JPH0321639B2 - - Google Patents
Info
- Publication number
- JPH0321639B2 JPH0321639B2 JP8545688A JP8545688A JPH0321639B2 JP H0321639 B2 JPH0321639 B2 JP H0321639B2 JP 8545688 A JP8545688 A JP 8545688A JP 8545688 A JP8545688 A JP 8545688A JP H0321639 B2 JPH0321639 B2 JP H0321639B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- nickel
- plating
- bath composition
- electroplating bath
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 238000009713 electroplating Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 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
- 239000000126 substance Substances 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 description 19
- 239000010408 film Substances 0.000 description 13
- 235000019646 color tone Nutrition 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 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
- 238000004070 electrodeposition Methods 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
- 239000004615 ingredient Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- -1 2-amino-3-mercaptopropionic acid 2,2'-diamino-3,3'-dithiodipropionic acid 2-amino-4-methylthiobutyric acid Chemical compound 0.000 description 1
- 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
- 239000003086 colorant 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 group [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
- 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
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
＜産業上の利用分野＞
本発明はスズ−ニツケル合金電気めつき浴組成
物に関する。
＜従来の技術＞
スズ−ニツケル合金被膜層を形成させる電気め
つき浴とする電着方法としては各種のものが従来
より知られている。
例えばテイー．エル．ラマチヤー、電気化学
25、573、昭32記載、エー．イー．ダビエス（A.
E.Davies）アール エム．アングレロ（RM.
Angleo）−トランス、インスト、メタルフイニイ
シング33 277 1956（Trans、Inst、Metal
Finishing）記載、エー．ブレナー（A.Brener）
−エレクトロデポジシヨン オブ アロイ 第２
巻339 1963（Electrodeposition of Alloy）記載
の方法等がある。
そしてこれら方法により生成せるスズ−ニツケ
ル合金被膜は耐食性、耐摩耗性にすぐれ、又その
色調は帯桃白色である。
＜発明が解決しようとする課題＞
然しこのスズ−ニツケル合金の色の巾が広くな
れば、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が可能となる。
＜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、Ｎ−Ｃ−Ｃ−Ｃ
−Ｓ又はＮ−Ｃ−Ｃ−Ｓ結合を有する有機化合物
を浴中に存在させた場合、浴中の成分やめつき条
件等を変化するのみで、その浴を用いることによ
り生成せる電気めつき被膜は褐色、深青色、黒色
な別々な色調を有することを確認して本発明を完
成した。
即ち本発明は(イ)合金被膜形成物質であるスズ及
びニツケルの塩化物、硫酸塩又は酢酸塩、(ロ)Ｎ−
Ｃ−Ｃ−Ｃ−Ｓ又はＮ−Ｃ−Ｃ−Ｓ結合を有する
有機化合物、(ハ)導電性塩を実質的主成分として含
有するスズ−ニツケル合金電気めつき浴組成物に
関する。
なおスズ塩は、二価のスズは浴中で酸化され易
いので四価のスズが好ましい。スズ及びニツケル
の塩化物、硫酸塩、又は酢酸塩の濃度は、それぞ
れ金属スズ、金属ニツケルとして３〜50ｇ／、
２〜25ｇ／である。
Ｎ−Ｃ−Ｃ−Ｃ−Ｓ又はＮ−Ｃ−Ｃ−Ｓ結合を
有する有機化合物としては、
２−アミノ−３−メルカプトプロピオン酸
２，2′−ジアミノ−３，3′−ジチオジプロピオ
ン酸
２−アミノ−４−メチルチオ酪酸
が好適に用いられる。
これらの有機化合物のめつき浴中の濃度は目的
とする被膜の色調によつて異なるが５〜120ｇ／
の範囲であることが実用的に必要である。
本発明のめつき浴組成物により生成せるめつき
被膜の色調は、めつき浴の組成の濃度、めつき条
件等により、次のように変化する。
例えば濃度以外の条件を同一にすると濃度が大
のときは、黒色被膜を得、濃度が小のときは褐色
被膜となり、濃度がこれらの中間の場合は鮮かな
深青色が得られる。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
が用いられる。その濃度も公知の範囲、即ち15〜
350ｇ／程度が用いられる。
さらに鎖イオン形成剤をめつき浴中に含有させ
ることにより、生成めつ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できる。そしてそれら
の浴中の実用的な濃度は50ｇ／〜300ｇ／の
範囲である。
次に本発明の電気めつき浴組成物のめつき条件
を示す。即ち浴温は25°〜55℃、陰極電流密度は
0.1A／ｄm2〜1A／ｄm2、陰極電流密度は0.1A／
ｄm2〜0.5A／ｄm2、PHは3.5〜8.0の範囲が好まし
い。
浴温が高いとスズ−ニツケル合金被膜の本来の
色調である帯桃色となり、低いと光沢のある被膜
が得られない。陰極電流密度が大であると高電流
密度部に焦げが発生、あるいはその部門が帯桃白
色となり、均一な色調の被膜をうることが不能と
なる。又陰極電流密度が小であるとめつき時間が
極めて長くなり実用的でない。
さらにPHが酸性側に、即ち小となると発色が充
分でなく、灰白色となり、又アルカリ側に、即ち
小となるとニツケルのみ析出し、合金被膜が得ら
れない。
陽極としては通常のめつき操作に用いられる黒
鉛やフエライト等の不溶性陽極、さらに被膜成分
であるスズ、ニツケルそのものを用いることもで
きる。
実施例
次に実施例により本発明を説明する。
即ち本発明のめつき浴組成物を作成し10cm×10
cm×0.5mmのニツケルめつき被膜を有するしんち
ゆう板にスズ−ニツケル被膜を、カソードロツカ
ー方式法により生成させた。
カソードロツカー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。
次にめつき浴組成、めつき条件、生成めつき被
膜の色調を次表に示す。
<Industrial Application Field> The present invention relates to a tin-nickel alloy electroplating bath composition. <Prior Art> Various types of electrodeposition methods have been known in the art for using electroplating baths to form tin-nickel alloy coating layers. For example, Tei. L. ramacharya, electrochemistry
25, 573, written in 1963, A. E. Davies (A.
E.Davies) R.M. Angrero (RM.
Angleo) - Trance, Instrument, Metal Finishing 33 277 1956 (Trans, Instrument, Metal
Finishing) description, A. Brener (A. Brener)
- Electrodeposition of Alloy 2nd
There are methods described in Vol. 339 1963 (Electrodeposition of Alloy). The tin-nickel alloy coatings produced by these methods have excellent corrosion resistance and abrasion resistance, and are pinkish white in color. <Problems to be Solved by the Invention> However, if the range of colors of these tin-nickel alloys were to be widened, their decorative value would further increase, and therefore their uses could be further expanded. <Means for solving the problem> As a result of various studies, the present inventors have found that N-C-C-C
When an organic compound having -S or N-C-C-S bonds is present in the bath, an electroplated film can be produced by using the bath by simply changing the components in the bath and the plating conditions. The present invention was completed by confirming that the color has different color tones of brown, deep blue, and black. That is, the present invention provides (a) chloride, sulfate or acetate of tin and nickel which are alloy film forming substances, and (b) N-
The present invention relates to a tin-nickel alloy electroplating bath composition containing as a substantial main component an organic compound having a C-C-C-S or N-C-C-S bond and (c) a conductive salt. Note that as the tin salt, tetravalent tin is preferable since divalent tin is easily oxidized in a bath. The concentration of tin and nickel chloride, sulfate, or acetate is 3 to 50 g/metal tin and metal nickel, respectively.
It is 2-25g/. As an organic compound having N-C-C-C-S or N-C-C-S bond, 2-amino-3-mercaptopropionic acid 2,2'-diamino-3,3'-dithiodipropionic acid 2-amino-4-methylthiobutyric acid is preferably used. The concentration of these organic compounds in the plating bath varies depending on the color tone of the desired coating, but is 5 to 120 g/
It is practically necessary that the value be within the range of . The color tone of the plating film produced by the plating bath composition of the present invention changes as follows depending on the concentration of the plating bath composition, plating conditions, etc. For example, when conditions other than density are the same, when the density is high, a black film is obtained, when the density is low, a brown film is obtained, and when the density 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. are used. Its concentration is also within a known range, i.e. 15~
About 350g/is used. Furthermore, by including a chain 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,
An example is potassium heptonate. And their practical concentration in the bath ranges from 50g/ to 300g/. Next, the plating conditions for the electroplating bath composition of the present invention will be shown. That is, the bath temperature is 25° to 55°C, and the cathode current density is
0.1A/dm 2 ~1A/dm 2 , cathode current density 0.1A/dm 2
dm 2 to 0.5 A/dm 2 and PH are preferably in the range of 3.5 to 8.0. If the bath temperature is high, the tin-nickel alloy film will have a pinkish color, which is the original color tone, and if the bath temperature is low, a glossy film will not be obtained. If the cathode current density is high, scorching occurs in the high current density area, or the area becomes pinkish white, making it impossible to obtain a film with a uniform color tone. Furthermore, if the cathode current density is low, the plating time becomes extremely long, which is not practical. Further, when the pH is on the acidic side, that is, low, the color development is not sufficient and the color becomes grayish white, and when the pH is on the alkaline side, that is, low, only nickel is precipitated, and an alloy film cannot be obtained. 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. Examples Next, the present invention will be explained by examples. That is, the plating bath composition of the present invention was prepared and a 10 cm x 10
A tin-nickel coating was produced on a brass plate having a nickel plating coating of cm x 0.5 mm by a cathode rocker method. The cathode rocker method has a cathode movement distance of 90mm/1.
The conditions were that the cathode was moved 16 times/min. Next, the plating bath composition, plating conditions, and color tone of the produced plating film are shown in the table below.
【表】【table】
【表】
生成せるめつき被膜にクロメート処理を施し、
JISZ2371の塩水噴霧試験を行つたが、めつき被
膜に変化はなかつた。
＜発明の効果＞
本発明により、めつき浴の成分種類は同じで、
その成分量をかえることにより異なつた色調の美
麗なスズ−ニツケルめつき被膜の形成が可能とな
つた。[Table] Chromate treatment is applied to the generated thin film,
A JISZ2371 salt water spray test was conducted, but there was no change in the plating film. <Effects of the Invention> According to the present invention, the types of ingredients in the plating bath are the same,
By changing the amount of the ingredients, it became possible to form beautiful tin-nickel plating films with different tones.
Claims (1)
ルの塩化物、硫酸塩又は酢酸塩、 (ロ) Ｎ−Ｃ−Ｃ−Ｃ−Ｓ又はＮ−Ｃ−Ｃ−Ｓ結合
を有する有機化合物、 (ハ) 導電性塩、 を実質的主成分として含有するスズ−ニツケル合
金電気めつき浴組成物。 ２ 合金被膜形成物質はスズとして３〜50ｇ／
、ニツケルとして２〜25ｇ／含まれる請求項
第１項のスズ−ニツケル合金電気めつき浴組成
物。 ３ 有機化合物含有量は５〜120／である請求
項第１項のスズ−ニツケル合金電気めつき浴組成
物。[Scope of Claims] 1 (a) Chloride, sulfate or acetate of tin and nickel which are alloy film forming substances, (b) N-C-C-C-S or N-C-C-S bond A tin-nickel alloy electroplating bath composition containing as a substantial main component an organic compound having the following: (iii) a conductive salt. 2 The alloy film forming substance is 3 to 50 g/tin as tin.
2. The tin-nickel alloy electroplating bath composition according to claim 1, wherein the tin-nickel alloy electroplating bath composition contains 2 to 25 g/nickel. 3. The tin-nickel alloy electroplating bath composition according to claim 1, wherein the content of organic compounds is from 5 to 120%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8545688A JPH01259190A (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 |
|---|---|---|---|
| JP8545688A JPH01259190A (en) | 1988-04-08 | 1988-04-08 | Composition of tin-nickel alloy electroplating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01259190A JPH01259190A (en) | 1989-10-16 |
| JPH0321639B2 true JPH0321639B2 (en) | 1991-03-25 |
Family
ID=13859385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8545688A Granted JPH01259190A (en) | 1988-04-08 | 1988-04-08 | Composition of tin-nickel alloy electroplating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01259190A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3433291B2 (en) * | 1999-09-27 | 2003-08-04 | 石原薬品株式会社 | Tin-copper-containing alloy plating bath, tin-copper-containing alloy plating method, and article formed with tin-copper-containing alloy plating film |
-
1988
- 1988-04-08 JP JP8545688A patent/JPH01259190A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01259190A (en) | 1989-10-16 |
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