JPS5855587A - Copper-tin alloy plating bath - Google Patents
Copper-tin alloy plating bathInfo
- Publication number
- JPS5855587A JPS5855587A JP15176181A JP15176181A JPS5855587A JP S5855587 A JPS5855587 A JP S5855587A JP 15176181 A JP15176181 A JP 15176181A JP 15176181 A JP15176181 A JP 15176181A JP S5855587 A JPS5855587 A JP S5855587A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- tin alloy
- pref
- bath
- alloy plating
- 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.)
- Pending
Links
Abstract
Description
【発明の詳細な説明】
本発明は銅−スズ合金めつ１浴に関するものでちゃ、光
沢のある銅−スズ合金めり龜を得るためのものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a copper-tin alloy bath, and is intended to obtain a shiny copper-tin alloy pot.
従来背化鋼−スズ酸アルカリを主成分とする銅−スズ合
金めり１浴に用いられる光沢剤としては酒石酸、クエン
酸、すり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、−一ナフトール、ハイド胃キノン、８
−ハイドロ中シキノリンのようなアル；−ル、・フェノ
ール類、エチレントリアミン、ピリジン、キノリン、シ
リエタノ−ルア電ンなどのようなアミン窒素化合物類、
べ／ゼンスルホン酸、了−Ｆルエンスルホン酸、２．７
−ナツメレンジスルホン酸すＦリクムのようなベン（ン
スルホン酸塩誘導体、２−メルカプトベンズチアゾール
、ニーメルカプトベンズイミダゾールのようなイオウ含
有複素環状化合物、界面活性１？４、更ＫＩ１％ ビス
マス、アンチモン、セレン、テルルのよ５な金属化合物
等が知らｎているが、こｎらは単独添加し１′Ｉ−もの
も複合添加したものも半５を沢乃至は無光沢状のめっき
となシやす（、を九光沢があっても使用可能な電［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。Conventional brighteners used in the copper-tin alloy polishing bath, which mainly consists of alkali stannate, include organic acids such as tartaric acid, citric acid, and licylic acid, ethylene glycol, phenol, and stannic acid. naphthol, hyde gastric quinone, 8
- alcohols such as hydrochloride, phenols, amine nitrogen compounds such as ethylenetriamine, pyridine, quinoline, sylethanol, etc.;
Be/zenesulfonic acid, Ryo-F luenesulfonic acid, 2.7
- sulfur-containing heterocyclic compounds such as sulfonate derivatives, 2-mercaptobenzthiazole, niemercaptobenzimidazole, surface activity 1-4, KI 1%, bismuth, antimony, Five-dimensional metal compounds such as selenium and tellurium are known, but these can be added alone, added in combination, or added in combination. (Even if it was shiny, there were many problems such as a narrow range of usable electric density, making it difficult to use it industrially.
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
研究を行なって亀た結果ｔ−もとに、光沢のある良好な
銅−スズ合金めつき浴を特徴とする特殊な光沢剤を含む
實化鋼−スズ酸アルカリ系銅−スズ合金めり１浴【提供
すること上目的とするものである。The present invention is based on the results of numerous experiments and studies in order to improve the above-mentioned problems.The present invention is based on a special brightening agent characterized by a copper-tin alloy plating bath with good gloss. It is an object of the present invention to provide a steel-stannic acid alkali-based copper-tin alloy milling bath.
本発１ｊＩＦｉ青化銅−スズ酸アルカリ系鋼−スズ合金
゛応つき浴においてチオシアン酸塩とポリエチレンイミ
ンあるいはその誘導体及び鉛塩を添加したこと’ｔ％黴
とするものである。The present invention is a 1j IFi copper cyanide-alkaline stannate steel-tin alloy which contains thiocyanate, polyethyleneimine or its derivatives, and lead salts in a reaction bath to reduce moldiness.
ここにいうチオシアン酸塩とは、青化銅−スズ酸アルカ
リ系鋼−スズ合金めっき浴に可溶のものであｎばよ（、
特にチオシアン酸ナトリク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などの問題
点が残る。しかし、ポリエチレンイミンあるいはその誘
導体及び鉛塩を併用することによ）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。The thiocyanate mentioned here is one that is soluble in a copper cyanide-alkaline stannate steel-tin alloy plating bath.
Particularly preferred is sodium thiocyanate. 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, by using polyethyleneimine or its derivatives and lead salts in combination, the usable current density range is significantly expanded.The present invention has repeatedly conducted Hull cell tests and observed the gloss state, and has found that a vast amount of This was reached as a result of studying the gloss effect of additives.
ポリエチレンイミンは完全な線状高分子重合体ではな（
、Ｍｌ 、第２．第３級丁ミノ窒素を含む枝分かれ構造
ｔｖしており、第１．２．３各級の窒素原子の比は大略
１：２：１なる分子形態であることは良く知らｎている
。それ故、１級ア電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イミンなど種々の誘導体が
容易に得られる。Polyethyleneimine is not a completely linear polymer (
, Ml, 2nd. It is well known that it has a branched structure containing tertiary nitrogen, and that the molecular form is such that the ratio of nitrogen atoms of each class 1, 2, and 3 is approximately 1:2:1. Therefore, like primary adenone compounds, it is highly reactive, and various derivatives such as oxyalkylated polyethyleneimine can be easily obtained.
鉛塩としては、實化鋼−スズ酸アルカリ系銅−スズ合金
めっき浴に可溶のものでＴｏｔＬばよ（酢酸鉛、硫酸鉛
、硝酸鉛、クエン酸鉛などの無機酸塩及ヒフエノールス
ルホン酸鉛、アルカノールスルホンａ鉛などのような１
機酸塩などが用いらｎる本発明の浴へのチオシアン酸塩
の添加量としては、１０−〇 〇 １１／ｌであること
が好ましい、ｌ０ＪＩ／を以下であると光沢効果があら
れれないし、また６ ０ ＩＩ／ｌｔ超えると高、低電
流密度部分よシ（も夛【生ずる。最も好ましくは２５〜
５５９／ｌであることがよい。Lead salts include those soluble in the steel-alkaline stannate copper-tin alloy plating bath (inorganic acid salts such as lead acetate, lead sulfate, lead nitrate, lead citrate, and hyphenolsulfone). 1 such as acid lead, alkanol sulfone a lead, etc.
The amount of thiocyanate added to the bath of the present invention in which thiocyanate is used is preferably 10-11/l; if it is less than 10JI/l, the gloss effect cannot be obtained. , and if it exceeds 60 II/lt, the high and low current density parts will be damaged. Most preferably, the
It is preferably 559/l.
ポリエチレンイミンあるいはその誘導体は青化銅−スズ
酸アルカリ系銅−スズ合金めっき浴に可溶のもので６２
’Ｌばよ（、その添加量としては０゜０３〜０．６１／
ｌである。０．０３＃／を未満であると光沢効果があら
れ肚ないし、また０、６１１／ｌ’に超凡ても光沢効果
の増大は望めない、最も好ましい添加量としては０．０
４〜ｏ、ｓｔｔ／ｌである。Polyethyleneimine or its derivatives are soluble in copper bronze-alkaline stannate copper-tin alloy plating baths62
'Lbayo (, the amount added is 0°03~0.61/
It is l. If the amount is less than 0.03#/l, the gloss effect is unbearable, and even if it exceeds 0.611/l', no increase in the gloss effect can be expected.The most preferable addition amount is 0.0
4-o, stt/l.
鉛塩の添加量としては酢酸鉛、硝酸鉛、（ｉＩｗ＆鉛、
クエン酸鉛などの無機酸塩は鉛塩として１〜１２ｔ４
／ Ａ テＩる。フェノールスルホン酸鉛、アルカノー
ルスルホン酸鉛などの有機酸塩は鉛塩として１〜１０
ｎｄｌ ／ ｔである。添加範囲以下だと効果があられ
れないし、また添加範囲以上だとめつき析出不良となる
。最も好ましい添２Ｋｌ童としては、無機酸塩が３〜１
０ ｖｙｉ＃ ／ ｔでおる。有機酸塩は２〜８−／Ｌ
であることが好ましい。The amount of lead salt added is lead acetate, lead nitrate, (iIw & lead,
Inorganic acid salts such as lead citrate are 1 to 12t4 as lead salts.
/ A teIru. Organic acid salts such as lead phenolsulfonate and lead alkanolsulfonate are 1 to 10 as lead salts.
ndl/t. If it is below the addition range, the effect will not be achieved, and if it is above the addition range, it will cause sticking and poor precipitation. The most preferred additive is 3 to 1 inorganic acid salts.
0 vyi # / t. Organic acid salts are 2-8-/L
It is preferable that
本発明による青化銅−スズ酸丁ルカリ系鋼−スズ合金め
っき浴でのめつき操作条件は、浴温４５〜６５Ｃ程度で
あるのがよい、陽極としては不溶性陽極が望ましく空気
攪拌を用いればより効果がある。The plating operation conditions for the copper bronze-stannate-based steel-tin alloy plating bath according to the present invention are preferably a bath temperature of about 45 to 65C, and an insoluble anode is preferably used as the anode, and air stirring is used. It's more effective.
以下実施例によシ本発明をさらに詳細に説明する。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 １ ｏ ｏ ｔｔ／を
青化ナト、リウム ２Ｂ、５ＩＩ／を實
化鋼 １１，５ＪＦ／Ａ水酸化す
）リウム ｘｏｔｉ７ｔチオシアン酸ナ
トリウム ４０１１／ｌボ９エチレンイ電ン＜
”ｓｒｓ水溶液）０．２ｓＬ／Ｌ
酢酸鉛（鉛塩としてン ５−／を上記の
ようにめり１浴ｔａ製し、浴温６０℃、Ｐｉｌ１３．５
．陽極としてカーボン板を用いて空気攪拌を行なうと、
銀白色の光沢めっきが０．５〜４ム／ｄ−の電流密度範
囲に得らｎた。Example-1 Sodium stannate 1 o o tt/ to blue sodium chloride, lium 2B, 5II/ to ferrochlorinated steel 11,5JF/A hydroxide) lithium xoti7t sodium thiocyanate 4011/l bo9 ethylene ion<
"srs aqueous solution) 0.2 sL/L lead acetate (as lead salt) was prepared in one bath as described above, bath temperature 60℃, Pil 13.5
．． When air agitation is performed using a carbon plate as an anode,
A silvery white bright plating was obtained at a current density range of 0.5 to 4 μm/d.
実施ｆ％−２
スズ酸ナシリウム ２０１／Ｌ青化ナト
リウム ２５１１／Ｌ育化鋼
２０１／を水酸化ナトリウム
１０１／ｌポリエチレンイζン（３１溶１’
ｌ［）０．３惧ｔ７ｔ
フェノールスルホン酸鉛（鉛塩として〕４１１ＩＪ／を
上記のようにめっき浴を調製し、浴温４５℃、１）ＨＩ
３゜５、陽也としてカーボン板を用い空気攪拌でめつ１
ｉｉを行なうと、黄金色の光沢めっきが０−５〜３−５
Ａ ／ ｄｔｈ嘗ノ１１ＩｃｆＩＬ密度範囲に得られ
た。Implementation f%-2 Nasylium stannate 201/L Sodium cyanide 2511/L Growth steel
201/ Sodium hydroxide
101/l polyethylene ζ ion (31 mol 1'
l[) 0.3 t7t Lead phenolsulfonate (as lead salt) 411 IJ/ was prepared in a plating bath as described above, the bath temperature was 45°C, 1) HI
3゜5, Metsu 1 with air agitation using a carbon plate as Yoya
When performing ii, the golden glossy plating will be 0-5 to 3-5.
A/dth was obtained in the IcfIL density range of 11.
以上述べてきたように本発明によれば光沢電流密度範回
が広く長期安定性にすぐｎｌまた均一な光沢が得らオＬ
る。工業的にも利用しうるものである。As described above, according to the present invention, it is possible to obtain a wide gloss current density range, long-term stability, and uniform gloss.
Ru. It can also be used industrially.
なお本発明は、種々の浴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 carried out in various baths, and that brighteners can also be used in appropriate combinations within the scope of the present invention.
以上that's all
Claims (1)
−いて、チオシアン酸塩とポリエチレンイミンあるいは
その紡導体シよび鉛塩を添加したことを特徴とする銅−
スズ合金めつ亀浴。Realized steel - Alkaline stannate steel - Tin alloy plating bath Ksi
- Copper characterized by adding thiocyanate, polyethyleneimine or its spinneret, and lead salt -
Tin alloy turtle bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15176181A JPS5855587A (en) | 1981-09-25 | 1981-09-25 | Copper-tin alloy plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15176181A JPS5855587A (en) | 1981-09-25 | 1981-09-25 | Copper-tin alloy plating bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5855587A true JPS5855587A (en) | 1983-04-01 |
Family
ID=15525713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15176181A Pending JPS5855587A (en) | 1981-09-25 | 1981-09-25 | Copper-tin alloy plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5855587A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02107795A (en) * | 1988-10-14 | 1990-04-19 | Tohoku Ricoh Co Ltd | Copper-tin alloy plating bath |
| US5614327A (en) * | 1994-09-09 | 1997-03-25 | Sarthoise De Revetements Electrolytiques | Process for protecting a silver or silver-coated part |
| EP1197587A2 (en) * | 2000-10-13 | 2002-04-17 | Shipley Co. L.L.C. | Seed layer repair and electroplating bath |
| EP1260614A1 (en) * | 2001-05-24 | 2002-11-27 | Shipley Co. L.L.C. | Tin plating |
| EP1479793A2 (en) * | 2003-05-23 | 2004-11-24 | Rohm and Haas Electronic Materials, L.L.C. | Plating method |
-
1981
- 1981-09-25 JP JP15176181A patent/JPS5855587A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02107795A (en) * | 1988-10-14 | 1990-04-19 | Tohoku Ricoh Co Ltd | Copper-tin alloy plating bath |
| JPH0413434B2 (en) * | 1988-10-14 | 1992-03-09 | Tohoku Riko Kk | |
| US5614327A (en) * | 1994-09-09 | 1997-03-25 | Sarthoise De Revetements Electrolytiques | Process for protecting a silver or silver-coated part |
| EP1197587A2 (en) * | 2000-10-13 | 2002-04-17 | Shipley Co. L.L.C. | Seed layer repair and electroplating bath |
| EP1197587A3 (en) * | 2000-10-13 | 2002-05-15 | Shipley Co. L.L.C. | Seed layer repair and electroplating bath |
| US6682642B2 (en) | 2000-10-13 | 2004-01-27 | Shipley Company, L.L.C. | Seed repair and electroplating bath |
| EP1260614A1 (en) * | 2001-05-24 | 2002-11-27 | Shipley Co. L.L.C. | Tin plating |
| US6797142B2 (en) | 2001-05-24 | 2004-09-28 | Shipley Company, L.L.C. | Tin plating |
| CN1296521C (en) * | 2001-05-24 | 2007-01-24 | 希普列公司 | Composition and method for tinplating |
| JP2009114548A (en) * | 2001-05-24 | 2009-05-28 | Rohm & Haas Electronic Materials Llc | Tin plating |
| EP1479793A2 (en) * | 2003-05-23 | 2004-11-24 | Rohm and Haas Electronic Materials, L.L.C. | Plating method |
| EP1479793A3 (en) * | 2003-05-23 | 2008-02-13 | Rohm and Haas Electronic Materials, L.L.C. | Plating method |
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