JPH09202990A - Copper plating liquid - Google Patents
Copper plating liquidInfo
- Publication number
- JPH09202990A JPH09202990A JP4198796A JP4198796A JPH09202990A JP H09202990 A JPH09202990 A JP H09202990A JP 4198796 A JP4198796 A JP 4198796A JP 4198796 A JP4198796 A JP 4198796A JP H09202990 A JPH09202990 A JP H09202990A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- plating liquid
- copper plating
- plating
- plating solution
- 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
【０００１】[0001]
【発明の属する技術分野】本発明は銅メッキ液、特にノ
ーシアン銅メッキ液に係るものであり、亜鉛，アルミニ
ウム，鉄など、酸性の銅メッキ液では密着しにくい金属
の表面上に、銅メッキを密着性よくメッキする為の浴に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper plating solution, in particular, a non-cyan copper plating solution, in which copper plating is performed on the surface of a metal such as zinc, aluminum or iron which is difficult to be adhered by an acidic copper plating solution. It relates to a bath for plating with good adhesion.
【０００２】[0002]
【従来の技術】亜鉛，アルミニウム，鉄などは、耐蝕性
を向上させるため、その表面上に、銅，ニッケル，クロ
ム，金などがメッキされている。これらの金属に銅メッ
キを施すには、従来では、シアン化銅メッキが行われて
いた。2. Description of the Related Art Zinc, aluminum, iron, etc. are plated with copper, nickel, chromium, gold, etc. on their surfaces in order to improve their corrosion resistance. In order to apply copper plating to these metals, copper cyanide plating has been conventionally performed.
【０００３】[0003]
【発明が解決しようとする課題】しかし、シアン系の銅
メッキは猛毒であり、排水処理をするのに多大の費用と
長い処理時間を要していた。However, the cyan copper plating is extremely poisonous, and it requires a great deal of expense and a long treatment time to treat the waste water.
【０００４】本発明は、上記従来技術に鑑み、猛毒のシ
アンを使用することなく、密着性が良好で且つ外観の優
れた銅メッキを実現することのできる銅メッキ液を提供
することを目的とする。In view of the above prior art, it is an object of the present invention to provide a copper plating solution capable of realizing copper plating having good adhesion and excellent appearance without using highly poisonous cyanide. To do.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決する本発
明は、銅イオンを５〜２００ｇ／ｌ含有することを特徴
とする。また、ｐＨが５以上であることを特徴とする。
また、銅とのキレート安定度定数が２．０以上である錯
化物を、銅と等モル以上含有することを特徴とする。更
に、電導塩として、硫酸塩，炭酸塩，硝酸塩，塩化物，
リン酸塩，水酸化アルカリの中から少なくとも１つを含
有し、しかも、含有した各電導塩の各濃度を１〜２００
ｇ／ｌとしたことを特徴とする。The present invention for solving the above-mentioned problems is characterized by containing copper ions in an amount of 5 to 200 g / l. Further, it is characterized in that the pH is 5 or more.
In addition, a complex compound having a chelate stability constant with copper of 2.0 or more is contained in an amount of equimolar or more with copper. Furthermore, as conductive salts, sulfates, carbonates, nitrates, chlorides,
It contains at least one of phosphate and alkali hydroxide, and the concentration of each conductive salt contained is 1 to 200
It is characterized by being set to g / l.
【０００６】[0006]
【発明の実施の形態】銅塩に対する錯化剤を銅と等モル
以上含有し、且つ、電導塩を１〜２００ｇ／ｌ含む本発
明の銅メッキ液によれば、シアンを用いることなく、密
着性が良好で外観の優れた銅メッキができる。BEST MODE FOR CARRYING OUT THE INVENTION According to the copper plating solution of the present invention containing a complexing agent for a copper salt in an amount of equimolar or more to copper and containing a conductive salt in an amount of 1 to 200 g / l, adhesion can be achieved without using cyan Copper plating with good properties and excellent appearance can be formed.
【０００７】ノーシアン銅塩，錯化剤，電導塩からなる
銅メッキ液は、亜鉛，アルミニウム，鉄材に対してすぐ
れた密着性を示し、また、光沢もよいので、装身具関係
の下地メッキとして最適である。A copper plating solution consisting of a non-cyan copper salt, a complexing agent, and a conductive salt exhibits excellent adhesion to zinc, aluminum and iron materials, and also has a good luster, so it is most suitable as an undercoat for accessories. is there.
【０００８】本発明の銅メッキ液において、仮に、銅イ
オンが５ｇ／ｌ未満では、つきまわりが悪く密着性もよ
くない。また銅イオンが２００ｇ／ｌ以上では錯化剤を
加えたときに沈澱を生ずる。ｐＨが５未満では、つきま
わりが悪く密着性も悪い。錯化剤が銅と等モル以下では
ｐＨを上げたときに沈澱を生ずる。また、キレート安定
度定数が２．０以下では電解したときに液が分解する。In the copper plating solution of the present invention, if the copper ion content is less than 5 g / l, the throwing power is poor and the adhesion is poor. When the copper ion content is 200 g / l or more, precipitation occurs when the complexing agent is added. When the pH is less than 5, the throwing power is poor and the adhesion is poor. If the complexing agent is less than equimolar to copper, precipitation will occur when the pH is raised. If the chelate stability constant is 2.0 or less, the liquid decomposes when electrolyzed.
【０００９】電導塩濃度が１ｇ／ｌ以下では電解電圧が
高くなり、銅が析出しにくくなり、電導塩濃度が２００
ｇ／ｌ以上では建浴コストが高くなり、また、溶解度の
関係で沈澱しやすくなる。錯化剤を電導塩をかねて多く
入れる方法もあるが、やはり建浴コストが高くなる。When the conductive salt concentration is 1 g / l or less, the electrolysis voltage becomes high, copper is less likely to deposit, and the conductive salt concentration is 200
If it is more than g / l, the bath cost is high, and it is likely to precipitate due to the solubility. There is also a method of adding a large amount of complexing agent to serve as a conductive salt, but this also increases the bath cost.
【００１０】[0010]
【実施例】以下本発明を実施例によってさらに詳細に説
明する。EXAMPLES The present invention will now be described in more detail with reference to Examples.
【００１１】＜実施例１＞硫酸銅１０ｇ／ｌ，クエン酸
ナトリウム５０ｇ／ｌ，硫酸ナトリウム１００ｇ／ｌを
水にとかし、カセイソーダでｐＨ７．０に調整した。常
法により前処理を施した２０ｍｍ×２０ｍｍの鉄板に５
０℃，１Ａ／ｄｍ２で３分間メッキした。さらに光沢硫
酸銅メッキを１０μｍ，光沢ニッケルメッキを５μｍ施
した。<Example 1> 10 g / l of copper sulfate, 50 g / l of sodium citrate, and 100 g / l of sodium sulfate were dissolved in water and adjusted to pH 7.0 with caustic soda. 5 mm on a 20 mm x 20 mm iron plate that has been pretreated by a conventional method
It was plated at 0 ° C. and 1 A / dm 2 for 3 minutes. Further, bright copper sulfate plating was applied to 10 μm and bright nickel plating was applied to 5 μm.
【００１２】上記の処理により出来上ったメッキ面は光
沢があり９０°におりまげてもメッキのハクリはなかっ
た。The plated surface produced by the above treatment was glossy and there was no peeling of the plating even if it was bent at 90 °.
【００１３】＜実施例２＞硝酸銅５０ｇ／ｌ，酒石酸カ
リウム１５０ｇ／ｌ，硝酸カリウム３０ｇ／ｌを水にと
かし、カセイカリでｐＨを１０に調整した。２５ｍｍ×
２５ｍｍの亜鉛板を常法により前処理を施し、前記メッ
キ液を４０℃に加熱し、２Ａ／ｄｍ２で５分間メッキし
た。さらに光沢硫酸銅メッキを１５μｍ，光沢ニッケル
メッキを５μｍ，クロムメッキを０．２μｍ施した。Example 2 50 g / l of copper nitrate, 150 g / l of potassium tartrate and 30 g / l of potassium nitrate were dissolved in water, and the pH was adjusted to 10 with caustic. 25 mm x
A 25 mm zinc plate was pretreated by a conventional method, the plating solution was heated to 40 ° C., and plated at 2 A / dm 2 for 5 minutes. Further, bright copper sulfate plating was applied to 15 μm, bright nickel plating was applied to 5 μm, and chromium plating was applied to 0.2 μm.
【００１４】上記の処理により出来上ったメッキ面は光
沢があり９０°におりまげてもメッキのハクリはなかっ
た。The plated surface produced by the above treatment was glossy and there was no peeling of the plating even if it was bent at 90 °.
【００１５】＜実施例３＞硫酸銅３０ｇ／ｌ，ＥＤＴＡ
（エチレンジアミンテトラ酢酸）・２Ｎａ １００ｇ／
ｌ，炭酸ソーダ５０ｇ／ｌを水にとかし、カセイソーダ
でｐＨを８．５に調整した。亜鉛ダイキャスト製のベル
ト用バックルを研磨した後、常法により前処理を施し、
４５℃に加熱した前記メッキ液中で３Ａ／ｄｍ２，３分
間メッキした。さらに光沢硫酸銅メッキを１２μｍ，光
沢ニッケルメッキを１０μｍ，金メッキを１μｍ施し
た。Example 3 Copper sulfate 30 g / l, EDTA
(Ethylenediaminetetraacetic acid) ・ 2Na 100 g /
1 and 50 g / l of sodium carbonate were dissolved in water, and the pH was adjusted to 8.5 with caustic soda. After polishing the buckle for belt made of zinc die-cast, pretreatment is performed by the usual method,
Plating was performed for 3 minutes at 3 A / dm 2 in the plating solution heated to 45 ° C. Further, bright copper sulfate plating was applied to 12 μm, bright nickel plating was applied to 10 μm, and gold was applied to 1 μm.
【００１６】このベルト用バックルをアンモニアバッキ
試験２４時間，人工汗試験２４時間，おりまげ試験を夫
々各２ピースづつ行ったが、いずれも異常なかった。This belt buckle was subjected to an ammonia backing test for 24 hours, an artificial sweat test for 24 hours, and a flapping test for each two pieces, each showing no abnormality.
【００１７】尚これらの試験に使用した試験液は次のと
おりである。The test solutions used in these tests are as follows.
【００１８】（１）人工汗試験における人工汗組成は、
食塩９．９ｇ／ｌ，尿素１．７ｇ／ｌ，硫化ナトリウム
０．８ｇ／ｌ，アンモニア水０．０７ｍｌ／ｌ，乳酸
１．１ｍｌ／ｌ，蔗糖０．２ｇ／ｌ，水で全容１リット
ルとする。(1) The artificial sweat composition in the artificial sweat test is
Salt 9.9 g / l, urea 1.7 g / l, sodium sulfide 0.8 g / l, ammonia water 0.07 ml / l, lactic acid 1.1 ml / l, sucrose 0.2 g / l, and water to a total volume of 1 liter. To do.
【００１９】（２）アンモニアバッキ試験における試験
液としては、アンモニア水４５ｍｌ，純水８５ｍｌを内
径２１０ｍｍφのデシケータに充填する。(2) As a test solution in the ammonia back test, 45 ml of ammonia water and 85 ml of pure water are filled in a desiccator having an inner diameter of 210 mmφ.
【００２０】[0020]
【発明の効果】本発明によれば、従来のシアン化銅を使
用した下地メッキとしての銅メッキと密着，外観の点で
遜色なく、猛毒のシアンを使用していないので危険性が
なく、取扱いも簡単で、排水処理も容易になる。EFFECTS OF THE INVENTION According to the present invention, there is no difference in terms of adhesion and appearance with copper plating as a base plating using conventional copper cyanide, and there is no danger because no toxic cyanide is used. It is also easy and wastewater treatment becomes easy.
Claims (4)
することを特徴とする銅メッキ液。1. A copper plating solution containing copper ions in an amount of 5 to 200 g / liter.
求項１の銅メッキ液。2. The copper plating solution according to claim 1, which has a pH of 5 or more.
である錯化物を、銅と等モル以上含有することを特徴と
する請求項１または請求項２の銅メッキ液。3. The copper plating solution according to claim 1 or 2, wherein a complex compound having a chelate stability constant with copper of 2.0 or more is contained in an amount of equimolar or more with copper.
塩，塩化物，リン酸塩，水酸化アルカリの中から少なく
とも１つを含有し、しかも、含有した各電導塩の各濃度
を１〜２００ｇ／リットルとしたことを特徴とする請求
項１または請求項２または請求項３の銅メッキ液。4. The conductive salt contains at least one of a sulfate, a carbonate, a nitrate, a chloride, a phosphate, and an alkali hydroxide, and the concentration of each conductive salt contained is 1 to 1. The copper plating solution according to claim 1, 2 or 3, wherein the amount is 200 g / liter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4198796A JPH09202990A (en) | 1996-01-24 | 1996-01-24 | Copper plating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4198796A JPH09202990A (en) | 1996-01-24 | 1996-01-24 | Copper plating liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09202990A true JPH09202990A (en) | 1997-08-05 |
Family
ID=12623557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4198796A Pending JPH09202990A (en) | 1996-01-24 | 1996-01-24 | Copper plating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09202990A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001007687A1 (en) * | 1999-07-26 | 2001-02-01 | Tokyo Electron Limited | Plating method and device, and plating system |
| WO2020158418A1 (en) * | 2019-02-01 | 2020-08-06 | 石原ケミカル株式会社 | Electrolytic copper plate or copper alloy plating bath |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6254397A (en) * | 1985-09-02 | 1987-03-10 | 松下電工株式会社 | Information transmitter |
| JPH01219187A (en) * | 1988-02-25 | 1989-09-01 | Ishihara Chem Co Ltd | Copper electroplating solution |
-
1996
- 1996-01-24 JP JP4198796A patent/JPH09202990A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6254397A (en) * | 1985-09-02 | 1987-03-10 | 松下電工株式会社 | Information transmitter |
| JPH01219187A (en) * | 1988-02-25 | 1989-09-01 | Ishihara Chem Co Ltd | Copper electroplating solution |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001007687A1 (en) * | 1999-07-26 | 2001-02-01 | Tokyo Electron Limited | Plating method and device, and plating system |
| US6607650B1 (en) | 1999-07-26 | 2003-08-19 | Tokyo Electron Ltd. | Method of forming a plated layer to a predetermined thickness |
| WO2020158418A1 (en) * | 2019-02-01 | 2020-08-06 | 石原ケミカル株式会社 | Electrolytic copper plate or copper alloy plating bath |
| US11946153B2 (en) | 2019-02-01 | 2024-04-02 | Ishihara Chemical Co., Ltd. | Copper or copper alloy electroplating bath |
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