JP2001107284A - Boric acid-free nickel plating bath - Google Patents
Boric acid-free nickel plating bathInfo
- Publication number
- JP2001107284A JP2001107284A JP28184699A JP28184699A JP2001107284A JP 2001107284 A JP2001107284 A JP 2001107284A JP 28184699 A JP28184699 A JP 28184699A JP 28184699 A JP28184699 A JP 28184699A JP 2001107284 A JP2001107284 A JP 2001107284A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- plating bath
- nickel plating
- nickel
- boric acid
- 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.)
- Granted
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、ほう酸を含まない
ニッケルめっき浴に関する。The present invention relates to a nickel plating bath containing no boric acid.
【0002】[0002]
【従来の技術】ニッケルめっきは、各種めっきのアンダ
ーコートおよびトップコートとして装飾用、工業用に広
く使用されている。硫酸ニッケルおよび塩化ニッケルを
主成とするニッケルめっき浴のpH変動を少なくして、
めっき膜の光沢性、平滑性および柔軟性をよくするため
に、従来からほう酸がめっき浴に添加されている。めっ
き浴を交換するときには、めっき浴中のニッケルなどの
金属成分は回収されるが、ほう酸は回収困難で、排水中
に放出されている。しかし最近はほう素が排水規制の対
象になりつつある。現に一部の府県では規制が実施され
ている。2. Description of the Related Art Nickel plating is widely used for decorative and industrial purposes as an undercoat and a top coat for various platings. Reduce pH fluctuation of nickel plating bath mainly composed of nickel sulfate and nickel chloride,
Conventionally, boric acid has been added to a plating bath in order to improve the gloss, smoothness and flexibility of the plating film. When the plating bath is replaced, metal components such as nickel in the plating bath are recovered, but boric acid is difficult to recover and is discharged into wastewater. However, recently boron has become a target of wastewater regulations. In fact, some prefectures have regulations.
【0003】このためほう酸を含有しないニッケルめっ
き浴が望まれている。ほう酸を含有しないニッケルめっ
き浴としては、ほう酸の代わりに酢酸を用いたものが考
えられ、一部で実用化されているが、めっき膜の仕上が
り(光沢性、平滑性)の点で見劣りがし、作業場で臭気
が発生するなど作業環境が悪く、ほう酸と併用されてい
る程度である。For this reason, a nickel plating bath containing no boric acid has been desired. As a nickel plating bath containing no boric acid, a bath using acetic acid instead of boric acid is conceivable, and some of them have been put to practical use, but the finish (brightness and smoothness) of the plating film is inferior. However, the working environment is poor, such as the generation of odor in the workplace, and it is only used together with boric acid.
【0004】[0004]
【発明が解決しようとする課題】本発明の目的は、ほう
酸を用いた場合と仕上がりが変わらず、かつ作業環境が
良好なほう酸を用いないニッケルめっき浴を提供するこ
とである。SUMMARY OF THE INVENTION An object of the present invention is to provide a nickel plating bath which does not use boric acid and has a good finish and a good working environment as compared with the case of using boric acid.
【0005】[0005]
【課題を解決するための手段】本発明は、硫酸ニッケル
および塩化ニッケルを主成分とするニッケルめっき浴に
脂肪族ジカルボン酸を0.01〜0.5mol/L添加
したことを特徴とするほう酸を含まないニッケルめっき
浴である。SUMMARY OF THE INVENTION The present invention provides a method for producing boric acid, comprising adding an aliphatic dicarboxylic acid to a nickel plating bath containing nickel sulfate and nickel chloride as main components in an amount of 0.01 to 0.5 mol / L. It is a nickel plating bath that does not contain.
【0006】本発明に従えば、pH緩衝作用が大きく、
かつ不揮発性の物質として脂肪族ジカルボン酸が用いら
れる。ニッケルめっき浴におけるほう酸の役割は、pH
変動を低く抑えること、すなわちpH緩衝性である。p
H緩衝性を有する物質としては、カルボン酸があり、そ
の中でも解離度が小さく、水に対する溶解性があり、か
つ無臭性のものが要求される。この要求に脂肪族ジカル
ボン酸が合致する。モノカルボン酸は臭気が強く、また
トリカルボン酸は水に対する溶解度が低く、ヒドロキシ
酸やアミノ酸には錯体を形成し、いずれもニッケルめっ
き浴に用いることはできない。その他芳香族系のガルボ
ン酸も水に対する溶解性が低く、ニッケルめっき浴には
適さない。According to the present invention, the pH buffering action is large,
In addition, an aliphatic dicarboxylic acid is used as a non-volatile substance. The role of boric acid in nickel plating baths is pH
Keep the fluctuations low, that is, pH buffering. p
Substances having H buffering properties include carboxylic acids, and among them, those having a low degree of dissociation, solubility in water, and odorlessness are required. Aliphatic dicarboxylic acids meet this requirement. Monocarboxylic acids have a strong odor, and tricarboxylic acids have low solubility in water, and form complexes with hydroxy acids and amino acids, none of which can be used in a nickel plating bath. Other aromatic garbonic acids also have low solubility in water and are not suitable for nickel plating baths.
【0007】脂肪族ジカルボン酸の添加量は、めっき浴
1L当たり0.01〜0.5molである。0.01m
ol未満ではpH緩衝性が低く充分な効果が得られな
い。また0.5molを超えると、めっき浴中に充分に
溶解せず適さない。The amount of the aliphatic dicarboxylic acid added is 0.01 to 0.5 mol per liter of the plating bath. 0.01m
If it is less than ol, the pH buffering property is low and a sufficient effect cannot be obtained. If it exceeds 0.5 mol, it does not dissolve sufficiently in the plating bath and is not suitable.
【0008】また本発明は、前記脂肪族ジカルボン酸が
マロン酸、コハク酸、グルタル酸またはアジピン酸であ
ることを特徴とする。[0008] The present invention is also characterized in that the aliphatic dicarboxylic acid is malonic acid, succinic acid, glutaric acid or adipic acid.
【0009】本発明に従えば、ニッケルめっき液に添加
する脂肪族ジカルボン酸としては、マロン酸、コハク
酸、グルタル酸、アジピン酸が入手しやすく、かつ水に
対する溶解度が大きく好ましい。According to the present invention, malonic acid, succinic acid, glutaric acid, and adipic acid are easily available as the aliphatic dicarboxylic acid to be added to the nickel plating solution, and the solubility in water is preferable because of its high solubility.
【0010】また本発明は、前記脂肪族ジカルボン酸1
molとニッケル塩0.1〜1.0molとをよく混合
し、前記混合物をニッケルめっき浴に添加したことを特
徴とする。The present invention also relates to the aliphatic dicarboxylic acid 1
mol and nickel salt of 0.1 to 1.0 mol are mixed well, and the mixture is added to a nickel plating bath.
【0011】本発明に従えば、前記脂肪族ジカルボン酸
は、予めニッケル塩溶液と混合される。これによって脂
肪族ジカルボン酸はニッケル塩と反応して塩を形成し、
速やかにニッケルめっき浴に溶解する。脂肪族ジカルボ
ン酸は、解離度が小さいため、めっき浴に直接添加した
のでは安定して溶解するのに時間がかかるが、ニッケル
塩とすれば速やかに溶解する。According to the present invention, the aliphatic dicarboxylic acid is previously mixed with a nickel salt solution. This causes the aliphatic dicarboxylic acid to react with the nickel salt to form a salt,
Dissolves quickly in nickel plating bath. Since the aliphatic dicarboxylic acid has a low degree of dissociation, it takes a long time to stably dissolve if it is directly added to the plating bath, but if it is a nickel salt, it dissolves quickly.
【0012】[0012]
【発明の実施の形態】以下、実施例によって本発明をよ
り詳細に説明する 実施例1 マロン酸0.05molと、炭酸ニッケル0.02mo
lを含む溶液を作成し、これをほう酸を含まないWat
ts浴に加え、表1に示す本発明のニッケルめっき浴を
得、これに被めっき物として70×100mmの真鍮板
を陰極とし、陽極にニッケル板を用いるハルセル槽で温
度50℃、電流2Aで10分間ニッケルめっきを行っ
た。被めっき物は、光沢のある平滑なニッケルめっきが
得られめっき浴のpH変動もほとんどなかった。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Examples. Example 1 0.05 mol of malonic acid and 0.02 mol of nickel carbonate
A solution containing l.
In addition to the ts bath, a nickel plating bath of the present invention shown in Table 1 was obtained, and a 70 × 100 mm brass plate was used as a cathode and a nickel plate was used as an anode in a Hull cell bath at a temperature of 50 ° C. and a current of 2 A. Nickel plating was performed for 10 minutes. As for the object to be plated, bright and smooth nickel plating was obtained, and there was almost no fluctuation in pH of the plating bath.
【0013】[0013]
【表1】 [Table 1]
【0014】実施例2〜4、比較例 マロン酸の代わりに表2に示す脂肪族ジカルボン酸を用
いる以外は、実施例1と同じ本発明のニッケルめっき液
および従来のほう酸を用いたニッケルめっき浴を用い、
実施例1と同じ被めっき物を、同条件でニッケルめっき
を行った。その結果を実施例1とともに表2に示す。Examples 2 to 4, Comparative Example The same nickel plating solution of the present invention as in Example 1 except that an aliphatic dicarboxylic acid shown in Table 2 was used instead of malonic acid, and a conventional nickel plating bath using boric acid. Using
The same plating object as in Example 1 was plated with nickel under the same conditions. The results are shown in Table 2 together with Example 1.
【0015】[0015]
【表2】 [Table 2]
【0016】表2の結果から、本発明のニッケルめっき
浴は、従来から用いられているほう酸を含むニッケルめ
っき浴に比べて、めっき外観は変わらず、柔軟性も変わ
らず割れも生じなかった。またpHの変動もほう酸より
も少なく、ほう酸を用いた従来のニッケルめっき浴より
も優れているものと考えられる。From the results shown in Table 2, the nickel plating bath of the present invention showed no change in plating appearance, no change in flexibility, and no cracking, as compared with the conventional nickel plating bath containing boric acid. Further, the fluctuation of pH is smaller than that of boric acid, and it is considered that the pH is superior to that of a conventional nickel plating bath using boric acid.
【0017】[0017]
【発明の効果】以上のように本発明によるニッケルめっ
き浴は、ほう酸を用いた場合よりもpH緩衝作用が大き
く、かつ不揮発性のため作業環境が良好である。また本
発明のめっき浴を用いたニッケルめっきは、従来のほう
酸を含んだニッケルめっき浴を用いたニッケルめっきと
比較して遜色がない。As described above, the nickel plating bath according to the present invention has a larger pH buffering action than the case where boric acid is used, and has a good working environment because of its non-volatility. Further, nickel plating using the plating bath of the present invention is comparable to conventional nickel plating using a nickel plating bath containing boric acid.
Claims (3)
分とするニッケルめっき浴に脂肪族ジカルボン酸を0.
01〜0.5mol/L添加したことを特徴とするほう
酸を含まないニッケルめっき浴。1. An aliphatic dicarboxylic acid is added to a nickel plating bath containing nickel sulfate and nickel chloride as main components.
A nickel plating bath containing no boric acid, which is added in an amount of 0.01 to 0.5 mol / L.
ハク酸、グルタル酸またはアジピン酸であることを特徴
とする請求項1記載のほう酸を含まないニッケルめっき
浴。2. The nickel plating bath according to claim 1, wherein the aliphatic dicarboxylic acid is malonic acid, succinic acid, glutaric acid or adipic acid.
ケル塩0.1〜1.0molとをよく混合し、前記混合
物をニッケルめっき浴に添加したことを特徴とする請求
項1または2に記載のほう酸を含まないニッケルめっき
浴。3. The boric acid according to claim 1, wherein 1 mol of the aliphatic dicarboxylic acid and 0.1 to 1.0 mol of a nickel salt are mixed well, and the mixture is added to a nickel plating bath. Does not contain nickel plating bath.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28184699A JP4737790B2 (en) | 1999-10-01 | 1999-10-01 | Nickel plating bath without boric acid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28184699A JP4737790B2 (en) | 1999-10-01 | 1999-10-01 | Nickel plating bath without boric acid |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2001107284A true JP2001107284A (en) | 2001-04-17 |
JP4737790B2 JP4737790B2 (en) | 2011-08-03 |
Family
ID=17644832
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28184699A Expired - Fee Related JP4737790B2 (en) | 1999-10-01 | 1999-10-01 | Nickel plating bath without boric acid |
Country Status (1)
Country | Link |
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JP (1) | JP4737790B2 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2706132A1 (en) * | 2012-09-10 | 2014-03-12 | Dr. Hesse GmbH & Cie KG | Zinc-nickel electrolyte free of boric acid |
DE102013113129A1 (en) * | 2013-11-27 | 2015-05-28 | RIAG Oberflächentechnik AG | Process for the galvanic deposition of nickel and corresponding electrolyte |
CN105220184A (en) * | 2015-08-11 | 2016-01-06 | 模德模具(苏州工业园区)有限公司 | A kind of Nickel Electroforming Electrolyte Solution and preparation method thereof |
DE102014118614A1 (en) | 2014-12-15 | 2016-06-16 | Harting Kgaa | Boric acid-free nickel bath |
DE102014019753A1 (en) | 2014-12-15 | 2016-06-16 | Harting Kgaa | Borsaur-free nickel bath |
WO2016095896A1 (en) | 2014-12-15 | 2016-06-23 | Harting Ag & Co. Kg | Method for the electrolytic deposition of a nickel coating on an electric contact element in a boric-acid free electrolytic bath |
CN110785516A (en) * | 2017-06-23 | 2020-02-11 | 德国艾托特克公司 | Nickel electroplating bath for depositing decorative nickel coatings on substrates |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62103387A (en) * | 1985-07-29 | 1987-05-13 | C Uyemura & Co Ltd | Electroplating liquid |
JPS62278293A (en) * | 1986-05-26 | 1987-12-03 | C Uyemura & Co Ltd | Production of electronic parts |
JPS62278292A (en) * | 1986-05-26 | 1987-12-03 | C Uyemura & Co Ltd | Production of electronic parts |
JPH09310194A (en) * | 1995-12-29 | 1997-12-02 | Lucent Technol Inc | Nickel electroplating for nickel ferritic device |
JPH10212591A (en) * | 1997-01-29 | 1998-08-11 | Shinko Electric Ind Co Ltd | Nickel electroplating bath or nickel alloy electroplating bath and plating method using the bath |
-
1999
- 1999-10-01 JP JP28184699A patent/JP4737790B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62103387A (en) * | 1985-07-29 | 1987-05-13 | C Uyemura & Co Ltd | Electroplating liquid |
JPS62278293A (en) * | 1986-05-26 | 1987-12-03 | C Uyemura & Co Ltd | Production of electronic parts |
JPS62278292A (en) * | 1986-05-26 | 1987-12-03 | C Uyemura & Co Ltd | Production of electronic parts |
JPH09310194A (en) * | 1995-12-29 | 1997-12-02 | Lucent Technol Inc | Nickel electroplating for nickel ferritic device |
JPH10212591A (en) * | 1997-01-29 | 1998-08-11 | Shinko Electric Ind Co Ltd | Nickel electroplating bath or nickel alloy electroplating bath and plating method using the bath |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2706132A1 (en) * | 2012-09-10 | 2014-03-12 | Dr. Hesse GmbH & Cie KG | Zinc-nickel electrolyte free of boric acid |
DE102012216011A1 (en) | 2012-09-10 | 2014-03-13 | Dr. Hesse GmbH & Cie. KG | Boric acid-free zinc-nickel electrolyte |
DE102013113129A1 (en) * | 2013-11-27 | 2015-05-28 | RIAG Oberflächentechnik AG | Process for the galvanic deposition of nickel and corresponding electrolyte |
DE102014118614A1 (en) | 2014-12-15 | 2016-06-16 | Harting Kgaa | Boric acid-free nickel bath |
DE102014019753A1 (en) | 2014-12-15 | 2016-06-16 | Harting Kgaa | Borsaur-free nickel bath |
WO2016095896A1 (en) | 2014-12-15 | 2016-06-23 | Harting Ag & Co. Kg | Method for the electrolytic deposition of a nickel coating on an electric contact element in a boric-acid free electrolytic bath |
CN105220184A (en) * | 2015-08-11 | 2016-01-06 | 模德模具(苏州工业园区)有限公司 | A kind of Nickel Electroforming Electrolyte Solution and preparation method thereof |
CN110785516A (en) * | 2017-06-23 | 2020-02-11 | 德国艾托特克公司 | Nickel electroplating bath for depositing decorative nickel coatings on substrates |
Also Published As
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