安定になり、浴そのものも安定化する。
PHは高いとスズの電着効率が金に比べて低くなる
が、析出物の外観はよくなる。PHがアルカリ側の
場合は第一スズイオンが不安定になるため、浴の
PHは４〜６、好ましくは4.5±0.5がよい。PHが４
未満では、シアン化金カリが分解しやすく、６を
こえると第一スズが分解しやすい。浴温は15〜90
℃で使用可能であり、高い方がメツキ外観は良く
なり析出速度は速くなる光沢剤、酸化防止剤の消
耗は速くなるので適性な浴温が決められる。 The alloy composition to be deposited depends on the concentration of each metal ion in the bath, complex compound concentration, pH, bath temperature, and cathode current density. In a range where the bath is stable, components with high concentrations tend to precipitate, and the greater the amount of gold metal ions, the slower the precipitation rate. The higher the concentration of the complex compound, the more stable the precipitated alloy composition will be, and the more stable the bath itself will be.
When the pH is high, the electrodeposition efficiency of tin is lower than that of gold, but the appearance of the deposit is improved. If the pH is on the alkaline side, stannous ions become unstable, so the bath
PH is 4-6, preferably 4.5±0.5. PH is 4
If it is less than 6, potassium gold cyanide will be easily decomposed, and if it is more than 6, stannous will be easily decomposed. Bath temperature is 15-90
It can be used at a temperature of 0.9 °C, and the higher the temperature, the better the plating appearance, the faster the precipitation rate, and the faster the brightener and antioxidant will be consumed, so an appropriate bath temperature can be determined.
陰極電流密度は0.1〜10aA／ｄm2が実用的な範
囲である。電流密度が高いと析出合金組成はスズ
が多くなり電流密度が低いと金が多くなる。 The practical range of cathode current density is 0.1 to 10 aA/dm 2 . If the current density is high, the precipitated alloy composition will be tin-rich, and if the current density is low, the deposited alloy composition will be gold-rich.
本発明によるメツキ浴は、ゼラチン、トルイジ
ン、フエニルアセトアミド、亜ヒ酸ナトリウム、
β−ナフトール、ペプトン、アセトアルデヒドと
Ｏ−トルイジンの反応生成物の少なくとも１種を
添加することによつて優れた光沢を得ることがで
きる。添加量は１〜３ｇ／である。１ｇ／未
満では光沢がでず、３ｇ／をこえてもそれ以上
光沢効果がなく、メツキ液を不安定にする。この
光沢剤の効果はメツキ作業温度が35℃以下で特に
顕著に現われる。これは、浴温が35℃以下では、
スズはなめらかな析出物を得ることができないた
めである。またこれらの光沢剤はメツキ浴の安定
性、析出条件等にほとんど影響を与えない。 The plating bath according to the present invention contains gelatin, toluidine, phenylacetamide, sodium arsenite,
Excellent gloss can be obtained by adding at least one of the reaction products of β-naphthol, peptone, acetaldehyde and O-toluidine. The amount added is 1 to 3 g/. If it is less than 1g/, no gloss will be produced, and if it exceeds 3g/, there will be no further gloss effect and the plating solution will become unstable. The effect of this brightener is particularly noticeable when the plating temperature is below 35°C. This means that when the bath temperature is below 35℃,
This is because tin cannot form a smooth precipitate. Furthermore, these brighteners have little effect on the stability of the plating bath, the precipitation conditions, etc.
一般に第一スズイオンは第二スズイオンに酸化
されやすい。第二スズイオンは析出に寄与しない
ばかりでなく均一電着性に悪影響をおよぼすた
め、メツキ浴に酸化防止剤を添加することが実用
上有効な手段である。酸化防止剤としては、硫酸
ヒドラジン、硫酸ヒドロキシルアミン、Ｌ−アス
コルビン酸、Ｐ−クレゾールスルホン酸、レゾル
シン、ホルマリン、ハイドロキノン、ソルビン酸
ソーダまたはブドウ糖が有効である。 Generally, stannous ions are easily oxidized to stannous ions. Since stannic ions not only do not contribute to precipitation but also have a negative effect on uniform electrodeposition, it is a practically effective means to add an antioxidant to the plating bath. As the antioxidant, hydrazine sulfate, hydroxylamine sulfate, L-ascorbic acid, P-cresolsulfonic acid, resorcinol, formalin, hydroquinone, sodium sorbate, or glucose are effective.
添加量は10〜50ｇ／である。10ｇ／未満で
は酸化防止効果が不足し、50ｇ／をこえてもそ
れ以上の効果がなくメツキ液を不安定とする。ま
た、これらの酸化防止剤は、メツキ浴の安定性、
析出条件等に何ら悪影響を与えない。 The amount added is 10-50g/. If the amount is less than 10 g, the antioxidant effect will be insufficient, and if it exceeds 50 g, there will be no further effect and the plating solution will become unstable. These antioxidants also improve the stability of the plating bath,
It does not have any adverse effect on the precipitation conditions, etc.
このメツキ浴に用いる陽極は白金、カーボン、
チタン白金、チタンロジウムが望ましい。また、
陽極に対する陽極の面積比は２倍以上が望まし
い。 The anode used in this plating bath is platinum, carbon,
Titanium platinum and titanium rhodium are preferable. Also,
The area ratio of the anode to the anode is preferably twice or more.
また、このメツキ浴は、十分かくはんすること
によつて析出合金の外観、均一性が向上する。か
くはん方法としては、カソードロツキング、噴流
あるいはその併用がよく、空気かくはんは行なう
べきでない。 Further, by sufficiently stirring this plating bath, the appearance and uniformity of the precipitated alloy will be improved. As a stirring method, cathode locking, jet flow, or a combination thereof is recommended; air stirring should not be used.
次に本発明の実施例を説明する。 Next, embodiments of the present invention will be described.
実施例 １
金（シアン化金カリウムとして） 35ｇ／
スズ（硫酸第一スズとして） 120ｇ／
リンゴ酸 600ｇ／
ニツケル（硫酸ニツケルとして） 10ｇ／
硫酸ヒドラジン 30ｇ／
ゼラチン １ｇ／
ペプトン 0.5ｇ／
ベンジリデンアセテート 0.5ｇ／
PH 4.5
浴 温 20℃
陰極電流密度 2A／ｄm2
陽 極 チタン白金
メツキ時間 ５分
上記メツキ浴組成、メツキ条件でかくはんしな
がらメツキを行なつたところ、金76％、スズ23.8
％、ニツケル0.2％、厚さ4μｍの半光沢の析出皮
膜が得られた。皮膜の外観は銀白色である。この
サンプルに金ワイヤをボンデイングして強度を測
定したところ、すべてワイヤ切れであつた。Example 1 Gold (as potassium gold cyanide) 35g / tin (as stannous sulfate) 120g / malic acid 600g / nickel (as nickel sulfate) 10g / hydrazine sulfate 30g / gelatin 1g / peptone 0.5g / benzylidene acetate 0.5g / PH 4.5 Bath temperature 20℃ Cathode current density 2A/dm 2 anode Titanium platinum plating time 5 minutes When plating was performed with stirring under the above plating bath composition and plating conditions, the result was 76% gold and 23.8% tin.
%, nickel 0.2%, a semi-gloss deposited film with a thickness of 4 μm was obtained. The appearance of the film is silvery white. When gold wire was bonded to this sample and its strength was measured, all wires were broken.
実施例 ２
金（シアン化金カリウムとして） 50ｇ／
スズ（塩化第一スズとして） 120ｇ／
クエン酸 600ｇ／
コバルト（塩化コバルトとして） 0.5ｇ／
ホルマリン 10c.c.／
トルイジン ２ｇ／
PH 4.5
浴 温 20℃
陰極電流密度 1A／ｄm2
陽 極 カーボン
メツキ時間 ５分
上記メツキ浴組成、メツキ条件でメツキを行な
つたところ、金85％、スズ14.9％、コバルト0.1
％、厚み2.5μｍのナシ地の析出皮膜が得られた。
皮膜は外観は銀白色である。Example 2 Gold (as potassium gold cyanide) 50g / Tin (as stannous chloride) 120g / Citric acid 600g / Cobalt (as cobalt chloride) 0.5g / Formalin 10c.c. / Toluidine 2g / PH 4.5 Bath Temperature 20 °C Cathode current density 1A/dm 2 anodes Carbon plating time 5 minutes When plating was performed with the above plating bath composition and plating conditions, the results were 85% gold, 14.9% tin, and 0.1% cobalt.
%, a blank deposited film with a thickness of 2.5 μm was obtained.
The film has a silvery white appearance.
実施例 ３
金（シアン化金カリウムとして） 50ｇ／
スズ（塩化第一スズとして） 120ｇ／
マロン酸 750ｇ／
銅（硫酸銅として） ５ｇ／
硫酸ヒドロキシルアミン 50ｇ／
β−ナフトール １ｇ／
PH 4.5
浴 温 45℃
陰極電流密度 2A／ｄm2
陽 極 チタン白色
メツキ時間 ５分
上記メツキ浴組成、メツキ条件でメツキを行な
つたところ、金83％、スズ16％、銅１％、厚み
4.5μｍの光沢ある析出皮膜が得られた。皮膜の外
観は銀白色である。Example 3 Gold (as gold potassium cyanide) 50g / Tin (as stannous chloride) 120g / Malonic acid 750g / Copper (as copper sulfate) 5g / Hydroxylamine sulfate 50g / β-naphthol 1g / PH 4.5 Bath temperature 45 °C Cathode current density 2A/dm 2 anodes Titanium white plating time 5 minutes When plating was performed with the above plating bath composition and plating conditions, the results were 83% gold, 16% tin, 1% copper, and thickness.
A shiny deposited film of 4.5 μm was obtained. The appearance of the film is silvery white.
実施例 ４
金（シアン化金カリウムとして） 20ｇ／
スズ（塩化第一スズとして） 150ｇ／
リンゴ酸 600ｇ／
鉄（塩化第一鉄として） １ｇ／
Ｐ−クレゾールスルホン酸 50ｇ／
Ｏ−トルイジン ３ｇ／
PH 4.5
浴 温 45℃
陰極電流密度 6A／ｄm2
陽 極 チタン白金
メツキ時間 ５分
上記メツキ浴組成、メツキ条件でメツキを行な
つたところ、金72％、スズ27.8％、鉄0.2％、厚
み13μｍの析出皮膜が得られた。この皮膜は光沢
があり、銀白色を呈する。Example 4 Gold (as gold potassium cyanide) 20g / Tin (as stannous chloride) 150g / Malic acid 600g / Iron (as ferrous chloride) 1g / P-cresolsulfonic acid 50g / O-toluidine 3g / PH 4.5 Bath temperature 45℃ Cathode current density 6A/dm 2 Anode Titanium platinum plating time 5 minutes When plating was performed with the above plating bath composition and plating conditions, it was found that 72% gold, 27.8% tin, 0.2% iron, and 13 μm thick. A deposited film was obtained. This film is shiny and has a silvery white color.
実施例 ５
金（シアン化金カリウムとして） 50ｇ／
スズ（硫酸第一スズとして） 150ｇ／
クエン酸 750ｇ／
コバルト（硫酸コバルトとして） ５ｇ／
ハイドロキノン 30ｇ／
亜ヒ酸ナトリウム １ｇ／
PH 4.5
浴 温 45℃
陰極電流密度 2A／ｄm2
陽 極 チタン白色
メツキ時間 ５分
上記メツキ浴組成、メツキ条件でメツキを行な
つたところ、金82％、スズ17.6％、コバルト0.4
％、厚み4.5μｍの光沢ある析出皮膜が得られた。
この皮膜の外観は銀白色である。Example 5 Gold (as gold potassium cyanide) 50g / Tin (as stannous sulfate) 150g / Citric acid 750g / Cobalt (as cobalt sulfate) 5g / Hydroquinone 30g / Sodium arsenite 1g / PH 4.5 Bath temperature 45°C Cathode current density 2A/dm 2 anodes Titanium white plating time 5 minutes When plating was performed with the above plating bath composition and plating conditions, the results were 82% gold, 17.6% tin, and 0.4% cobalt.
%, a glossy deposited film with a thickness of 4.5 μm was obtained.
The appearance of this film is silvery white.
実施例 ６
金（シアン化金カリウムとして） 50ｇ／
スズ（塩化第一スズとして） 150ｇ／
マロン酸 750ｇ／
ニツケル（塩化ニツケルとして） ５ｇ／
レゾルシン 50ｇ／
β−ナフトール ２ｇ／
PH 4.5
浴 温 45℃
陰極電流密度 8A／ｄm2
陽 極 チタン白色
メツキ時間 ５分
上記メツキ浴組成、メツキ条件でメツキを行な
つたところ、金69％、スズ29.5％、ニツケル0.5
％、厚み14μｍの光沢ある析出皮膜が得られた。Example 6 Gold (as gold potassium cyanide) 50g / Tin (as stannous chloride) 150g / Malonic acid 750g / Nickel (as nickel chloride) 5g / Resorcinol 50g / β-naphthol 2g / PH 4.5 Bath temperature 45°C Cathode Current density 8A/dm 2 anode Titanium white plating time 5 minutes When plating was performed with the above plating bath composition and plating conditions, the results were 69% gold, 29.5% tin, and 0.5% nickel.
A glossy deposited film with a thickness of 14 μm was obtained.
以上に述べた実施例は本発明の一部であり、こ
れらは本発明を限定するものではない。 The embodiments described above are part of the invention and are not intended to limit the invention.
次に、本発明によつて得られる効果を次に挙げ
る。 Next, the effects obtained by the present invention will be listed below.
(1) メツキ浴が安定である。(1) Metsuki bath is stable.
シアン化金カリウムおよび錯化剤は多いほど
メツキ浴を安定化するが、前者は20ｇ／を越
えるとその効果が著しい。 The more gold potassium cyanide and the complexing agent are added, the more the plating bath will be stabilized, but the former's effect is significant when it exceeds 20 g.
(2) 優れた光沢が得られ、スズが120ｇ／を越
えるとその効果は著しい。また、厚メツキによ
つても光沢性、均一性、密着性に変化がない。(2) Excellent gloss can be obtained, and the effect is remarkable when the amount of tin exceeds 120g/. Furthermore, even with thick plating, there is no change in gloss, uniformity, or adhesion.
(3) 金−スズ合金に第３元素を添加することによ
つて、硬度が増加する。(3) Hardness increases by adding a third element to the gold-tin alloy.
(4) 金属成分が高いため、高速メツキが可能であ
る。(4) High-speed plating is possible due to the high metal content.
(5) 浴組成、電流密度によつて析出合金組成を任
意に、かつ広範囲に変化させることができる。(5) The composition of the precipitated alloy can be changed arbitrarily and over a wide range by changing the bath composition and current density.
(6) 常温でもすぐれた析出物を得ることができ
る。これは、メツキ浴の安定性をさらに高める
効果をもつ。(6) Excellent precipitates can be obtained even at room temperature. This has the effect of further increasing the stability of the plating bath.
(7) 浴濃度が減少した場合、濃厚な補充液をあら
かじめつくつておいてこれを補充すればよく、
長時間の使用が可能である。(7) If the bath concentration decreases, you can prepare a concentrated replenisher solution in advance and replenish it.
Can be used for a long time.
本発明によるメツキ浴は上記に述べたように顕
著な諸効果を示す。このメツキ浴の用途として
は、次のようなものが挙げられる。 The plating bath according to the present invention exhibits remarkable effects as described above. The uses of this plating bath include the following.
(a) 硬度の高い装飾用ホワイトゴールドメツキ
金とスズの組成を変化させることによつて金
色から白色まで巾広い色調を得ることができ、
析出物の硬度も高いので装飾用メツキとして利
用できる。具体的には、優れた外観、硬度、耐
食性が求められている腕時計、メガネフレーム
およびネツクレス等の装飾品などに用いること
ができる。(a) Decorative white gold plating with high hardness By changing the composition of gold and tin, a wide range of colors can be obtained from gold to white.
The hardness of the precipitates is high, so they can be used as decorative plating. Specifically, it can be used for ornaments such as wristwatches, eyeglass frames, and neckpieces that require excellent appearance, hardness, and corrosion resistance.
(b) 低品位、高強度の電気接点材料
優れた耐摩耗性、耐食性、導電性を利用した
電気接点材料として用いることができる。(b) Low-grade, high-strength electrical contact material Can be used as an electrical contact material that takes advantage of its excellent wear resistance, corrosion resistance, and conductivity.
(c) ボンデイング用メツキ
金にスズを適量添加することによつて融点は
著しく低下する。これを利用してICのワイヤ
ボンデイングが行なわれるリードフレームへ用
いることができる。従来の純金メツキに比べ、
金相が低下すると同時に、ボンデイング時の加
熱温度を下げることができるためサイクルタイ
ムを短縮できるという利点がある。(c) Plating for bonding By adding an appropriate amount of tin to gold, the melting point is significantly lowered. Utilizing this, it can be used in lead frames where IC wire bonding is performed. Compared to traditional pure gold plating,
At the same time as the gold phase is lowered, the heating temperature during bonding can be lowered, which has the advantage of shortening the cycle time.
(d) 低融点、高強度ろう材
金80％、スズ20％の合金およびこれに第３元
素が添加された合金は融点がほぼ300℃前後で
強度がハンダ類の10倍以上とすぐれている。ろ
う材メツキの用途として具体的には次のような
ものがある。腕時計などの水晶振動子において
プラグ先端のリード線に本発明のメツキを施
し、加熱溶融して水晶振動子をリード線にろう
付する場合、また、水晶振動子を封入するパツ
ケージにおいて、パツケージに本発明のメツキ
を施して加熱溶融し、パツケージをろう付封止
する場合がある。また、ICチツプとテープキ
ヤリア方式の導電用フインガー部のろう付とし
てチツプ又はフインガー部に本発明を施す場
合、同じくフエイスダウンと呼ばれる半導体実
装方法において、回路基板とICのろう付とし
てチツプ又は回路基板に本発明のメツキ施す場
合等がある。(d) Low melting point, high strength brazing metal Alloys of 80% gold and 20% tin, as well as alloys to which a third element is added, have a melting point of approximately 300°C and a strength that is more than 10 times that of solder. . Specific uses for brazing metal plating include the following. When the lead wire of the plug tip of a crystal resonator such as a wristwatch is coated with the plating of the present invention, heated and melted to braze the crystal resonator to the lead wire, and when the crystal resonator is enclosed in a package, the plating of the present invention is applied to the lead wire at the tip of the plug. In some cases, the plating of the invention is applied, the material is heated and melted, and the package is sealed by brazing. In addition, when the present invention is applied to a chip or a finger part for brazing an IC chip and a conductive finger part of a tape carrier method, the present invention can also be applied to a chip or a circuit board for brazing a circuit board and an IC in a semiconductor mounting method called face-down. There are cases where the plating of the present invention is applied to.
この金とスズを主成分とした合金メツキをろ
う材として用いる場合、析出物の成分生成は金
がほぼ10〜85％、スズがほぼ15〜90％、第３元
素の１種以上の合計が０〜60％で融点は280℃
〜550℃、メツキ厚み2μｍ以上であれば実用上
差支えない。 When this alloy plating mainly composed of gold and tin is used as a brazing material, the composition of precipitates is approximately 10-85% gold, approximately 15-90% tin, and a total of one or more third elements. 0-60%, melting point is 280℃
There is no practical problem as long as the temperature is ~550°C and the plating thickness is 2 μm or more.
以上述べたように、本発明による金合金メツキ
浴は装飾用メツキ、機能メツキおよびろう材メツ
キなどさまざまな用途に使用できるため、実用上
極めて有用な発明である。 As described above, the gold alloy plating bath according to the present invention can be used for various purposes such as decorative plating, functional plating, and brazing material plating, and is therefore an extremely useful invention in practice.
Claims (1)
ｇ／と、鉄（Fe）、コバルト（Co）、ニツケル
（Ni）、銅（Cu）のうちの少なくとも１種の金属
が0.5〜10ｇ／と、第一スズが120〜150ｇ／
と、前記金属を錯化する少なくとも一種類の化合
物が600〜750ｇ／と、光沢剤が１〜３ｇ／
と、前記第一スズの酸化防止剤の少なくとも１種
が10〜50ｇ／とが添加され、PHが４〜６である
ことを特徴とする金合金メツキ浴。[Claims] 1. In an aqueous bath suitable for electrodeposition of a gold alloy, the amount of gold added as potassium gold cyanide is 20 to 50%.
g/, at least one metal of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) is 0.5 to 10 g/, and stannous is 120 to 150 g/
, 600 to 750 g of at least one compound that complexes the metal, and 1 to 3 g of a brightener.
and 10 to 50 g of at least one of the stannous antioxidants are added, and the gold alloy plating bath has a pH of 4 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8124280A JPS575887A (en) | 1980-06-16 | 1980-06-16 | Gold alloy plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8124280A JPS575887A (en) | 1980-06-16 | 1980-06-16 | Gold alloy plating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS575887A JPS575887A (en) | 1982-01-12 |
| JPS6312956B2 true JPS6312956B2 (en) | 1988-03-23 |
Family
ID=13740949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8124280A Granted JPS575887A (en) | 1980-06-16 | 1980-06-16 | Gold alloy plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS575887A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4958485A (en) * | 1988-12-22 | 1990-09-25 | Springs Industries, Inc. | Corespun yarn for fire resistant safety apparel |
-
1980
- 1980-06-16 JP JP8124280A patent/JPS575887A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS575887A (en) | 1982-01-12 |
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