JPS6012435B2 - Copper-tin alloy plating bath - Google Patents
Copper-tin alloy plating bathInfo
- Publication number
- JPS6012435B2 JPS6012435B2 JP14726181A JP14726181A JPS6012435B2 JP S6012435 B2 JPS6012435 B2 JP S6012435B2 JP 14726181 A JP14726181 A JP 14726181A JP 14726181 A JP14726181 A JP 14726181A JP S6012435 B2 JPS6012435 B2 JP S6012435B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- tin alloy
- nickel
- alloy plating
- sodium
- 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 title claims description 20
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 8
- 229940071182 stannate Drugs 0.000 claims description 8
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 6
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 125000005402 stannate group Chemical group 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- -1 amine nitrogen compounds Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 5
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229940079864 sodium stannate Drugs 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 3
- 239000010959 steel Substances 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YLZGVPCTROQQSX-UHFFFAOYSA-N [K].[Ni](C#N)C#N Chemical compound [K].[Ni](C#N)C#N YLZGVPCTROQQSX-UHFFFAOYSA-N 0.000 description 2
- LXWJYIBQIPSFSE-UHFFFAOYSA-N dipotassium;nickel(2+);tetracyanide Chemical compound [K+].[K+].[Ni+2].N#[C-].N#[C-].N#[C-].N#[C-] LXWJYIBQIPSFSE-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 229960004889 salicylic acid Drugs 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】
本発明は銅−スズ合金めつき俗に関するものであり、光
沢のある銅−スズ合金めつきを得るためのものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to copper-tin alloy plating, and is intended to obtain glossy copper-tin alloy plating.
従来青化鋼−スズ酸アルカリを主成分とする銅−スズ合
金めつき俗に用いられる光沢剤としては酒石酸、クエン
酸、サリチル酸等のような有機酸類、エチレングリコー
ル、フェノール、８ーナフトール、ハイドロキノソ、８
−ハイドロキシキノリンのようなアルコール、フェノー
ル類、エチレントリアミソ、ピリジン、キノリン、トリ
エタノールアミン等のようなアミン窒素化合物類、ベン
ゼンスルホン酸、Ｐ−トルェンスルホン酸、２，７−ナ
フタレンジスルホン酸ナトリウムのようなベンゼンスル
ホン酸塩誘導体、２山メルカプトベンズチアゾール、２
−メルカプトベンズイミダゾールのようなィオウ含有複
素環状化合物、界面活性剤、さらに銀、鉄、ビスマス、
アンチモン、セレン、テルルのような金属化合物等が知
られているが、これらは単独添加したものも複合添加し
たものも半光沢乃至は無光沢状のめつきとなりやすく、
また光沢があっても使用可能な電流密度範囲が狭いなど
の問題点が多く、工業的に使用することは困難であった
。本発明は上記のような問題点を改善する為数々の実験
と研究を行ってきた結果をもとに、光沢のある良好な銅
−スズ合金めつきを可能する特殊な光沢剤を含む青化繊
ースズ酸アルカリ系の銅−スズ合金めつき浴を提供する
ことを目的とするものである。Conventional blued steel - Copper-tin alloy plating whose main component is alkali stannate. Brightening agents commonly used include organic acids such as tartaric acid, citric acid, and salicylic acid, ethylene glycol, phenol, 8-naphthol, and hydroquinosol. , 8
- Alcohols such as hydroxyquinoline, phenols, amine nitrogen compounds such as ethylene triamiso, pyridine, quinoline, triethanolamine, etc., benzenesulfonic acid, P-toluenesulfonic acid, sodium 2,7-naphthalenedisulfonate benzene sulfonate derivatives such as 2-mercaptobenzthiazole, 2
- Sulfur-containing heterocyclic compounds such as mercaptobenzimidazole, surfactants, as well as silver, iron, bismuth,
Metal compounds such as antimony, selenium, and tellurium are known, but these tend to produce a semi-gloss or matte finish whether added alone or in combination.
Furthermore, even if it is glossy, there are many problems such as a narrow usable current density range, making it difficult to use it industrially. The present invention is based on the results of numerous experiments and research conducted in order to improve the above-mentioned problems.The present invention is based on the results of a number of experiments and studies conducted in order to improve the above-mentioned problems. The object of the present invention is to provide an alkaline stannate-based copper-tin alloy plating bath.
本発明は青化銅−スズ酸アルカリ系の銅−スズ合金めつ
き俗においてチオシアン酸塩とポＩＪエチレンィミンあ
るいはその誘導体及びそのニッケル塩を添加したことを
特徴とするものである。The present invention is characterized in that a thiocyanate, poly-IJ ethyleneimine or a derivative thereof, and a nickel salt thereof are added to a copper-tin alloy plating based on a copper bronze-alkali stannate system.
ここにいうチオシアン酸塩とは、青化鋼−スズ酸アルカ
リ系の銅−スズ合金めつき格に可溶のものであればよく
、特にチオシアン酸ナトリウムであることが好ましい。
このチオシアン酸塩を単独で使用した場合でも一応光沢
効果があるが、使用可能な電流密度範囲が狭い等の問題
点が残る。しかし、ポリエチレンィミンあるいはその誘
導体及びニッケル塩を併用することにより使用可能な電
流密度範囲が著しく拡大するものであることを本発明は
ハルセル試験を繰返して光沢状態などを観察し、膨大な
添加剤の光沢効果を検討した結果到達したものである。
ポリエチレンィミンは完全な線状高分子重合体ではなく
、第１、第２、第３級アミノ窒素を含む枝分かれ構造を
有しており、第１、第２、第３各級の窒素原子の比は、
大略１：２：１なる分子形体であることは良く知られて
いる。The thiocyanate referred to herein may be anything that is soluble in the cyanized steel-alkali stannate copper-tin alloy plating, and sodium thiocyanate is particularly preferred.
Even when this thiocyanate is used alone, there is a certain gloss effect, but there remain problems such as a narrow usable current density range. However, the current density range that can be used is significantly expanded by the combined use of polyethyleneimine or its derivatives and nickel salts.The present invention has repeatedly conducted Hull cell tests and observed the gloss state, and has found that a large number of additives can be used. This was reached as a result of studying the gloss effect of.
Polyethyleneimine is not a completely linear polymer, but has a branched structure containing primary, secondary, and tertiary amino nitrogen atoms. The ratio is
It is well known that the molecular form is approximately 1:2:1.
それ故１級のアミン化合物と同様に反応性に富み、オキ
シアルキル化ポリエチレンィミンなどの種々の誘導体が
容易に得られる。ニッケル塩としては、青化鋼−スズ酸
アルカリ系の銅−スズ合金めつき俗に可溶のものであれ
ばよく硫酸ニッケル、酢酸ニッケル、塩化ニッケル、ク
エン酸ニッケル、シアン化ニッケルカリウム、硝酸ニッ
ケル、スルフアミン酸ニッケル等が用いられる。Therefore, like primary amine compounds, it is highly reactive, and various derivatives such as oxyalkylated polyethyleneimine can be easily obtained. Nickel salts that are commonly soluble in cyanized steel-alkaline stannate copper-tin alloy plating include nickel sulfate, nickel acetate, nickel chloride, nickel citrate, potassium nickel cyanide, and nickel nitrate. , nickel sulfamate, etc. are used.
本発明の浴へのチオシアン酸塩の添加量としては、１０
〜６０夕／そであることが好ましい。The amount of thiocyanate added to the bath of the present invention is 10
~60 evenings/sleeve is preferable.
１０タ′そ以下であると光沢効果があらわれないし、ま
た６０夕／夕を超えると高、低電流密度部分よりくもり
を生ずる。If the current density is less than 10 ta, no gloss effect will be obtained, and if it exceeds 60 m/m, cloudiness will occur in the high and low current density areas.
最も好ましくは２５〜５５夕／そであることがよい。ポ
リエチレンィミンあるいはその誘導体は青化鋼−スズ酸
アルカリ系銅−スズ合金めつき浴に可溶のものであれば
よく、その添加量としては０．０３〜０．６夕／そであ
る。Most preferably, it is 25 to 55 days per sleeve. Polyethyleneimine or its derivatives may be soluble in the cyanized steel-alkali stannate copper-tin alloy plating bath, and the amount added is 0.03 to 0.6 t/s.
０．１３夕／そ未満であると光沢効果があらわれないし
、また０．６夕／そを超えても光沢効果の増大は望めな
い。If it is less than 0.13 evening/so, no gloss effect will be obtained, and even if it exceeds 0.6 evening/so, no increase in the gloss effect can be expected.
最も好ましい添加量としては０．０４〜０．３夕／そで
ある。ニッケル塩の添加量としては塩化ニッケルの場合
は、金属塩として、１０〜８０の９／そである。The most preferable addition amount is 0.04 to 0.3 evening/sleeve. In the case of nickel chloride, the amount of nickel salt added is 10 to 80 9/s as a metal salt.
硫酸ニッケル、硝酸ニッケル、シアン化ニッケルカリウ
ムなどは金属塩として２０〜１５０の９／その添加範囲
である。添加範囲以下だと効果があらわれないし、また
添加範囲以上だと光沢ムラとなり陰極電流効果が著しく
低下する。最も好ましい添加量としては塩化ニッケルが
２５〜７５ｍ９／そであることが好ましく、硫酸ニッケ
ル、硝酸ニッケル、シアン化ニッケルカリウムなどは３
０〜１２０の９／そであることが望ましい。本発明によ
る青化鋼−スズ酸アルカリ系銅−スズ合金めつき格での
めつき操作条件としては、格温４５〜６５ｏｏ程度であ
るのがよい。Nickel sulfate, nickel nitrate, nickel potassium cyanide, etc. are added as metal salts in the range of 20 to 150/9. If it is below the addition range, no effect will be obtained, and if it is above the addition range, the gloss will be uneven and the cathode current effect will be significantly reduced. The most preferable addition amount is 25 to 75 m9/sleeve for nickel chloride, and 3 m/s for nickel sulfate, nickel nitrate, potassium nickel cyanide, etc.
It is desirable that it is 9/sleeve of 0 to 120. The plating operation conditions for the cyanized steel-alkali stannate copper-tin alloy plating according to the present invention are preferably at a temperature of about 45 to 65 oo.
陽極としては、不糟性陽極が望ましく空気撹洋を用いれ
ばより効果がある。以下実施例により本発明をさらに詳
細に説明する。As the anode, a non-porous anode is preferable, and it is more effective if air agitation is used. The present invention will be explained in more detail with reference to Examples below.
実施例 １
スズ酸ナトリウム １００夕／夕青化ナト
リウム ２８．５夕／そ青化鋼
１１．５夕／そ水酸化ナトリウム
１０夕／Ｚチオシアン酸ナトリウム
４０夕／そポリエチレンィミン（３０％水溶液）
０．４の【／と硫酸ニッケル（金属塩として） １０
０の９／そ上記のようにめつき格を調製し、俗温６０ｑ
ｏ、ｐＨ１３．う陽極としてカーボン板を用い空気燈拝
でめつきを行なうと、銀白色の光沢めつきが０．５〜５
Ａ／ｄあの電流密度範囲に得られた。Example 1 Sodium stannate 100 t/sodium stannate 28.5 t/sodium blued steel
11.5 evening/sodium hydroxide
10/Sodium Z thiocyanate
40/So polyethyleneimine (30% aqueous solution)
0.4 [/ and nickel sulfate (as metal salt) 10
9 of 0 / So prepare the metsuki grade as above, and the ordinary temperature is 60q.
o, pH 13. When plating is performed using an air lamp using a carbon plate as an anode, a silvery white glossy plating of 0.5 to 5
A/d current density range was obtained.
実施例 ２
スズ酸ナトリウム １００夕／夕青化ナ
トリウム ３０夕／そ青化鋼
１２夕／そ水酸化ナトリウム１０タ
′〆チオシアン酸ナトリウム ３５夕／そポリ
エチレンイミン（３０％水溶液）０．３肌′そ塩化ニッ
ケル（金属塩として） ６０の９／〆上記のようにめ
つき格を調製し、俗温５５ｑｏ、ＰＨ１３．ふ陽極とし
てカーボン板を用い空気櫨枠でめつきを行なうと、銀白
色の光沢めつきが０．＄／ｄあの電流密度範囲に得られ
た。Example 2 Sodium stannate 100 t/sodium stannate 30 t/sodium blued steel
12 parts/Sodium hydroxide 10 parts Sodium thiocyanate 35 parts/1 Polyethyleneimine (30% aqueous solution) 0.3 parts Nickel chloride (as metal salt) 60 parts/9 parts Plating grade as above was prepared, and the temperature was 55 qo and the pH was 13. When a carbon plate is used as an anode and plating is carried out using an air frame, a silvery white glossy plating of 0. A current density range of $/d was obtained.
実施例 ３スズ酸ナトリウム ２０タ′
そ青化ナトリウム ３５夕／夕青化鋼
２０夕／夕水酸化ナトリウ
ム １０夕／そチオシアン酸ナトリウム
２０タ′そポリエチレンィミン（３０％水溶
液）０．４の‘／そシアン化ニッケルカリウム（金属塩
として）８０の９／夕上記のようにめつき液を調製し、
俗温４５ｑｏ、ｐＨ１３．５、陽極としてカーボン板を
用い空気蝿梓でめつきを行なうと、黄金色の光沢めつき
が０．５〜４Ａ／ｄ〆の電流密度範囲に得られた。Example 3 Sodium stannate 20 t'
Sodium cyanide 35 Yu/Yu Seika Steel
20 minutes/night Sodium hydroxide 10 minutes/Sodium thiocyanate 20 days Polyethyleneimine (30% aqueous solution) 0.4 minutes/So Nickel potassium cyanide (as metal salt) 80 minutes/Day As above Prepare the glitter solution,
When plating was carried out with air fly azure at a normal temperature of 45 qo and a pH of 13.5 using a carbon plate as an anode, a golden glossy plating was obtained at a current density range of 0.5 to 4 A/d.
以上述べてきたように本発明によれば光沢電流密度範囲
が広く長期安定性にすぐれ、また均一な光沢が得られる
という極めて優秀なめつき格で工業的にも利用しうるも
のである。As described above, the present invention has a wide gloss current density range, has excellent long-term stability, and has extremely excellent plating properties such as uniform gloss and can be used industrially.
なお本発明は、種々の格において実施できることはもち
ろんのこと、光沢剤についても本発明の範囲内において
適宜組合せて使用できることはいうまでもない。It goes without saying that the present invention can be practiced in a variety of ways, and that brighteners can also be used in appropriate combinations within the scope of the present invention.
Claims (1)
において、チオシアン酸塩、ポリエチレンイミンあるい
はその誘導体およびニツケル塩を添加したことを特徴と
する銅−スズ合金めつき浴。1. A copper-tin alloy plating bath based on copper bronze-alkaline stannate, characterized in that a thiocyanate, polyethyleneimine or a derivative thereof, and a nickel salt are added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14726181A JPS6012435B2 (en) | 1981-09-18 | 1981-09-18 | Copper-tin alloy plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14726181A JPS6012435B2 (en) | 1981-09-18 | 1981-09-18 | Copper-tin alloy plating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5848690A JPS5848690A (en) | 1983-03-22 |
| JPS6012435B2 true JPS6012435B2 (en) | 1985-04-01 |
Family
ID=15426225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14726181A Expired JPS6012435B2 (en) | 1981-09-18 | 1981-09-18 | Copper-tin alloy plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6012435B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60226196T2 (en) * | 2001-05-24 | 2009-05-14 | Shipley Co., L.L.C., Marlborough | Tin-plating |
-
1981
- 1981-09-18 JP JP14726181A patent/JPS6012435B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5848690A (en) | 1983-03-22 |
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