JPH01259191A - Composition of tin-nickel alloy electroplating bath - Google Patents
Composition of tin-nickel alloy electroplating bathInfo
- Publication number
- JPH01259191A JPH01259191A JP8545788A JP8545788A JPH01259191A JP H01259191 A JPH01259191 A JP H01259191A JP 8545788 A JP8545788 A JP 8545788A JP 8545788 A JP8545788 A JP 8545788A JP H01259191 A JPH01259191 A JP H01259191A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- acid
- plating
- electroplating bath
- nickel
- 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
- 238000009713 electroplating Methods 0.000 title claims abstract description 11
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical group [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 title claims description 11
- 229910000990 Ni alloy Inorganic materials 0.000 title claims description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- 239000000956 alloy Substances 0.000 claims abstract description 6
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- DUYAAUVXQSMXQP-UHFFFAOYSA-N ethanethioic S-acid Chemical compound CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000007747 plating Methods 0.000 abstract description 25
- 235000019646 color tone Nutrition 0.000 abstract description 9
- 229910052718 tin Inorganic materials 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract 3
- 229910000967 As alloy Inorganic materials 0.000 abstract 1
- 229910020938 Sn-Ni Inorganic materials 0.000 abstract 1
- 229910008937 Sn—Ni Inorganic materials 0.000 abstract 1
- 150000001242 acetic acid derivatives Chemical class 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 150000003841 chloride salts Chemical class 0.000 abstract 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- ORUCCVLWOQSRMC-UHFFFAOYSA-M potassium;2,3,4,5,6,7-hexahydroxyheptanoate Chemical compound [K+].OCC(O)C(O)C(O)C(O)C(O)C([O-])=O ORUCCVLWOQSRMC-UHFFFAOYSA-M 0.000 description 1
- FIJPWGLOBMXXSF-UHFFFAOYSA-M potassium;2-hydroxyacetate Chemical compound [K+].OCC([O-])=O FIJPWGLOBMXXSF-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FMYOMWCQJXWGEN-UHFFFAOYSA-M sodium;2,3,4,5,6,7-hexahydroxyheptanoate Chemical compound [Na+].OCC(O)C(O)C(O)C(O)C(O)C([O-])=O FMYOMWCQJXWGEN-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はスズ−ニッケル合金電気めっき浴組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to tin-nickel alloy electroplating bath compositions.
〈従来の技術〉
スズ−ニッケル合金被膜層を形成させる電気めっき浴と
する電着方法としては各種のものか従来より知られてい
る。<Prior Art> Various electrodeposition methods have been known in the art for forming an electroplating bath for forming a tin-nickel alloy coating layer.
例えばティー、エル、ラマチャー、電気化学２５．５７
３、昭３２記載、ニー、イー、タビニス（Ａ、Ｅ。For example, T, L, Ramachar, Electrochemistry 25.57
3, written in 1963, Nie, E., Tabinis (A, E.
Ｄａｖｉｅｓ ）アール エム、アンクレロ（ＲＭ 。Davies) RM, Anclello (RM).
Ａｎｇｌｅｏ ） −ｈランス、インスト、メタルフイ
ニイシンク ３３２７７１９５［ｉ（Ｔｒａｎｓ、Ｉｎ
５ｔ、Ｍｅｔａｌ Ｆｉｎｉｓｔ＋−ｉｎｇ ）記載、
ニー、フレナー（Δ、Ｂｒｅｎｅｒ ）−エレクトロチ
ポジション オツ アロイ 第２巻３３９１９５３（Ｅ
ｌｅｃｔｒｏｄｅｐｏｓｉｔｉｏｎ ｏｆ Ａロｏｙ
）記載の方法等がある。Angleo) -h Lance, Instrument, Metal Fine Sync 33277195 [i(Trans, In
5t, Metal Finist+-ing) description,
Brener (Δ, Brener) - Electrochiposition Otsu Alloy Volume 2 3391953 (E
Electrodeposition of Arooy
) There is a method of description, etc.
そしてこれらの方法により生成せるスズ−ニッケル合金
被膜は耐食性、耐摩耗性にすぐれ、又その色調は帯積白
色である。The tin-nickel alloy coating produced by these methods has excellent corrosion resistance and abrasion resistance, and its color tone is banded white.
〈発明か解決しようとする課題〉
然しこのスズ−ニッケル合金の色の［１］か広くなれは
、装飾的価値もさらに増加し、そのためそれらの用途も
更に拡大か可能となる。<Problem to be Solved by the Invention> However, if the color [1] of this tin-nickel alloy is widened, the decorative value will further increase, and therefore, their uses can be further expanded.
〈課題を解決するための手段〉
本発明者らは種々研究の結果、チオグリコール酸、メル
カプトコハク酸又はエタンチオ酸を浴中に存在させた電
気めっき浴を用いて電気めっきを行うことにより生成さ
せた被膜は、その成分やめっき条件等を変化させること
により深青色、褐色、黒色の別々な色調を有することを
確認して本発明を完成した。<Means for Solving the Problems> As a result of various studies, the present inventors have found that thioglycolic acid, mercaptosuccinic acid, or ethanethioic acid can be produced by electroplating using an electroplating bath in which they are present. The present invention was completed by confirming that the coated film has different color tones of deep blue, brown, and black by changing its components, plating conditions, etc.
即ち本発明は（イ）合金被膜形成物質であるスズ及びニ
ッケルの塩化物、硫酸塩又は酢酸塩、（ロ）チオグリコ
ール酸、メルカプトコハク酸又はエタンチオ酸、（ハ）
導電性塩を実質的主成分として含有するスズ−ニッケル
合金電気めっき浴組成物に関する。That is, the present invention provides (a) chloride, sulfate or acetate of tin and nickel which are alloy film forming substances, (b) thioglycolic acid, mercaptosuccinic acid or ethanethioic acid, (c)
The present invention relates to a tin-nickel alloy electroplating bath composition containing a conductive salt as a substantial main component.
なおスズ塩は、二価のスズは浴中て酸化され易いのて四
価のスズか好ましい。スズ及びニッケルの塩化物、硫酸
塩、又は酢酸塩の濃度は、それぞれ金属スズ、金属ニッ
ケルとして３〜５０ｇ／Ｕ、２〜２５ｇ／ｇである。As the tin salt, tetravalent tin is preferable because divalent tin is easily oxidized in a bath. The concentrations of tin and nickel chloride, sulfate, or acetate are 3 to 50 g/U and 2 to 25 g/g as metal tin and metal nickel, respectively.
チオグリコール酸、メルカプトコハク酸又はエタンチオ
酸のめっき浴中の濃度は目的とする色調によって異なる
か５〜１２０ ｇ／ｆｌの範囲であることか実用的に必
要である。The concentration of thioglycolic acid, mercaptosuccinic acid, or ethanethioic acid in the plating bath varies depending on the desired color tone, or is practically required to be in the range of 5 to 120 g/fl.
本発明のめっき浴組成物により生成せるめっき被膜の色
調は、めっき浴の組成濃度、めっき条件等により変化す
る。The color tone of the plating film produced by the plating bath composition of the present invention changes depending on the composition concentration of the plating bath, plating conditions, etc.
例えは法度以外の条件を同一とすると、黒色被膜を得、
濃度か小のときは褐色被膜となり、濃度かこれらの中間
の場合は鮮かな深青色か得られる。導電性塩としては公
知のもの、即ち塩化ナトリウム、塩化カリウム、硫酸カ
リウム、硫酸アンモニウム、塩化アンモニウム等か用い
られる。その濃度も公知の範囲、即ち１５〜３５０ｇ／
ｇ程度か用いられる。For example, if the conditions other than legality are the same, a black film will be obtained,
When the concentration is low, a brown coating is obtained, and when the concentration is between these, a bright deep blue color is obtained. As the conductive salt, known ones such as sodium chloride, potassium chloride, potassium sulfate, ammonium sulfate, ammonium chloride, etc. can be used. Its concentration is also within the known range, i.e. 15-350g/
Approximately 100 g is used.
さらに錯イオン形成剤をめっき浴中に含有させることに
より、生成めっき被膜は極めて安定化する。実用的に好
適な錯イオン形成剤としてはヒドロキシ酢酸、ヒドロキ
シ酢酸カリウム、クエン酸、クエン酸カリウム、ヘプト
ン酸ナトリウム、ヘプトン酸カリウムを例示てきる。そ
してそれらの浴中の実用的な濃度は５０ｇ／Ｕ〜３００
ｇ／ｇ の範囲である。Furthermore, by including a complex ion forming agent in the plating bath, the resulting plating film is extremely stabilized. Practically suitable complex ion forming agents include hydroxyacetic acid, potassium hydroxyacetate, citric acid, potassium citrate, sodium heptonate, and potassium heptonate. And their practical concentration in the bath is 50g/U~300
g/g range.
次に本発明の電気めっき浴組成物のめっき条件を示ず。Next, plating conditions for the electroplating bath composition of the present invention are not shown.
即ち浴温は２５°〜５５°Ｃ１陰極電流密度は０．１
Ａ／ｄｍ２〜ｌ Ａ／ｄｍ２．陽極電流密度は０．１
Ａ／ｄｍ２〜０．５ Ａ／ｄｍ２． ｐＨは３．５〜８
．０の範囲か好ましい。That is, the bath temperature is 25° to 55°C, the cathode current density is 0.1
A/dm2~l A/dm2. Anode current density is 0.1
A/dm2~0.5 A/dm2. pH is 3.5-8
．． A range of 0 is preferred.
浴温か高いとスズ−ニッケル合金被膜の本来の色調であ
る帯積色となり、低いと光沢のある被膜か得られない。If the bath temperature is high, the tin-nickel alloy coating will have a banded color, which is the original color tone, and if the bath temperature is low, a glossy coating will not be obtained.
陰極電流密度か大であると高電流密度部に焦げか発生、
あるいはその部門か帯積白色となり、均一な色調の被膜
をうることか不能となる。又陰極電流密度か小であると
めっき時間か極めて長くなり実用的てない。If the cathode current density is high, charring will occur in the high current density area.
Otherwise, the area becomes banded and white, making it impossible to form a film with a uniform color tone. Also, if the cathode current density is low, the plating time will be extremely long, making it impractical.
さらにｐｕか酸性側に、即ち小となると発色か充分てな
く、灰白色となり、又アルカリ側に、即ち小となるとニ
ッケルのみ析出し、合金被膜か得られない。Furthermore, if the pu value is on the acidic side, that is, small, the color will not be sufficiently developed and the color will become grayish white, and if it is on the alkaline side, that is, small, only nickel will precipitate, making it impossible to obtain an alloy coating.
陽極としては通常のめっき操作に用いられる黒鉛やフェ
ライト等の不溶性陽極、さらに被膜成分であるスズ、ニ
ッケルそのものを用いることもてきる。As the anode, insoluble anodes such as graphite and ferrite used in ordinary plating operations, and tin and nickel themselves, which are coating components, can also be used.
実施例： 次に実施例により本発明を説明する。Example: Next, the present invention will be explained with reference to examples.
即ち本発明のめっき浴組成物を作成し１０ｃｕ＋ｘ１０
ｃｍＸ Ｏ，５ｍｍのニッケルめっき被膜を有するしん
ちゅう板にスズ−ニッケル被膜を、カソードロッカ一方
式法により生成させた。That is, the plating bath composition of the present invention was prepared and 10 cu + x 10
A tin-nickel coating was produced on a brass plate with a nickel plating coating of cmX O, 5 mm by a cathode rocker one-way method.
カソードロッカ一方式は陰極移動距離
’ ９０ｍｍ／１回、陰極移動回数１６回／分という
条件を採用した。For the one-type cathode rocker, conditions were adopted in which the cathode movement distance was 90 mm/time and the cathode movement number was 16 times/min.
次にめっき浴組成、めっき条件、生成めっき被膜の色調
を法衣に示す。Next, the plating bath composition, plating conditions, and color tone of the resulting plating film are shown on the robe.
生成せるめっき被膜にクロメート処理を施し、ＪＩＳＺ
２３７１の塩水噴霧試験を行ったか、めっき被膜に変
化はなかった。Chromate treatment is applied to the plating film that is generated, and JISZ
2371 was subjected to a salt spray test, and there was no change in the plating film.
〈発明の効果〉
本発明により、めっき浴の成分種類は同して、その成分
量をかえることにより異なった色調の美麗なスズ−ニッ
ケルめっき被膜の形成か可能となった。<Effects of the Invention> According to the present invention, it has become possible to form beautiful tin-nickel plating films with different tones by changing the amounts of the components while keeping the same types of components in the plating bath.
Claims (1)
塩化物、硫酸塩又は酢酸塩、 （ロ）チオグリコール酸、メルカプトコハク酸およびエ
タンチオ酸、 （ハ）導電性塩、 を実質的主成分として含有するスズ−ニッケル合金電気
めっき浴組成物。 ２）合金被膜形成物質はスズとして３〜５０ｇ／ｌ、ニ
ッケルとして２〜２５ｇ／ｇ含まれる請求項第１項のス
ズ−ニッケル合金電気めっき浴組成物。 ３）（ロ）成分の含有量は５〜１２０ｇ／ｇである請求
項第１項のスズ−ニッケル合金電気めっき浴組成物。[Claims] 1) (a) Chloride, sulfate or acetate of tin and nickel which are alloy film forming substances, (b) thioglycolic acid, mercaptosuccinic acid and ethanethioic acid, (c) conductive salts , A tin-nickel alloy electroplating bath composition containing as a substantial main component. 2) The tin-nickel alloy electroplating bath composition according to claim 1, wherein the alloy film-forming substance contains 3 to 50 g/l as tin and 2 to 25 g/l as nickel. 3) The tin-nickel alloy electroplating bath composition according to claim 1, wherein the content of component (b) is 5 to 120 g/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8545788A JPH01259191A (en) | 1988-04-08 | 1988-04-08 | Composition of tin-nickel alloy electroplating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8545788A JPH01259191A (en) | 1988-04-08 | 1988-04-08 | Composition of tin-nickel alloy electroplating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01259191A true JPH01259191A (en) | 1989-10-16 |
| JPH0343358B2 JPH0343358B2 (en) | 1991-07-02 |
Family
ID=13859410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8545788A Granted JPH01259191A (en) | 1988-04-08 | 1988-04-08 | Composition of tin-nickel alloy electroplating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01259191A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5332347A (en) * | 1976-09-08 | 1978-03-27 | Tokyo Shibaura Electric Co | Secondary alkaline battery |
-
1988
- 1988-04-08 JP JP8545788A patent/JPH01259191A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5332347A (en) * | 1976-09-08 | 1978-03-27 | Tokyo Shibaura Electric Co | Secondary alkaline battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0343358B2 (en) | 1991-07-02 |
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