JPH0598488A - Copper-nickel alloy electroplating bath - Google Patents
Copper-nickel alloy electroplating bathInfo
- Publication number
- JPH0598488A JPH0598488A JP15988491A JP15988491A JPH0598488A JP H0598488 A JPH0598488 A JP H0598488A JP 15988491 A JP15988491 A JP 15988491A JP 15988491 A JP15988491 A JP 15988491A JP H0598488 A JPH0598488 A JP H0598488A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- nickel
- nickel alloy
- bath
- 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.)
- Withdrawn
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、銅−ニッケル合金電
気メッキ浴に関する。更に詳しくは、本発明は、銅塩、
ニッケル塩及び四ほう酸ナトリウムを主成分とする銅−
ニッケル合金電気メッキ浴の改良に関する。FIELD OF THE INVENTION This invention relates to copper-nickel alloy electroplating baths. More specifically, the present invention provides a copper salt,
Copper containing nickel salt and sodium tetraborate as main components
Improvement of nickel alloy electroplating bath.
【０００２】[0002]
【従来の技術】一般に、銅−ニッケル合金は、耐食性に
優れており、展延性もよく、加工性の高い合金である。
銅とニッケルとは結晶の格子定数も近いため、互いに固
容しやすく、その状態図は全率固溶型を示す。そのた
め、あらゆる組成で合金を形成し、その合金の諸特性は
組成変化によって徐々に変化する。したがって、実用合
金として、Ｎｉが約２０〜３０重量％のものは白銅（キ
ュプロニッケル）、Ｎｉが約６０〜７０重量％のものは
モネルメタルと呼ばれている。合金電気めっきとして
も、従来シアン浴、くえん酸浴、酢酸浴、酒石酸浴、チ
オ硫酸浴、ピロリン酸浴など多くの浴が研究されている
が、実用化に至るほどには十分なものではない。2. Description of the Related Art Generally, a copper-nickel alloy is an alloy having excellent corrosion resistance, good spreadability, and high workability.
Since the crystal lattice constants of copper and nickel are close to each other, they are likely to be solidified with each other, and the phase diagram shows a solid solution type in all cases. Therefore, an alloy is formed with any composition, and the characteristics of the alloy gradually change due to the composition change. Therefore, as a practical alloy, nickel alloy having about 20 to 30% by weight is called white copper (cupronickel), and nickel alloy having about 60 to 70% by weight is called monel metal. As for alloy electroplating, many baths such as cyanide bath, citric acid bath, acetic acid bath, tartaric acid bath, thiosulfuric acid bath, and pyrophosphoric acid bath have been studied, but they are not enough for practical use. ..
【０００３】[0003]
【発明が解決しようとする課題】この銅−ニッケル合金
めっきの実用化が今日までなされ得なかった理由として
は、銅の析出電位がニッケルに比べて非常に貴であり、
銅の優先的な析出が起こり、良好な電析皮膜を得ること
ができないことである。くえん酸浴からは比較的良好な
合金皮膜が得られるが、浴の安定性が極めて悪い。チオ
硫酸浴は、銅−ニッケル合金の析出の際に硫黄が共析
し、耐食性が問題となる。また、特開昭５８−１３３３
９１号にピロリン酸浴が開示されているが、めっき膜厚
が薄く、高耐食性皮膜として実用性が乏しい。本発明
は、上記のような実情に鑑みてなされたものであって、
低電流密度から高電流密度に渡って外観が良好でかつ均
一性のある優れた銅−ニッケル合金皮膜を得るための電
気めっき浴を提供することを目的とする。The reason why the copper-nickel alloy plating could not be put into practical use to date is that the deposition potential of copper is extremely noble as compared with nickel.
That is, preferential deposition of copper occurs and a good electrodeposition film cannot be obtained. A relatively good alloy film can be obtained from a citric acid bath, but the stability of the bath is extremely poor. In the thiosulfate bath, sulfur is co-deposited during the precipitation of the copper-nickel alloy, which causes a problem of corrosion resistance. In addition, JP-A-58-1333
No. 91 discloses a pyrophosphoric acid bath, but its plating film thickness is thin and its practicality as a highly corrosion resistant film is poor. The present invention has been made in view of the above circumstances,
An object of the present invention is to provide an electroplating bath for obtaining an excellent copper-nickel alloy film having a good appearance and a uniform appearance from low current density to high current density.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記の目的
を達成するため鋭意検討を行なった結果、銅塩とニッケ
ル塩に四ほう酸ナトリウムを添加してなる銅−ニッケル
合金電気めっき浴に、りんご酸、グルコン酸及びサリチ
ル酸の１種又は２種以上と更にサッカリンを添加するこ
とにより、ブライトからセミブライト系白銅色の良好な
外観を有する銅−ニッケル合金皮膜を形成することが可
能となり、しかもこの浴は経時安定性に優れ、比較的厚
いめっきもできることを見出し、本発明を完成するに至
った。したがって、本発明の主題は、銅塩、ニッケル塩
及び四ほう酸ナトリウムよりなる銅−ニッケル合金電気
メッキ浴において、りんご酸、グルコン酸及びサリチル
酸の１種又は２種以上とサッカリンとを添加したことを
特徴とする銅−ニッケル合金電気メッキ浴にある。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that a copper-nickel alloy electroplating bath prepared by adding sodium tetraborate to a copper salt and a nickel salt is used. , By adding one or more of malic acid, gluconic acid and salicylic acid and further saccharin, it becomes possible to form a copper-nickel alloy film having a good appearance of bright to semi-bright white copper color, Moreover, they have found that this bath is excellent in stability over time and can perform relatively thick plating, and thus completed the present invention. Therefore, the subject of the present invention is that in a copper-nickel alloy electroplating bath consisting of a copper salt, a nickel salt and sodium tetraborate, one or more of malic acid, gluconic acid and salicylic acid and saccharin are added. Characterized in a copper-nickel alloy electroplating bath.
【０００５】[0005]
【発明の具体的な説明】本発明の合金めっき浴に使用さ
れる銅塩としては、硫酸銅、塩化第二銅、硝酸銅、塩基
性炭酸銅、スファミン酸銅、酢酸銅、しゅう酸銅、メタ
ンスルホン酸銅、２−ヒドロキシプロパンスルホン酸
銅、フェノールスルホン酸銅、ほう弗化銅などが例示で
きる。また、ニッケル塩としては、硫酸ニッケル、塩化
ニッケル、蟻酸ニッケル、酢酸ニッケル、しゅう酸ニッ
ケル、メタンスルホン酸ニッケル、２−ヒドロキシプロ
パンスルホン酸ニッケル、フェノールスルホン酸ニッケ
ル、ほう弗化ニッケルなどが例示できる。これら銅塩と
ニッケル塩のめっき浴中の含有量は種々選定されるが、
銅塩は銅として０．５〜５０ｇ／ｌ、好ましくは３〜２
０ｇ／ｌであり、ニッケル塩はニッケルとして１０〜１
００ｇ／ｌ、好ましくは３０〜６０ｇ／ｌである。DETAILED DESCRIPTION OF THE INVENTION Examples of the copper salt used in the alloy plating bath of the present invention include copper sulfate, cupric chloride, copper nitrate, basic copper carbonate, copper sphamate, copper acetate, copper oxalate, Examples include copper methane sulfonate, copper 2-hydroxypropane sulfonate, copper phenol sulfonate, and copper borofluoride. Examples of the nickel salt include nickel sulfate, nickel chloride, nickel formate, nickel acetate, nickel oxalate, nickel methanesulfonate, nickel 2-hydroxypropanesulfonate, nickel phenolsulfonate, and nickel borofluoride. The content of these copper salts and nickel salts in the plating bath is selected variously,
The copper salt is 0.5 to 50 g / l as copper, preferably 3 to 2
It is 0 g / l, and the nickel salt is 10 to 1 as nickel.
The amount is 00 g / l, preferably 30 to 60 g / l.
【０００６】高電流密度で電解すると電極近傍で水素ガ
スが発生し、ｐＨの変動が大きくなり、めっきに支障を
来すため、ｐＨ緩衝剤として四ほう酸ナトリウム添加す
る。四ほう酸ナトリウムの添加量としては、１０〜１０
０ｇ／ｌ、好ましくは４０〜６０ｇ／ｌである。ｐＨの
範囲としては２〜６、好ましくは３．５〜４．５であ
る。When electrolyzing at a high current density, hydrogen gas is generated in the vicinity of the electrode, the pH fluctuation becomes large, and plating is hindered. Sodium tetraborate is added as a pH buffering agent. The amount of sodium tetraborate added is 10 to 10
It is 0 g / l, preferably 40-60 g / l. The pH range is 2 to 6, preferably 3.5 to 4.5.
【０００７】前述したように、本発明のめっき浴におい
ては、銅とニッケルとの析出電位が離れているために単
純浴では目的とする合金電析ができない。この銅とニッ
ケルの析出電位を接近せしめる添加剤として、本発明で
はりんご酸、グルコン酸及びサリチル酸が選ばれる。こ
れらは単独で又は併用してもよい。これらの添加量は１
０〜２００ｇ／ｌ、好ましくは３０〜１００ｇ／ｌであ
る。As described above, in the plating bath of the present invention, the intended alloy electrodeposition cannot be performed in the simple bath because the deposition potentials of copper and nickel are different from each other. In the present invention, malic acid, gluconic acid and salicylic acid are selected as the additives that bring the deposition potentials of copper and nickel close to each other. These may be used alone or in combination. The addition amount of these is 1
It is 0 to 200 g / l, preferably 30 to 100 g / l.
【０００８】また、本発明のめっき浴では、めっき表面
の平滑性又は光沢を向上させるため平滑剤又は光沢剤と
してサッカリンが添加される。添加量は０．１〜１０ｇ
／ｌ、好ましくは１〜５ｇ／ｌである。Further, in the plating bath of the present invention, saccharin is added as a smoothing agent or brightening agent in order to improve the smoothness or gloss of the plating surface. Addition amount is 0.1-10g
/ L, preferably 1-5 g / l.
【０００９】本発明の銅−ニッケル合金電気めっき浴を
使用してめっきを行なう場合の条件としては、特に制限
されるものではないが、陰極電流密度は２〜６Ａ／ｄｍ
2 とすることができ、めっき浴温度は１５〜５０℃を採
用することができる。また、撹拌は液流、カソードロッ
カーなどの機械的撹拌を採用することができる。The conditions for plating using the copper-nickel alloy electroplating bath of the present invention are not particularly limited, but the cathode current density is 2 to 6 A / dm.
2, and the plating bath temperature may be 15 to 50 ° C. Further, mechanical stirring such as liquid flow and cathode rocker can be adopted for stirring.
【００１０】[0010]
【実施例】次に、本発明の実施例によるめっき浴の組成
及びめっき条件を以下に示すが、本発明はこれらの実施
例に限定されるものではなく、前述したような均質で平
滑な白銅色のめっきを得るという趣旨に添ってめっき浴
の組成及びめっき条件を任意に変更することができる。実施例１〜８及び比較例１〜３ 本発明の実施例１〜８及び比較例１〜３の各めっき浴を
下記の表１に示す組成に従って調製し、そして表１に記
載のめっき条件に従ってめっきを行なった。めっきは、
試験片に０．４×３０×３０ｍｍのステンレス板を、ま
た陽極にニッケル板を使用し、浴量を２５０ｍｌとし、
浴温を２５〜３５℃の間とし、カソードロッカーを２．
５ｍ／ｍｉｎとし、電流密度を２〜６Ａ／ｄｍ2 の間と
して実施した。得られためっきの外観は、上記の条件で
８〜１０μｍのめっきを施した後に評価した。また、電
析物の組成は、試験片からめっき皮膜を剥し、濃硫酸を
加えて加熱溶解させ、化学分析により銅の含有率を調査
した。得られためっき皮膜の外観及び皮膜中のＣｕの量
を表１に示す。EXAMPLES Next, the composition of the plating bath and the plating conditions according to the examples of the present invention are shown below, but the present invention is not limited to these examples, and the homogeneous and smooth white copper as described above is used. The composition of the plating bath and the plating conditions can be arbitrarily changed according to the purpose of obtaining color plating. Examples 1 to 8 and Comparative Examples 1 to 3 The plating baths of Examples 1 to 8 and Comparative Examples 1 to 3 of the present invention were prepared according to the compositions shown in Table 1 below, and according to the plating conditions described in Table 1. Plated. Plating is
A stainless steel plate of 0.4 × 30 × 30 mm was used for the test piece, and a nickel plate was used for the anode, and the bath volume was 250 ml.
The bath temperature was between 25 and 35 ° C., and the cathode locker was 2.
The current density was set to 5 m / min and the current density was set to 2 to 6 A / dm 2 . The appearance of the obtained plating was evaluated after applying 8 to 10 μm plating under the above conditions. Further, regarding the composition of the electrodeposit, the plating film was peeled from the test piece, concentrated sulfuric acid was added, and the mixture was heated and dissolved. Table 1 shows the appearance of the obtained plating film and the amount of Cu in the film.
【００１１】[0011]
【表１】 [Table 1]
【００１２】[0012]
【発明の効果】本発明の合金めっき浴によれば、Ｃｕ量
が２０〜６５％の範囲にあり、しかも均一で白銅色の銅
−ニッケル合金めっきを広い電流密度範囲にわたって形
成することができ、更にめっき浴の経時安定性も優れて
いるので耐食性の銅−ニッケル合金めっきとして工業的
に十分に利用できるという効果が得られた。According to the alloy plating bath of the present invention, the amount of Cu is in the range of 20 to 65%, and a uniform white copper-colored copper-nickel alloy plating can be formed over a wide current density range. Further, since the stability of the plating bath over time is excellent, the effect that it can be industrially sufficiently utilized as a corrosion-resistant copper-nickel alloy plating was obtained.
Claims (1)
ムよりなる銅−ニッケル合金電気メッキ浴において、り
んご酸、グルコン酸及びサリチル酸の１種又は２種以上
とサッカリンとを添加したことを特徴とする銅−ニッケ
ル合金電気メッキ浴。1. A copper-nickel alloy electroplating bath comprising a copper salt, a nickel salt and sodium tetraborate, wherein one or more of malic acid, gluconic acid and salicylic acid and saccharin are added. Copper-nickel alloy electroplating bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15988491A JPH0598488A (en) | 1991-06-05 | 1991-06-05 | Copper-nickel alloy electroplating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15988491A JPH0598488A (en) | 1991-06-05 | 1991-06-05 | Copper-nickel alloy electroplating bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0598488A true JPH0598488A (en) | 1993-04-20 |
Family
ID=15703294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15988491A Withdrawn JPH0598488A (en) | 1991-06-05 | 1991-06-05 | Copper-nickel alloy electroplating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0598488A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0892087A2 (en) * | 1997-06-18 | 1999-01-20 | ATOTECH Deutschland GmbH | Electroplating of low-stress nickel |
| KR19990007076A (en) * | 1998-04-23 | 1999-01-25 | 라이더 존 피. | Electroplating of Low Stress Nickel |
| EP1092790A3 (en) * | 1999-10-14 | 2002-09-11 | Atofina Chemicals, Inc. | Electroplating of copper from alkanesulfonate electrolytes |
| WO2013157639A1 (en) | 2012-04-19 | 2013-10-24 | ディップソール株式会社 | Copper-nickel alloy electroplating bath and plating method |
| WO2016021369A1 (en) * | 2014-08-08 | 2016-02-11 | ディップソール株式会社 | Copper-nickel alloy electroplating bath |
| JP2017197836A (en) * | 2016-04-30 | 2017-11-02 | 新日鐵住金株式会社 | Copper-nickel alloy material and mechanical component covered therewith |
-
1991
- 1991-06-05 JP JP15988491A patent/JPH0598488A/en not_active Withdrawn
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0892087A3 (en) * | 1997-06-18 | 2000-06-07 | ATOTECH Deutschland GmbH | Electroplating of low-stress nickel |
| EP0892087A2 (en) * | 1997-06-18 | 1999-01-20 | ATOTECH Deutschland GmbH | Electroplating of low-stress nickel |
| KR19990007076A (en) * | 1998-04-23 | 1999-01-25 | 라이더 존 피. | Electroplating of Low Stress Nickel |
| EP1092790A3 (en) * | 1999-10-14 | 2002-09-11 | Atofina Chemicals, Inc. | Electroplating of copper from alkanesulfonate electrolytes |
| CN104321470B (en) * | 2012-04-19 | 2017-03-15 | 迪普索尔化学株式会社 | The electroplate liquid and coating method of corronil |
| WO2013157639A1 (en) | 2012-04-19 | 2013-10-24 | ディップソール株式会社 | Copper-nickel alloy electroplating bath and plating method |
| KR20140130546A (en) * | 2012-04-19 | 2014-11-10 | 딥솔 가부시키가이샤 | Copper-nickel alloy electroplating bath and plating method |
| CN104321470A (en) * | 2012-04-19 | 2015-01-28 | 迪普索尔化学株式会社 | Copper-nickel alloy electroplating bath and plating method |
| JPWO2013157639A1 (en) * | 2012-04-19 | 2015-12-21 | ディップソール株式会社 | Copper-nickel alloy electroplating bath and plating method |
| US9828686B2 (en) | 2012-04-19 | 2017-11-28 | Dipsol Chemicals Co., Ltd. | Copper-nickel alloy electroplating bath and plating method |
| WO2016021369A1 (en) * | 2014-08-08 | 2016-02-11 | ディップソール株式会社 | Copper-nickel alloy electroplating bath |
| CN106574387A (en) * | 2014-08-08 | 2017-04-19 | 迪普索股份公司 | Copper-nickel alloy electroplating bath |
| JP2016037649A (en) * | 2014-08-08 | 2016-03-22 | ディップソール株式会社 | Copper-nickel alloy electroplating bath |
| RU2666391C1 (en) * | 2014-08-08 | 2018-09-07 | Дипсол Кемикалз Ко., Лтд. | Bath for electrolytic coating with copper-nickel alloys |
| US10316421B2 (en) | 2014-08-08 | 2019-06-11 | Dipsol Chemicals Co., Ltd. | Copper-nickel alloy electroplating bath |
| JP2017197836A (en) * | 2016-04-30 | 2017-11-02 | 新日鐵住金株式会社 | Copper-nickel alloy material and mechanical component covered therewith |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980903 |