JPS6312954B2 - - Google Patents
Info
- Publication number
- JPS6312954B2 JPS6312954B2 JP7739880A JP7739880A JPS6312954B2 JP S6312954 B2 JPS6312954 B2 JP S6312954B2 JP 7739880 A JP7739880 A JP 7739880A JP 7739880 A JP7739880 A JP 7739880A JP S6312954 B2 JPS6312954 B2 JP S6312954B2
- Authority
- JP
- Japan
- Prior art keywords
- gold
- plating
- bath
- alloy
- 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 45
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 20
- 239000010931 gold Substances 0.000 claims description 20
- 229910052737 gold Inorganic materials 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 229910001020 Au alloy Inorganic materials 0.000 claims description 12
- 239000003353 gold alloy Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 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 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910001128 Sn alloy Inorganic materials 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 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
- 239000008139 complexing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004070 electrodeposition Methods 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
- JVPLOXQKFGYFMN-UHFFFAOYSA-N gold tin Chemical compound [Sn].[Au] JVPLOXQKFGYFMN-UHFFFAOYSA-N 0.000 description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 2
- 239000012493 hydrazine sulfate Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-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 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 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
- 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
- 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006073 displacement reaction Methods 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
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 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
- 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
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 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
- 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
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 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
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000004992 toluidines Chemical class 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
Landscapes
- 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
なる金合金ストライク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 gold alloy strike plating bath consisting of gold, tin and a third element.
従前より金とスズの合金メツキ浴は数多く提案
されている。これらの多くはアルカリシアン化物
としての金と第一スズイオンおよび錯化剤より成
つている。しかし、金とスズの合金メツキ浴は光
沢を得ることが困難であり、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。 Many alloy plating baths of gold and tin have been proposed. Most of these consist of gold as alkali cyanide, stannous ions, and complexing agents. However, gold and tin alloy plating baths have the disadvantage that it is difficult to obtain gloss, and stannous ions are easily oxidized to stannic ions, making them unstable as plating solutions.
本発明の目的は、かかる上記の欠点を改善し、
耐食性、機械的特性がすぐれ、光沢ある析出皮膜
が得られる安定な、金属スズをベースとしたスト
ライク用金合金メツキ浴を提供するものである。
本発明の金合金ストライクメツキ浴は、
金合金のストライクメツキに適した金合金スト
ライクメツキ浴において、
シアン化金カリウムとして添加した金が0.2〜
0.8ｇ／と、金属としてニツケルが0.1〜５ｇ／
と、第一スズが0.2〜10ｇ／と、前記金属を
錯化する少なくとも１種類の化合物が150ｇ／
〜750ｇ／と、光沢剤が0.2〜30ｇ／と、前記
第一スズの酸化防止剤の少なくとも１種が0.5〜
50ｇ／とが添加され、PHが４〜６であることを
特徴とする。 The purpose of the present invention is to improve the above-mentioned drawbacks,
The object of the present invention is to provide a stable gold alloy plating bath for strikes based on metallic tin, which has excellent corrosion resistance and mechanical properties, and provides a glossy deposited film.
The gold alloy strike plating bath of the present invention is a gold alloy strike plating bath suitable for strike plating of gold alloys, in which the amount of gold added as gold potassium cyanide is 0.2 to 0.
0.8g/, and nickel as metal is 0.1~5g/
and 0.2 to 10 g of stannous, and 150 g of at least one compound that complexes the metal.
~750g/, the brightener is 0.2~30g/, and at least one of the stannous antioxidants is 0.5~750g/.
It is characterized by the addition of 50 g/day and a pH of 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、
0.2〜0.8ｇ／である。金の量が0.2ｇ／未満で
は析出による金の消耗がはげしく、0.8ｇ／を
こえると、析出皮膜の密着性に乏しい。この密着
性の向上は次のような理由による。すなわち金は
析出電位は高いが、低濃度で錯化することによつ
て析出電位が低くなり密着性の悪い置換反応を防
ぐことができるためである。 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 0.2-0.8g/. If the amount of gold is less than 0.2 g/g, the gold is rapidly consumed by precipitation, and if it exceeds 0.8 g/g, the adhesion of the deposited film is poor. This improvement in adhesion is due to the following reasons. That is, although gold has a high deposition potential, complexing at a low concentration lowers the deposition potential and can prevent a substitution reaction that causes poor adhesion.
現実に金が0.8ｇ／以上の浴では銅、ニツケ
ル板などを浸漬すると金が置換析出してくる。 In reality, when copper or nickel plates are immersed in a bath containing 0.8 g or more of gold, gold will precipitate by displacement.
次に、第一スズイオンの量は0.2〜10ｇ／で
ある。0.2ｇ／未満ではメツキによる第一スズ
イオンの消耗が激しく、10ｇ／こえると析出す
るスズ量が多すぎるため、本発明の目的である耐
食性が低下するので望ましくない。 Next, the amount of stannous ions is 0.2-10 g/. If it is less than 0.2 g/l, the stannous ions will be severely consumed by plating, and if it exceeds 10 g/l, the amount of tin precipitated will be too large, which is undesirable because the corrosion resistance, which is the object of the present invention, will deteriorate.
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
度とくに硬度を著しく向上させることができる。
２種以上の添加をすれば、さらにその効果は相乗
的に現われる。前記の元素は、たとえばチタン、
ニオブ、モリブデン、レニウム、鉄、ニツケル、
コバルト、ロジウム、パラジウム、銅、銀、ケイ
素、リンなどが考えられるが、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。このな
かでもニツケルが最も添加しやすいか、機械的強
度か、メツキのつき回りをよくするかの３点で適
している。これらのうちニツケルのイオンは0.1
〜５ｇ／である。 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 precipitate in the gold-tin alloy and can significantly improve mechanical strength, especially hardness.
If two or more types are added, the effect will be even more synergistic. The aforementioned elements are, for example, titanium,
Niobium, molybdenum, rhenium, iron, nickel,
Cobalt, rhodium, palladium, copper, silver, silicon, phosphorus, etc. are conceivable, each being added in the form of a compound suitable for aqueous solution. Among these, nickel is the most suitable for three reasons: it is easy to add, it has mechanical strength, and it improves plating coverage. Of these, the nickel ion is 0.1
~5g/.
５ｇ／より多い場合は、錯化が困難であり、
また多量に析出すれば添加元素としての目的にあ
わなくなるので適さない。また0.1ｇ／未満で
は機械的な強度が上がらない。 If the amount is more than 5g/, complexation is difficult;
Moreover, if it precipitates in large amounts, it will not serve the purpose of being an additive element, so it is not suitable. Moreover, if it is less than 0.1 g/g/m, the mechanical strength will not increase.
上記の金属を錯化する化合物の量は150〜750
ｇ／である。150ｇ／より少ないと錯化作用
が小さく、またメツキ浴の緩衝作用がなくなつて
メツキ浴が不安定になる。また750ｇ／より多
い場合は浴の粘性が高くなるため実用的でない。
この錯化剤は多い方がメツキ浴が安定であると同
時に、作業電流密度が高くとれ、析出合金組成の
電流密度による変化が小さくなる。 The amount of compounds complexing the above metals is 150-750
g/. If the amount is less than 150 g, the complexing effect will be small and the plating bath will lose its buffering effect, making the plating bath unstable. Moreover, if the amount is more than 750 g, the viscosity of the bath becomes high, which is not practical.
The more complexing agent there is, the more stable the plating bath will be, and at the same time, the higher the working current density will be, and the less change in the composition of the deposited alloy due to the current density will occur.
錯化合物としてはリンゴ酸、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
酸が望ましい。これは、有機カルボン酸は錯化作
用、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。 Desirable complex compounds include organic carboxylic acids such as malic acid, citric acid, gluconic acid, malonic acid, and maleic acid. This is because organic carboxylic acids have strong complexing and buffering effects, and can allow gold potassium cyanide to exist stably even on the acidic side.
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、ペプトンおよびアセトアルデヒ
ドと０−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0.2〜30ｇ／である。0.2
ｇ／未満では光沢が得られず、30ｇ／をこえ
ても光沢効果はなくメツキ液を不安定とさせる。
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
スズのなめらかな析出が得られないことによる。
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,
At least one of the reaction products of β-naphthol, peptone and acetaldehyde with O-toluidine
Excellent shine can be obtained by adding seeds. The amount added is 0.2 to 30g/. 0.2
If it is less than 30g/, no gloss will be obtained, and if it exceeds 30g/, there will be no 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 is because tin cannot be deposited smoothly if the bath temperature is below 35°C.
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
化されやすく、浴温が高いほどこれは著しい。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。添加量は0.5〜50ｇ／で
ある。0.5ｇ／未満では酸化防止効果がなく、
50ｇ／をこえても、それ以上の効果はなくメツ
キ液を不安定にする。また、これらの酸化防止剤
は２種以上を添加することによつてその効果は相
乗的に現われ、メツキ浴の安定性、光沢、析出条
件等に悪影響を与えることはない。 Generally, stannous ions are more easily oxidized to stannous ions, and this becomes more pronounced as the bath temperature is higher. 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 antioxidants, hydrazine sulfate, hydroxylamine sulfate, L-ascorbic acid, P-
Cresolsulfonic acid, resorcinol, formalin, hydroquinone, sodium sorbate or glucose are effective. The amount added is 0.5 to 50g/. If it is less than 0.5g/, there is no antioxidant effect;
Even if the amount exceeds 50g, there will be no further effect and the glazing solution will become unstable. Furthermore, when two or more of these antioxidants are added, their effects appear synergistically, and the stability, gloss, precipitation conditions, etc. of the plating bath are not adversely affected.
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。金と錯化合物濃度は許される範囲で
高い方が望ましい。これは、金と錯化合物量の多
い方が電流密度に対して析出金組成の変化が少な
くなり、浴組成を決定すれば、析出合金組成はほ
ぼ一定になるためである。 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. It is desirable that the concentration of gold and complex compound be as high as possible. This is because the larger the amount of gold and complex compound, the less the change in the deposited gold composition with respect to the current density, and once the bath composition is determined, the deposited alloy composition will be approximately constant.
PHは高いとスズの電着は少なくなるが、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。 Higher pH results in less tin electrodeposition, but improves the appearance of the precipitates. If the pH is on the alkaline side, stannous ions become unstable, so the pH of the bath should be 4 to 6.
Preferably it is 4.5±0.5.
PHが４未満ではシアン化金カリを分解させ、PH
が６をこえると第一スズを分解させる。浴温は15
〜90℃で使用可能であり、高い方がメツキ外観が
よくなり析出速度ははやくなるが光沢剤、酸化防
止剤の消耗がはげしくなるので適正な浴温が決め
られる。 If the PH is less than 4, gold potassium cyanide is decomposed and the PH
When it exceeds 6, stannous is decomposed. Bath temperature is 15
It can be used at temperatures up to 90°C, and the higher the temperature, the better the plating appearance and the faster the precipitation rate, but the more the brightener and antioxidant are consumed, so the appropriate bath temperature must be determined.
陰極電流密度は0.1〜10A／ｄm2が実用的な範
囲である。 The practical range of cathode current density is 0.1 to 10 A/dm 2 .
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、
陰極に対する陽極の面責比は２倍以上が望まし
い。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
べきではない。 The anode used in this plating bath is platinum, carbon,
Titanium platinum and titanium rhodium are preferable. Also,
It is desirable that the surface area ratio of the anode to the cathode is two times or more. 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） 0.8ｇ／
スズ（硫酸第１スズとして） ２ｇ／
ニツケル（硫酸ニツケルとして） １ｇ／
リンゴ酸 300ｇ／
硫酸ヒドラジン 30ｇ／
ゼラチン １ｇ／
ペプトン 0.5ｇ／
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
上記のメツキ浴組成、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85％、スズ
14.8％、ニツケル0.2％、厚み0.5μｍの光沢ある析
出皮膜が得られた。Example 1 Gold (as gold potassium cyanide) 0.8g / Tin (as stannous sulfate) 2g / Nickel (as nickel sulfate) 1g / Malic acid 300g / Hydrazine sulfate 30g / Gelatin 1g / Peptone 0.5g / PH 4.5 bath Temperature: 20°C Cathode current density: 1A/dm 2 anodes Carbon plating time: 5 minutes When plating was performed with stirring under the above plating bath composition and plating conditions, the results were 85% gold and tin.
A glossy deposited film containing 14.8% nickel and 0.2% nickel and a thickness of 0.5 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) メツキ液が安定しており、析出したメツキが
緻密となるので密着性が優れた金合金メツキの
下地としてのストライクメツキを提供できる。(1) Since the plating solution is stable and the precipitated plating becomes dense, it is possible to provide strike plating as a base for gold alloy plating with excellent adhesion.
低濃度金属イオン、高電流密度により、優れ
た密着性のよいメツキ皮膜が得られる。 A plating film with excellent adhesion can be obtained due to the low concentration of metal ions and high current density.
(2) 優れた光沢が得られる。(2) Excellent gloss can be obtained.
(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ので、下地として固い皮膜
を提供でき、上付けのメツキを任意に選ぶこと
ができる。(3) Hardness is increased by adding a third element to the gold-tin alloy, so a hard film can be provided as a base layer, and the top plating can be arbitrarily selected.
(4) 浴組成、電流密度によつて析出合金組成を自
由に変化させることができるので、上付けメツ
キが変つても、浴組成をいちいち変えなくても
よい。(4) Since the precipitated alloy composition can be freely changed by changing the bath composition and current density, there is no need to change the bath composition every time the top plating changes.
(5) 析出皮膜の耐食性がよい。(5) Good corrosion resistance of the deposited film.
(6) 常温でもすぐれた析出物を得ることができ
る。(6) Excellent precipitates can be obtained even at room temperature.
(7) メツキ浴が安定である。(7) Metsuki bath is stable.
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。 The plating bath according to the present invention exhibits remarkable effects as described above.
このメツキ浴の用途としては、次のようなも
のが考えられる。 Possible uses for this plating bath include the following:
(a) 特に下づけメツキに応用途が大きい。さら
にこのまま使用しても用途によつて差支えな
い。 (a) It has a wide range of applications, especially for underlay plating. Furthermore, it may be used as is, depending on the purpose.
(b) 硬度の高い白色装飾用メツキ
具体的には、優れた外観、硬度、耐食性が
求められる装飾品、腕時計のケース、メガネ
フレームなどのストライクメツキ用として用
いることができる。 (b) White decorative plating with high hardness Specifically, it can be used for strike plating of ornaments, watch cases, eyeglass frames, etc. that require excellent appearance, hardness, and corrosion resistance.
(c) 電気接点用メツキ
耐摩耗性、耐食性、導電性に優れているた
め、電気接点に用いることができる。 (c) Plating for electrical contacts Because it has excellent wear resistance, corrosion resistance, and conductivity, it can be used for electrical contacts.
(d) ICボンテイング用メツキ
金にスズを適量添加すると、融点は著しく
低下することを利用して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のメツ
キに用いることができる。 (d) Plating for IC bonding When an appropriate amount of tin is added to gold, the melting point is significantly lowered, which can be used to plate lead frames for IC wire bonding.
以上に述べたように、本発明による金合金スト
ライクメツキ浴は装飾用、接点用、ボンデイング
用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 strike plating bath according to the present invention can be used for various purposes such as decoration, contacts, and bonding, and is therefore an extremely useful invention in practice.
Claims (1)
トライクメツキ浴において、 シアン化金カリウムとして添加した金が0.2〜
0.8ｇ／と、金属としてニツケルが0.1〜５ｇ／
と、第一スズが0.2〜10ｇ／と、前記金属を
錯化する少なくとも１種類の化合物が150ｇ／
〜750ｇ／と、光沢剤が0.2〜30ｇ／と、前記
第一スズの酸化防止剤の少なくとも１種が0.5〜
50ｇ／とが添加され、PHが４〜６であることを
特徴とする金合金ストライクメツキ浴。[Claims] 1. In a gold alloy strike plating bath suitable for strike plating of gold alloys, the amount of gold added as potassium gold cyanide is from 0.2 to
0.8g/, and nickel as metal is 0.1~5g/
and 0.2 to 10 g of stannous, and 150 g of at least one compound that complexes the metal.
~750g/, the brightener is 0.2~30g/, and at least one of the stannous antioxidants is 0.5~750g/.
A gold alloy strike plating bath characterized by adding 50 g/g/g of gold and having a pH of 4 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7739880A JPS572890A (en) | 1980-06-09 | 1980-06-09 | Gold alloy plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7739880A JPS572890A (en) | 1980-06-09 | 1980-06-09 | Gold alloy plating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS572890A JPS572890A (en) | 1982-01-08 |
| JPS6312954B2 true JPS6312954B2 (en) | 1988-03-23 |
Family
ID=13632785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7739880A Granted JPS572890A (en) | 1980-06-09 | 1980-06-09 | Gold alloy plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS572890A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0455839U (en) * | 1990-09-19 | 1992-05-13 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6773573B2 (en) * | 2001-10-02 | 2004-08-10 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
-
1980
- 1980-06-09 JP JP7739880A patent/JPS572890A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0455839U (en) * | 1990-09-19 | 1992-05-13 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS572890A (en) | 1982-01-08 |
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