JPH0730467B2 - Silver plating stripper - Google Patents
Silver plating stripperInfo
- Publication number
- JPH0730467B2 JPH0730467B2 JP13858291A JP13858291A JPH0730467B2 JP H0730467 B2 JPH0730467 B2 JP H0730467B2 JP 13858291 A JP13858291 A JP 13858291A JP 13858291 A JP13858291 A JP 13858291A JP H0730467 B2 JPH0730467 B2 JP H0730467B2
- Authority
- JP
- Japan
- Prior art keywords
- silver plating
- hydrogen peroxide
- silver
- mol
- present
- 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 - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、銀めっきを施された物
品から不要の銀めっきを除くための銀めっき剥離液に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver plating stripping solution for removing unnecessary silver plating from silver-plated articles.
【０００２】[0002]
【従来の技術】ＩＣのリードフレーム等の電子部品に銀
めっきを施した場合、不要部分に形成された銀めっきを
剥離する必要が生じることがある。そのような場合、銀
めっきの剥離は、銀めっきされた物品を銀めっき剥離作
用を有する薬液に浸漬する方法により行うのが普通であ
る。従来、銀めっき剥離液としては、硝酸系、エチレン
ジアミン−過酸化水素系、アンモニウム塩−過酸化水素
系、シアン化合物−過酸化水素系など、多数のものが知
られている。しかしながら、これら従来の銀めっき剥離
液は、剥離作用があまり強くない一方で、銅または銅合
金からなることが多い電子部品の基体金属を腐食もしく
は汚染する傾向が強く、また、溶解した銀の安定性が悪
く再び基体表面に析出したりすることがあり、さらに、
不快臭発生、シアン化合物の毒性、排水処理の問題な
ど、改良の余地の多いものであった。2. Description of the Related Art When silver plating is applied to an electronic component such as an IC lead frame, it may be necessary to remove the silver plating formed on an unnecessary portion. In such a case, the peeling of the silver plating is usually performed by a method of immersing the silver-plated article in a chemical solution having a silver plating peeling action. Conventionally, a large number of silver plating strippers such as nitric acid-based, ethylenediamine-hydrogen peroxide-based, ammonium salt-hydrogen peroxide-based, cyanide-hydrogen peroxide-based are known. However, while these conventional silver plating strippers have a weak stripping action, they have a strong tendency to corrode or contaminate the base metal of electronic components, which are often made of copper or copper alloys, and to stabilize dissolved silver. It has poor properties and may precipitate again on the substrate surface.
There was a lot of room for improvement such as generation of unpleasant odor, toxicity of cyanide compound, and problem of wastewater treatment.
【０００３】[0003]
【発明が解決しようとする課題】そこで本発明の目的
は、従来品よりも銀めっき剥離作用にすぐれ、金属基体
に対する悪影響が少なく、溶解した銀が処理液中で安定
で基体表面に析出する恐れがなく、しかも安全性の点で
もすぐれた銀めっき剥離液を提供することにある。SUMMARY OF THE INVENTION The object of the present invention is, therefore, to excel in the silver plating peeling action as compared with the conventional products and to have less adverse effect on the metal substrate, and the dissolved silver may be stable in the treatment liquid and deposited on the substrate surface. The purpose of the present invention is to provide a silver plating stripping solution which is free from the problems and is excellent in safety.
【０００４】[0004]
【課題を解決するための手段】本発明が提供することに
成功した新規な銀めっき剥離液は、ホウ酸およびホウ砂
からなる群から選ばれたホウ素化合物ならびに過酸化水
素を必須の成分として含有するものである。本発明はま
た、上記本発明による銀めっき剥離液にさらにポリエチ
レングリコールまたは（および）グリコールエーテル類
を含有することを特徴とする銀めっき剥離液を提供する
ものである。The novel silver plating stripper successfully provided by the present invention contains a boron compound selected from the group consisting of boric acid and borax and hydrogen peroxide as essential components. To do. The present invention also provides a silver plating stripping solution, characterized in that the silver plating stripping solution according to the present invention further contains polyethylene glycol and / or glycol ethers.
【０００５】[0005]
【作用】本発明の銀めっき剥離液において、過酸化水素
は従来の過酸化水素系銀めっき剥離液の場合と同様に、
酸化剤として作用して金属銀をイオン化させる主剤であ
る。この過酸化水素を上記ホウ素化合物と併用すると、
ホウ素化合物の作用機構は定かでないが、過酸化水素単
独の場合よりも、またエチレンジアミン、アンモニウム
塩、シアン化合物等を過酸化水素と併用した従来の過酸
化水素系銀めっき剥離液の場合よりも、速やかに且つ好
ましくない現象や問題点を伴うことなしに、銀めっきが
溶解して除かれる。[Function] In the silver plating stripper of the present invention, hydrogen peroxide is the same as in the conventional hydrogen peroxide-based silver plating stripper.
It is the main agent that acts as an oxidant to ionize metallic silver. When this hydrogen peroxide is used in combination with the above boron compound,
Although the mechanism of action of the boron compound is not clear, than in the case of hydrogen peroxide alone, and in the case of the conventional hydrogen peroxide-based silver plating stripper using ethylenediamine, ammonium salt, cyanide compound, etc. in combination with hydrogen peroxide, The silver plating is dissolved and removed promptly and without any undesirable phenomena or problems.
【０００６】過酸化水素とホウ素化合物による銀めっき
の剥離は、処理液中にポリエチレングリコール、非イオ
ン界面活性剤等を共存させると上記基本２成分だけの場
合よりもむら無く均一に進行するようになり、一層好結
果が得られる。この目的で添加するポリエチレングリコ
ールとしては、分子量が約１００〜２０,０００のもの
が適当である。本発明の銀めっき剥離液は、上記諸成分
のほかにも、基本２成分の作用を損なわない範囲で、任
意の成分を含有させることができる。たとえば、不安定
な過酸化水素の分解を防止し、長期間保存を可能にする
ための安定剤、pＨ調整剤を含有させることができる。
過酸化水素の安定剤として有効な化合物は多数あるが、
グリコールエーテル類、たとえばエチレングリコールモ
ノアリルエーテル、エチレングリコールモノブチルエー
テル等は、本発明の銀めっき剥離液に使用する過酸化水
素安定剤として特に優れており好ましい。The peeling of silver plating with hydrogen peroxide and a boron compound proceeds evenly and uniformly when polyethylene glycol, a nonionic surfactant and the like are coexistent in the treatment liquid as compared with the case of only the above two basic components. , And even better results are obtained. Polyethylene glycol having a molecular weight of about 100 to 20,000 is suitable for this purpose. The silver plating stripper of the present invention may contain, in addition to the above-mentioned components, any component as long as the action of the two basic components is not impaired. For example, a stabilizer and a pH adjusting agent for preventing unstable decomposition of hydrogen peroxide and enabling long-term storage can be contained.
There are many compounds that are effective as stabilizers of hydrogen peroxide,
Glycol ethers such as ethylene glycol monoallyl ether and ethylene glycol monobutyl ether are particularly preferable as the hydrogen peroxide stabilizer used in the silver plating stripping solution of the present invention.
【０００７】本発明の銀めっき剥離液は、安定剤を含有
させて保存可能な薬液として提供してもよく、また、使
用直前に構成成分を配合して調製してもよい。本発明の
銀めっき剥離液を構成する各成分の好適濃度（銀めっき
剥離に使用する状態における濃度）は次のとおりであ
る。 過酸化水素：０.１〜５モル/l（好ましくは０.３〜３モル
/l） ホウ素化合物：０.０５〜１.０モル/l（好ましくは０.１
〜０.５モル/l） ポリエチレングリコール：０.０００１〜１モル/l（好ま
しくは０.００１〜０.７モル/l） グリコールエーテル：０.０００１〜１モル/l（好ましく
は０.００１〜０.２モル/l）The silver plating stripping solution of the present invention may be provided as a storable chemical solution containing a stabilizer, or may be prepared by mixing the components immediately before use. The preferred concentration of each component constituting the silver plating stripping solution of the present invention (concentration in a state used for silver plating stripping) is as follows. Hydrogen peroxide: 0.1-5 mol / l (preferably 0.3-3 mol)
/ l) Boron compound: 0.05 to 1.0 mol / l (preferably 0.1)
-0.5 mol / l) Polyethylene glycol: 0.0001-1 mol / l (preferably 0.001-0.7 mol / l) Glycol ether: 0.0001-1 mol / l (preferably 0.001) ~ 0.2 mol / l)
【０００８】過酸化水素の濃度が高いほど銀めっきの剥
離は速くなるが、５モル/lをこえる高濃度では反応が過激
になり、発泡による処理液の飛散、発熱、自己分解など
を招くので、上記濃度範囲をこえないことが望ましい。
また、０.１モル/l未満では、剥離速度が極端に遅くな
り、実用的でない。ホウ素化合物、ポリエチレングリコ
ールおよびグリコールエーテルは、上記範囲よりも低濃
度では使用効果がほとんどなく、一方、使用効果は上記
範囲の上限付近で限界に達し、それ以上高濃度にしても
無駄である。本発明の銀めっき剥離液による銀めっき剥
離は、上記好適濃度範囲に調整し且つ温度を常温ないし
約４０℃に調整した剥離液に、被処理物品を、またはそ
の被処理部分を、約１〜１５分間浸漬することにより行
う。[0008] The higher the concentration of hydrogen peroxide, the faster the peeling of the silver plating, but at a concentration higher than 5 mol / l, the reaction becomes radical and the treatment liquid is scattered due to foaming, causing heat generation and self-decomposition. It is desirable that the concentration range is not exceeded.
On the other hand, if it is less than 0.1 mol / l, the peeling rate becomes extremely slow, which is not practical. Boron compounds, polyethylene glycols and glycol ethers have almost no use effect at concentrations lower than the above range, while the use effects reach their limits near the upper limit of the above range, and higher concentrations are useless. The silver plating stripping with the silver plating stripping solution of the present invention is carried out with the stripping solution adjusted to the above-mentioned suitable concentration range and the temperature of from room temperature to about 40 ° C. to treat the article to be treated It is performed by soaking for 15 minutes.
【０００９】[0009]
実施例１ 銅からなる基体に電気めっきにより銀皮膜を３μmの厚
さに施し、それを、過酸化水素溶液（濃度３０％）２０
０ml/l（Ｈ2Ｏ2として２モル/l）、ホウ砂５０g/l（０.１
２モル/l）、エチレングリコールモノアリールエーテル１
g/l（０.００１モル/l）、ポリエチレングリコール（分子
量４０００）１g/l（０.０００３モル/l）の水溶液によ
り、温度４０℃で浸漬処理した。銀めっきは５分で完全
に剥離され、また、基体金属銅の腐食も認められなかっ
た。Example 1 A substrate made of copper was electroplated to form a silver film having a thickness of 3 μm, which was applied with a hydrogen peroxide solution (concentration: 30%) 20
0 ml / l (2 mol / l as H 2 O 2 ), borax 50 g / l (0.1
2 mol / l), ethylene glycol monoaryl ether 1
Immersion treatment was carried out at a temperature of 40 ° C. with an aqueous solution of g / l (0.001 mol / l) and polyethylene glycol (molecular weight 4000) 1 g / l (0.0003 mol / l). The silver plating was completely peeled off in 5 minutes, and no corrosion of the base metal copper was observed.
【００１０】実施例２ 銅からなる基体に電気めっきにより銀皮膜を３μmの厚
さに施し、それを、過酸化水素溶液（濃度３０％）２０
０ml/l（Ｈ2Ｏ2として０.５モル/l）、ホウ酸３０g/l
（０.１２モル/l）、エチレングリコールモノブチルエー
テル０.５g/l（０.００１モル/l）、ポリエチレングリコ
ール（分子量４０００）１g/l（０.０００３モル/l）の水
溶液により、温度４０℃で浸漬処理した。銀めっきは５
分で完全に剥離され、また、基体金属銅の腐食も認めら
れなかった。Example 2 A silver coating was applied to a substrate made of copper by electroplating so as to have a thickness of 3 μm, and this was applied with a hydrogen peroxide solution (concentration: 30%) 20
0 ml / l (0.5 mol / l as H 2 O 2 ), boric acid 30 g / l
(0.12 mol / l), ethylene glycol monobutyl ether 0.5 g / l (0.001 mol / l), polyethylene glycol (molecular weight 4000) 1 g / l (0.0003 mol / l) aqueous solution at a temperature of 40 Immersion treatment was performed at ° C. 5 for silver plating
It completely peeled off in minutes, and no corrosion of the base metal copper was observed.
【００１１】実施例３ 銅からなる基体に電気めっきにより銀皮膜を３μmの厚
さに施し、それを、過酸化水素溶液（濃度３０％）２０
０ml/l（Ｈ2Ｏ2として０.５モル/l）、ホウ酸３０g/l
（０.１２モル/l）の水溶液により、温度４０℃で５分間
浸漬処理した。処理後の銅基体表面には若干の色むらが
観察されたが腐食は認められず、銀めっきは完全に剥離
された。Example 3 A silver film was applied by electroplating to a thickness of 3 μm on a substrate made of copper, and the silver film was applied to a hydrogen peroxide solution (concentration: 30%) 20
0 ml / l (0.5 mol / l as H 2 O 2 ), boric acid 30 g / l
Immersion treatment was carried out for 5 minutes at a temperature of 40 ° C. with an aqueous solution of (0.12 mol / l). Although some color unevenness was observed on the surface of the copper substrate after the treatment, no corrosion was observed and the silver plating was completely peeled off.
【００１２】上記各例で銀を剥離した後の銅金属基体に
ついてＥＰＭＡによる表面元素分析を行なったが、銀は
検出されず、溶解した銀の置換析出はなかったことが確
認された。また、実施例１，２で銀を剥離した後の銅金
属基体に市販の非フッ化半光沢はんだめっきを５μmの
膜厚に施し、折り曲げ試験および加熱試験を行なった
が、いずれについてもはんだ皮膜の脱落、フクレやコブ
の発生は認められず、銀めっき剥離処理が基体に腐食等
の悪影響を及ぼさなかったことが確認された。Surface elemental analysis by EPMA was carried out on the copper metal substrate after the silver was peeled off in each of the above examples, and it was confirmed that silver was not detected and substitutional deposition of the dissolved silver was not present. Further, commercially available non-fluorinated semi-bright solder plating was applied to the copper metal substrate after peeling silver in Examples 1 and 2 to a film thickness of 5 μm, and a bending test and a heating test were performed. No dropouts, blisters or lumps were observed, and it was confirmed that the silver plating peeling treatment did not adversely affect the substrate such as corrosion.
【００１３】[0013]
【発明の効果】ホウ酸およびホウ砂からなる群から選ば
れたホウ素化合物、過酸化水素を必須成分とし、必要に
応じて添加する助剤がポリエチレングリコール、グリコ
ールエーテル等である本発明の銀めっき剥離液は、上述
のように基体金属に損傷を与えることなしに速やかに且
つ確実に、銀めっきを剥離し、銀の置換析出もない。ま
た、シアン化合物など危険物質を含有せず、有害ガスの
発生も無いので、保存や取り扱いが容易であり、作業環
境も良好に保たれるという特長がある。[Effect of the Invention] The silver plating of the present invention in which a boron compound selected from the group consisting of boric acid and borax and hydrogen peroxide are essential components, and the auxiliary agent to be added as necessary is polyethylene glycol, glycol ether or the like. The stripping solution quickly and reliably strips the silver plating without damaging the base metal as described above, and does not cause substitutional deposition of silver. Further, since it does not contain a dangerous substance such as a cyanide compound and does not generate a harmful gas, it is easy to store and handle, and the working environment can be kept good.
Claims (3)
れたホウ素化合物ならびに過酸化水素を含有することを
特徴とする銀めっき剥離液。1. A silver plating stripper containing a boron compound selected from the group consisting of boric acid and borax and hydrogen peroxide.
れたホウ素化合物、過酸化水素、ならびにポリエチレン
グリコールを含有することを特徴とする銀めっき剥離
液。2. A silver plating stripper containing a boron compound selected from the group consisting of boric acid and borax, hydrogen peroxide, and polyethylene glycol.
れたホウ素化合物ならびに過酸化水素を含有し、さらに
過酸化水素の安定剤としてグリコールエーテル類を含有
することを特徴とする銀めっき剥離液。3. A silver plating stripper containing a boron compound selected from the group consisting of boric acid and borax and hydrogen peroxide, and further containing glycol ethers as stabilizers of hydrogen peroxide. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13858291A JPH0730467B2 (en) | 1991-05-15 | 1991-05-15 | Silver plating stripper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13858291A JPH0730467B2 (en) | 1991-05-15 | 1991-05-15 | Silver plating stripper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04337088A JPH04337088A (en) | 1992-11-25 |
| JPH0730467B2 true JPH0730467B2 (en) | 1995-04-05 |
Family
ID=15225491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13858291A Expired - Fee Related JPH0730467B2 (en) | 1991-05-15 | 1991-05-15 | Silver plating stripper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730467B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018047210A1 (en) * | 2016-09-09 | 2018-03-15 | パナソニックＩｐマネジメント株式会社 | Etching solution and etching concentrate for multilayer film, and etching method |
-
1991
- 1991-05-15 JP JP13858291A patent/JPH0730467B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04337088A (en) | 1992-11-25 |
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