JP2939181B2 - Silver electrolytic peeling agent and electrolytic peeling method - Google Patents
Silver electrolytic peeling agent and electrolytic peeling methodInfo
- Publication number
- JP2939181B2 JP2939181B2 JP8142304A JP14230496A JP2939181B2 JP 2939181 B2 JP2939181 B2 JP 2939181B2 JP 8142304 A JP8142304 A JP 8142304A JP 14230496 A JP14230496 A JP 14230496A JP 2939181 B2 JP2939181 B2 JP 2939181B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- methyl
- bath
- electrolytic
- copper
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/20—Separation of the formed objects from the electrodes with no destruction of said electrodes
- C25D1/22—Separating compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F5/00—Electrolytic stripping of metallic layers or coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銀の電解剥離剤お
よび銀の電解剥離方法に関するものであり、特には銀め
っき皮膜の不要部分を電解剥離するのに好適な銀の電解
剥離剤および銀の電解剥離方法に関する。本発明はま
た、銅または銅合金等を被処理物とする場合に電解剥離
後の保管中の素材の変色あるいは腐食を防止することを
可能とする銀の電解剥離剤および電解剥離方法に関す
る。本発明の電解剥離剤および電解剥離方法は銀剥離後
のボンディング特性に悪影響を及ぼさない。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver electrolytic stripping agent and a silver electrolytic stripping method, and more particularly to a silver electrolytic stripping agent and silver suitable for electrolytic stripping an unnecessary portion of a silver plating film. And a method for electrolytic stripping. The present invention also relates to a silver electrolytic stripping agent and an electrolytic stripping method that can prevent discoloration or corrosion of a material during storage after electrolytic stripping when copper or a copper alloy or the like is to be processed. The electrolytic stripping agent and the electrolytic stripping method of the present invention do not adversely affect the bonding characteristics after silver stripping.
【０００２】[0002]
【従来の技術】半導体リードフレームやコネクタピンな
どの電子部品に対しては、銀の部分めっきが行われるこ
とが多い。この際、銀めっき不要部分にはマスキングな
どの処理が施されるが、銀めっき皮膜が不要部分にもは
み出す場合がある。そのような場合には、はみ出した銀
めっき皮膜を剥離する必要がある。不要部分の銀めっき
皮膜を剥離する方法としては、電解剥離法が知られてい
る。電解剥離法は、剥離剤（剥離液）の浴中に目的とす
る銀めっきされた被処理物を浸漬して、該被処理物を陽
極として電解することによって銀めっき皮膜を剥離する
方法である。2. Description of the Related Art Silver plating is often performed on electronic components such as semiconductor lead frames and connector pins. At this time, a process such as masking is performed on the portion not requiring silver plating, but the silver plating film may protrude into the unnecessary portion in some cases. In such a case, it is necessary to peel off the protruding silver plating film. As a method of peeling an unnecessary portion of the silver plating film, an electrolytic peeling method is known. The electrolytic stripping method is a method in which a silver-plated object to be treated is immersed in a bath of a stripping agent (stripping solution), and the object is used as an anode to electrolyze the silver-plated film. .
【０００３】従来、銀の電解剥離剤としては、濃硫酸に
硝酸ナトリウムを添加したもの、シアン化合物を含むも
の、チオ硫酸ナトリウムを主成分としたものなどが用い
られてきたが、下地素材（銅や銅合金）をエッチング
し、必要部分の銀まで侵食したり、毒性の高いシアン化
合物を用いるため取扱いに注意を要するなどの問題点が
あった。[0003] Conventionally, silver electrolytic stripping agents containing concentrated sulfuric acid to which sodium nitrate has been added, those containing a cyanide compound, those containing sodium thiosulfate as a main component, and the like have been used. And copper alloys) to etch the required portion of silver and to use a highly toxic cyanide compound, which requires attention to handling.
【０００４】そのため、危険な濃硫酸や毒性の高いシア
ン化合物を使用しない剥離剤としてコハク酸イミドまた
はフタル酸イミドとアルカリ金属水酸化物を主成分とす
るもの（特開平２−１０４６９９号（特公平５−８７５
９８））や、２−ピロリドン−５−カルボン酸を含有す
るもの及びそれに加えて糖類を更に含有するもの（特開
平６−４１８００号）など、分子中に１個の窒素原子を
含む環状酸イミドを主成分とする剥離剤が開発されてい
る。また、特開平２−１７５８２５号は、バルビツール
酸、ウラシル、グルタルイミド等の−ＮＨ−を有する５
員環または６員環化合物を記載している。特開平７−２
４３１００号は、錯形成剤としてヒダントイン化合物を
用いることを提唱している。[0004] Therefore, as a stripping agent which does not use dangerous concentrated sulfuric acid or a highly toxic cyanide, a stripping agent containing succinimide or phthalic imide and an alkali metal hydroxide as main components (Japanese Patent Laid-Open No. 2-104699 (Japanese Patent Publication No. 5-875
98)) and cyclic acid imides containing one nitrogen atom in the molecule, such as those containing 2-pyrrolidone-5-carboxylic acid and those further containing saccharides in addition thereto (JP-A-6-41800). A release agent containing as a main component has been developed. Japanese Patent Application Laid-Open No. 2-175825 discloses a compound having -NH- such as barbituric acid, uracil and glutarimide.
A six-membered or six-membered ring compound is described. JP-A-7-2
No. 43100 proposes using a hydantoin compound as a complexing agent.
【０００５】[0005]
【発明が解決しようとする課題】しかし、分子中に１個
の窒素原子を含む環状酸イミドを主成分とする化合物か
らなる剥離剤は、アルカリにより加水分解を起こし易
く、分解物が浴中に蓄積すると、銀めっき表面の不働態
化や変色、ムラなどの必要部分の銀めっき面への悪影響
を与え、主成分の消耗量が多く、浴の寿命が短いという
問題があった。また、高電流密度の条件で剥離を行う
と、銀めっき表面が不働態化したり、ムラになりやすい
という問題もあった。However, a stripping agent comprising a compound containing a cyclic acid imide containing one nitrogen atom as a main component in a molecule is liable to be hydrolyzed by an alkali, and the decomposed product is left in the bath. Accumulation has a problem in that passivation, discoloration, unevenness, and the like of the silver plating surface have an adverse effect on required portions of the silver plating surface, the main components are consumed in a large amount, and the bath life is short. In addition, when peeling is performed under conditions of high current density, there is a problem that the surface of the silver plating is likely to be passivated or uneven.
【０００６】また、半導体デバイスでは、ダイ・ボンデ
ィングやワイヤー・ボンディングといったボンディング
工程を経由する。ダイ・ボンディングは、半導体チップ
とリードフレームをエポキシ樹脂で接着する工程であ
り、ここでエポキシ・ブリードアウトが発生すると、ダ
イパッドが有機物で汚染されグランドボンディング不良
となり、外部との導通が取れなくなる。ワイヤー・ボン
ディングは半導体チップとリードフレームインナーリー
ドをＡｕ、Ａｌ線等で配線する工程であり、インナーリ
ード部Ａｇ面が汚染されていたり、表面状態が非常にラ
フな場合、外部との導通が取れなくなる。従って、銀剥
離後のボンディング特性に悪影響を及ぼさないものであ
ることは重要である。上述した銀剥離剤はこうした要求
を満足するものではない。In a semiconductor device, a bonding process such as die bonding or wire bonding is performed. Die bonding is a process in which a semiconductor chip and a lead frame are bonded with an epoxy resin. If epoxy bleed-out occurs here, the die pad is contaminated with an organic substance and ground bonding failure occurs, so that conduction to the outside cannot be achieved. Wire bonding is a process of wiring the semiconductor chip and the lead frame inner lead with Au, Al wire, etc. If the inner lead portion Ag surface is contaminated or the surface condition is very rough, conduction with the outside can be obtained. Disappears. Therefore, it is important that the bonding characteristics after silver separation are not adversely affected. The silver release agents described above do not satisfy these requirements.
【０００７】そこで、本発明は、主成分の加水分解が生
じ難く、浴寿命が長いと同時に、高電流密度での銀の剥
離を可能とし、しかもボンディング特性に悪影響を及ぼ
さない、銀の電解剥離剤および電解剥離方法を開発する
ことを第１の課題とした。Accordingly, the present invention provides an electrolytic silver exfoliating method which hardly causes hydrolysis of the main component, has a long bath life, enables exfoliation of silver at a high current density, and has no adverse effect on bonding characteristics. The first task was to develop an agent and an electrolytic stripping method.
【０００８】加えて、銀の電解剥離剤において、被処理
物が銅または銅合金等の場合には、素材の若干の溶解が
起こり、素材表面が活性化するために電解剥離後の保管
中に変色あるいは腐食が発生しやすいという問題があっ
た。そこで、本発明は、銅または銅合金等を被処理物と
する場合に電解剥離後の保管中の素材の変色あるいは腐
食を防止することを可能とする銀の電解剥離剤および電
解剥離方法を開発することを第２の課題とした。[0008] In addition, when the object to be treated is a copper or copper alloy in the silver electrolytic stripping agent, the material slightly dissolves and the material surface is activated. There was a problem that discoloration or corrosion easily occurred. Therefore, the present invention has developed a silver electrolytic stripping agent and an electrolytic stripping method that can prevent discoloration or corrosion of a material during storage after electrolytic stripping when copper or a copper alloy or the like is to be processed. Is the second task.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、上記の問
題点を解決するために鋭意研究を行った結果、環内にＮ
原子を２個以上有する含窒素環状化合物またはそれらの
誘導体の特定種は、電子の分極状態がＮ原子１個の場合
とは異なり、加水分解が生じにくく、そのため浴寿命が
長くなり、また、高電流密度での剥離が可能とし、更に
そこにホウ酸化合物を加えることによりボンディング特
性への悪影響を防止することができることを見いだし
た。この知見に基づいて、本発明は、主成分としてヒダ
ントイン、５，５−ジメチルヒダントイン、シアヌル
酸、６−メチル−３−ピリダゾン、３−メチル−５−ピ
ラゾロン及びアラントインから成る群から選択される銀
の剥離成分と、副成分としてホウ酸系化合物を含む銀の
電解剥離剤を提供する。界面活性剤を更に添加すること
ができる。Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, N
A specific kind of nitrogen-containing cyclic compound having two or more atoms or a derivative thereof is different from the case where the electron polarization state is one N atom, unlikely to be hydrolyzed, so that the bath life is prolonged. It has been found that peeling can be performed at a current density, and that a boric acid compound can be added thereto to prevent adverse effects on bonding characteristics. Based on this finding, the present invention provides a silver selected from the group consisting of hydantoin, 5,5-dimethylhydantoin, cyanuric acid, 6-methyl-3-pyridazone, 3-methyl-5-pyrazolone and allantoin as main components. And a silver electrolytic release agent containing a boric acid compound as a secondary component. Surfactants can be further added.
【００１０】更に、銀の電解剥離成分に特定種の銅のイ
ンヒビターを添加し、これを素材表面に吸着させること
によって保管中の素材の変色あるいは腐食を防止するこ
とが可能であることを見いだした。この知見に基づい
て、本発明はまた、銅のインヒビターとして、ベンゾト
リアゾール、ベンズイミダゾール、チオウラシル、チオ
バルビツル酸、ベンゾチアゾール、ベンゾオキサゾー
ル、インダゾール、インドール、イミダゾール、イミダ
ゾリンまたはこれらの誘導体から選択された１種または
それ以上を更に含む上記の銀の電解剥離剤を提供する。Furthermore, it has been found that discoloration or corrosion of the material during storage can be prevented by adding a specific type of copper inhibitor to the silver electrolytic peeling component and adsorbing the inhibitor on the material surface. . Based on this finding, the present invention also provides as an inhibitor of copper one selected from benzotriazole, benzimidazole, thiouracil, thiobarbituric acid, benzothiazole, benzoxazole, indazole, indole, imidazole, imidazoline or derivatives thereof. Or an electrolytic stripping agent for silver as described above, further comprising:
【００１１】さらに、本発明は、表面が銀めっきされた
銅乃至銅合金製被処理物を上記の電解剥離剤溶液に浸漬
し、該被処理物を陽極として電解することを特徴とする
銀の電解剥離方法をも提供する。電解剥離を剥離剤のｐ
Ｈ：７〜１４、浴電流密度：０．１〜５０Ａ／ｄｍ2 及
び浴温度：１０〜６０℃の条件で攪拌下で実施すること
が好ましい。Further, the present invention is characterized in that an object to be processed made of copper or a copper alloy having a silver-plated surface is immersed in the above electrolytic stripping agent solution, and the object is electrolyzed using the object as an anode. An electrolytic stripping method is also provided. Electrolytic delamination is performed using p
H: 7-14, bath current density: 0.1 to 50 A / dm 2, and bath temperature: 10 to 60 ° C., preferably under stirring.
【００１２】本発明における剥離剤の主成分は、環内に
Ｎ原子を２個以上有するために電子の分極状態がＮ原子
１個の場合とは異なり、加水分解が生じにくい。そのた
め浴寿命が長くなり、また、高電流密度での剥離が可能
となるものと考えられる。本発明においては、銅のイン
ヒビターが銅または銅合金素材表面に吸着し、それによ
り素材の若干の溶解が起こっても、素材表面の活性化を
抑制し、電解剥離後の保管中の変色または腐食を防止す
るものと考えられる。Since the main component of the release agent in the present invention has two or more N atoms in the ring, unlike the case where the electron polarization state is one N atom, hydrolysis hardly occurs. Therefore, it is considered that the bath life is prolonged and peeling at a high current density becomes possible. In the present invention, even if the copper inhibitor is adsorbed on the surface of the copper or copper alloy material, thereby slightly dissolving the material, the activation of the material surface is suppressed, and the discoloration or corrosion during storage after electrolytic peeling is suppressed. It is thought that it prevents.
【００１３】[0013]
【発明の実施の形態】本発明の銀の電解剥離剤の主成分
は、環内にＮ原子を２個以上有する含窒素環状化合物ま
たはそれらの誘導体の特定種であり、ヒダントイン、
５，５−ジメチルヒダントイン、シアヌル酸、６−メチ
ル−３−ピリダゾン、３−メチル−５−ピラゾロン及び
アラントインから成る群から選択される。これら主成分
の化学式を参考までに化学式１として示しておく。BEST MODE FOR CARRYING OUT THE INVENTION The main component of the silver electrolytic stripping agent of the present invention is a specific type of a nitrogen-containing cyclic compound having two or more N atoms in a ring or a derivative thereof, such as hydantoin,
It is selected from the group consisting of 5,5-dimethylhydantoin, cyanuric acid, 6-methyl-3-pyridazone, 3-methyl-5-pyrazolone and allantoin. The chemical formulas of these main components are shown as Chemical Formula 1 for reference.
【００１４】[0014]
【化１】 Embedded image
【００１５】これら主成分の浴中での濃度範囲は、５〜
２００ｇ／ｌ、好ましくは１５〜１００ｇ／ｌである。
濃度が低すぎると銀の不働態化が生じ易く、他方濃度が
高すぎると剥離剤（剥離液）の汲みだしが問題となるた
め好ましくない。The concentration range of these main components in the bath is 5 to 5.
It is 200 g / l, preferably 15 to 100 g / l.
If the concentration is too low, passivation of silver is likely to occur, while if the concentration is too high, pumping of the release agent (stripping solution) becomes a problem, which is not preferable.
【００１６】副成分として、基本的にはｐＨ緩衝剤とし
て、四ホウ酸カリウム、（オルト）ホウ酸、二ホウ酸カ
リウム、ホウ酸ナトリウム、五ホウ酸ナトリウム、のよ
うなホウ酸塩や二、四、五ホウ酸塩などのホウ酸化合物
が加えられる。ホウ酸化合物の濃度範囲は、５〜１００
ｇ／ｌ、好ましくは１０〜５０ｇ／ｌである。濃度が低
すぎるとｐＨ緩衝性が小さく、他方濃度が高すぎても効
果は飽和し、好ましくない。この副成分はボンディング
特性に大きく寄与する。As an accessory component, basically as a pH buffer, borates such as potassium tetraborate, (ortho) boric acid, potassium diborate, sodium borate, sodium pentaborate, A boric acid compound such as a tetrapentaborate is added. The concentration range of the boric acid compound is 5 to 100.
g / l, preferably 10 to 50 g / l. If the concentration is too low, the pH buffering property is low, while if the concentration is too high, the effect is saturated, which is not preferable. This subcomponent greatly contributes to the bonding characteristics.
【００１７】更に、必要に応じて界面活性剤を加える。
界面活性剤としては、アニオン系、カチオン系及びノニ
オン系のいずれかまたはそれらを混合したものを用いる
ことが可能である。界面活性剤の濃度範囲は、０．１μ
ｇ／ｌ〜１０ｇ／ｌ、好ましくは１０μｇ／ｌ〜１ｇ／
ｌである。濃度が低すぎると界面活性効果がなく、他方
濃度が高すぎても効果が飽和し、好ましくない。Further, a surfactant is added as required.
As the surfactant, any of anionic, cationic and nonionic surfactants or a mixture thereof can be used. The concentration range of the surfactant is 0.1μ
g / l to 10 g / l, preferably 10 μg / l to 1 g /
l. If the concentration is too low, there is no surface active effect, while if the concentration is too high, the effect is saturated, which is not preferable.
【００１８】銅インヒビターとしては、ベンゾトリアゾ
ール、ベンズイミダゾール、チオウラシル、チオバルビ
ツル酸、ベンゾチアゾール、ベンゾオキサゾール、イン
ダゾール、インドール、イミダゾール、イミダゾリンま
たはこれらの誘導体から選択された１種またはそれ以上
を用いることができる。銅インヒビターの濃度範囲は、
１〜１０００ｍｇ／ｌ、好ましくは５〜５００ｇ／ｌで
ある。濃度が低すぎると変色防止効果がなく、他方濃度
が高すぎてもそれ以上の効果がない。これら銅インヒビ
ターは、次の構造式を有する：As the copper inhibitor, one or more selected from benzotriazole, benzimidazole, thiouracil, thiobarbituric acid, benzothiazole, benzoxazole, indazole, indole, imidazole, imidazoline and derivatives thereof can be used. . The concentration range of the copper inhibitor is
It is 1 to 1000 mg / l, preferably 5 to 500 g / l. If the concentration is too low, there is no effect of preventing discoloration, while if the concentration is too high, no further effect is obtained. These copper inhibitors have the following structural formula:
【００１９】[0019]
【化２】 Embedded image
【００２０】上記の剥離剤を用いて、所定の条件で銀の
電解剥離を行う。剥離剤は、ｐＨが７〜１４、好ましく
は７〜１２となるように、水酸化ナトリウム等のアルカ
リ金属水酸化物またはアルカリ土類金属水酸化物のよう
なｐＨ調整剤で調整する。ｐＨが低すぎると剥離速度が
遅く銀の面がムラになり易く、選択剥離性が悪い。他方
ｐＨが高すぎてもメリットがない。Electrolytic stripping of silver is performed under predetermined conditions using the above-mentioned stripping agent. The release agent is adjusted with a pH adjuster such as an alkali metal hydroxide such as sodium hydroxide or an alkaline earth metal hydroxide so that the pH is 7-14, preferably 7-12. If the pH is too low, the peeling speed is slow, the silver surface tends to be uneven, and the selective peelability is poor. On the other hand, there is no merit if the pH is too high.
【００２１】なお、本発明は被処理物として、銅、銅合
金、４２合金のような鉄−ニッケル合金、ステンレスス
チール、ニッケル合金などの各種金属下地素材の上に銀
めっき、銀ロウなどによって銀の皮膜を形成したものを
剥離対象とする。In the present invention, the object to be treated is silver plating or silver brazing on various metal base materials such as copper, copper alloy, iron-nickel alloy such as 42 alloy, stainless steel, nickel alloy and the like. The film on which the film is formed is the object to be peeled.
【００２２】このような、表面に銀の皮膜が形成された
被処理物を、上記のように調整された電解剥離剤の浴に
浸漬し、該被処理物を陽極として電解する。陰極の材質
は特に制限されないが、一般にステンレススチールが使
用される。電流密度は、剥離する銀の面積に対して０．
１〜５０Ａ／ｄｍ2 、好ましくは０．５〜１０Ａ／ｄｍ
2 とする。電流密度が低すぎると剥離速度が遅く、他方
電流密度が高すぎると銀の不働態化が起こり易くなるた
め好ましくない。また、浴の温度は１０〜６０℃、好ま
しくは１５〜４０℃で電解を行う。浴の温度が低すぎる
と剥離速度が遅く、他方高すぎると浴が不安定になるた
め好ましくない。なお、電解中には浴の撹拌を行うこと
が望ましく、特に電流密度が高い場合には不働態化を起
こさないために撹拌速度は速い方が良い。The object having the silver film formed on the surface is immersed in a bath of the electrolytic stripping agent adjusted as described above, and the object is electrolyzed using the object as an anode. The material of the cathode is not particularly limited, but stainless steel is generally used. The current density was set at 0.
1 to 50 A / dm 2 , preferably 0.5 to 10 A / dm 2
Assume 2 . If the current density is too low, the peeling rate is low, while if the current density is too high, passivation of silver tends to occur, which is not preferable. The electrolysis is performed at a bath temperature of 10 to 60C, preferably 15 to 40C. If the temperature of the bath is too low, the stripping rate is low, while if it is too high, the bath becomes unstable, which is not preferable. It is desirable to stir the bath during the electrolysis, and especially when the current density is high, the stirring speed is preferably high so as not to cause passivation.
【００２３】銅または銅合金の下地素材の上に銀めっ
き、銀ロウなどによって銀の皮膜を形成したものを剥離
対象とする場合には、銅インヒビターを更に含む浴に浸
漬し、上述した条件で該被処理物を陽極として電解す
る。銀の剥離電解に先立ってもしくはその後に、銅イン
ヒビター溶液に被処理物を浸漬することも効果的であ
る。液中に１秒以上浸漬すれば銅の変色防止効果は十分
にある。When a silver or a silver film is formed on a copper or copper alloy base material by silver plating, silver brazing or the like to be peeled, the substrate is immersed in a bath further containing a copper inhibitor and subjected to the above-described conditions. Electrolysis is performed using the object as an anode. It is also effective to immerse the object to be treated in a copper inhibitor solution before or after the electrolysis of silver. If it is immersed in the solution for 1 second or more, the effect of preventing discoloration of copper is sufficient.
【００２４】被処理物の銀めっき皮膜の一部を剥離剤浴
により剥離する場合、剥離すべきでない必要部分の銀め
っき皮膜はマスキングを施したり、剥離すべき部分のみ
を局所的に浸漬するといった方法を採用することができ
る。また、必要部分の銀めっき皮膜が十分に厚く、剥離
すべき不要部分と同じ程度剥離されても差し支えない場
合には全体を浸漬してもよい。また、リードフレームを
被処理物とする場合には、パッド部分等の必要部分の銀
めっき皮膜は通常電解剥離時に低電流密度部分となりそ
してその周辺の不要部分の銀めっき皮膜は高電流部分と
なることから、必要部分の銀めっき部分にマスキングす
ることなくそのまま電解剥離しても不要部分の銀めっき
皮膜のみを剥離することが可能である。When a part of the silver plating film of the object to be processed is peeled off by a release agent bath, a necessary portion of the silver plating film which should not be peeled off is masked or only the portion to be peeled is locally immersed. A method can be adopted. If the silver plating film in the necessary portion is sufficiently thick and may be peeled off to the same extent as the unnecessary portion to be peeled off, the whole may be immersed. When the lead frame is to be processed, the silver plating film of a necessary portion such as a pad portion usually has a low current density portion during electrolytic stripping, and the silver plating film of an unnecessary portion around the portion has a high current portion. Therefore, even if electrolytic peeling is performed without masking the required portion of the silver plating portion, only the unnecessary portion of the silver plating film can be removed.
【００２５】[0025]
【実施例】以下、実施例並びに参考例および比較例によ
って本発明をさらに詳細に説明する。The present invention will be described below in more detail with reference to Examples, Reference Examples and Comparative Examples.
【００２６】（実施例Ｉ）表１の実施例Ｎｏ．１〜６に
示すような組成の剥離剤浴を調製した。銅を素材とする
リードフレームのパット部分に厚さ５μｍの部分銀めっ
きを行ったもの（パッド部分周辺の不要部分にも銀めっ
き皮膜が形成されている）をサンプルとして、上記の各
剥離剤浴中に浸漬し、表１に示す剥離条件で電解剥離を
行った。すなわち、ｐＨ：８〜１１、電流密度：３．０
〜５．０Ａ／ｄｍ2 、浴温：２５℃、撹拌速度：１．０
ｍ／秒、時間：３０秒で電解を行い不要部分の銀の剥離
を行った。(Embodiment I) Release baths having compositions as shown in 1 to 6 were prepared. Each of the above release agent baths was prepared by using a sample of a lead frame made of copper in which a pad portion was subjected to partial silver plating with a thickness of 5 μm (a silver plating film was also formed on unnecessary portions around the pad portion). Then, electrolytic peeling was performed under the peeling conditions shown in Table 1. That is, pH: 8-11, current density: 3.0
~ 5.0 A / dm 2 , bath temperature: 25 ° C, stirring speed: 1.0
Electrolysis was performed at m / sec for a time of 30 sec to peel off silver at unnecessary portions.
【００２７】剥離後のサンプルについて銀表面外観およ
び素材外観並びに煮沸後素材外観を顕微鏡観察（×１０
０）により評価した。同時に、銀剥離膜厚を蛍光Ｘ線に
より測定した。また、ダイボンディングとワイヤーボン
ディングとを行い、前者についてはエポキシブリードア
ウトの発生の有無を調査し、後者についてはワイヤーボ
ンディング結果の状態を調査した。With respect to the sample after peeling, the silver surface appearance and the material appearance and the material appearance after boiling were observed with a microscope (× 10
0). At the same time, the peeled silver film thickness was measured by X-ray fluorescence. In addition, die bonding and wire bonding were performed, and the presence or absence of epoxy bleed-out was examined for the former, and the state of the wire bonding result was examined for the latter.
【００２８】また、剥離剤の建浴後４２日後に同様の電
解剥離を行い、上記と同様の評価を行った。Further, 42 days after bathing of the release agent, the same electrolytic peeling was performed, and the same evaluation as above was performed.
【００２９】［結果］銀表面外観および素材外観ともに
良好であった。煮沸後素材外観は多少の変色を示した
が、使用に耐えられないほどではなかった。銀剥離膜厚
は、０．９〜１．６μｍと十分な剥離性能を示した。ボ
ンディング特性も良好であった。建浴後４２日後の試験
においても、全く同じ結果を得た。このことからまだ浴
寿命には達していないことがわかる。[Results] Both the silver surface appearance and the material appearance were good. After boiling, the appearance of the material showed some discoloration, but not so much that it could not be used. The silver release film thickness showed sufficient release performance of 0.9 to 1.6 μm. The bonding characteristics were also good. The same results were obtained in the test 42 days after the bathing. This indicates that the bath life has not yet been reached.
【００３０】（参考例）表１の参考例Ｎｏ．１〜２に示
すように、ヒダントイン単独の浴及びヒダントインと副
成分のｐＨ緩衝剤として、ホウ酸化合物でないピロリン
酸カリウムを添加した浴を用いて同様に銀電解剥離を行
った。(Reference Example) Reference Example No. As shown in Figs. 1 and 2, silver electrolysis was similarly performed using a bath containing hydantoin alone and a bath containing potassium pyrophosphate, which is not a boric acid compound, as a pH buffer of hydantoin and an accessory component.
【００３１】［結果］ヒダントイン単独の浴の場合には
銀表面外観および素材外観ともに良好であったが、煮沸
後素材外観は変色を示した。ヒダントインと副成分のｐ
Ｈ緩衝剤としてピロリン酸カリウムを添加した浴の場合
には、銀表面外観および素材外観ともに不良であった。
ボンディング特性も共に不良であった。これは、ヒダン
トイン等の本発明の剥離成分とホウ酸化合物との組み合
わせの重要性を意味する。建浴後４２日後の試験におい
ても、全く同じ結果であった。[Results] In the case of the bath containing only hydantoin, both the silver surface appearance and the material appearance were good, but after boiling, the material appearance showed discoloration. Hydantoin and secondary component p
In the case of a bath to which potassium pyrophosphate was added as an H buffer, both the silver surface appearance and the material appearance were poor.
Both bonding characteristics were poor. This means the importance of the combination of the release component of the present invention such as hydantoin and the boric acid compound. The same result was obtained in the test 42 days after the bathing.
【００３２】（比較例）表１の比較例Ｎｏ．１〜２に示
すような従来用いられていたコハク酸イミドを主成分と
する剥離剤浴及びそれに四ホウ酸カリウムを添加した浴
を調製した。実施例と同様に銅を素材とするリードフレ
ームのパット部分に厚さ５μｍの部分銀めっきを行った
ものをサンプルとして、上記の剥離剤浴中に浸漬して、
表１に示す剥離条件で電解剥離を行った。すなわち、ｐ
Ｈ：９、電流密度：３．０Ａ／ｄｍ2 、浴温：２５℃、
撹拌速度：１．０ｍ／秒、時間：３０秒で電解を行い不
要部分の銀の剥離を行った。(Comparative Example) Comparative Example No. A stripper bath containing succinimide as a main component and a bath to which potassium tetraborate was added as shown in Examples 1 and 2 were prepared. A sample obtained by subjecting a pad portion of a lead frame made of copper to partial silver plating with a thickness of 5 μm in the same manner as the example was immersed in the above-mentioned stripping agent bath.
Electrolytic peeling was performed under the peeling conditions shown in Table 1. That is, p
H: 9, current density: 3.0 A / dm 2 , bath temperature: 25 ° C.
Electrolysis was performed at a stirring speed of 1.0 m / sec and a time of 30 sec to peel off unnecessary silver.
【００３３】［結果］剥離後のサンプルについて同じく
評価した。建浴初期の試験では銀表面外観および素材外
観ともに良好であった。しかし、煮沸後素材外観は変色
を示した。銀剥離膜厚は、０．８μｍであった。建浴後
４２日後の試験においては、銀表面外観、素材外観とも
ムラがあり不良であった。ボンディング特性も不良とな
った。また、銀剥離膜厚は０．４μｍと著しく低下して
おり、既に浴寿命を過ぎていることがわかった。[Results] The sample after peeling was evaluated in the same manner. In the initial tests of the bath, both the silver surface appearance and the material appearance were good. However, after boiling, the material appearance showed discoloration. The silver release film thickness was 0.8 μm. In the test 42 days after the bathing, both the silver surface appearance and the material appearance were uneven and poor. The bonding characteristics were also poor. In addition, the silver peeling film thickness was remarkably reduced to 0.4 μm, and it was found that the bath life had already passed.
【００３４】[0034]
【表１】 [Table 1]
【００３５】（実施例ＩＩ）本例は銅のインヒビターを
添加した例である。表２の実施例Ｎｏ．１〜７に示すよ
うな組成の浴を調製した。銅を素材とするリードフレー
ムのパット部分に厚さ５μｍの部分銀めっきを行ったも
の（パッド部分周辺の不要部分にも銀めっき皮膜が形成
されている）をサンプルとして、上記の各剥離剤浴中に
浸漬し、表２に示す剥離条件で電解剥離を行った。すな
わち、ｐＨ：８〜１２、電流密度：３．０〜５．０Ａ／
ｄｍ2 、浴温：２５℃、撹拌速度：１．０ｍ／秒、時
間：３０秒で電解を行い不要部の銀の剥離を行った。剥
離後のサンプルについて、実施例Ｉの場合と同様に評価
を行った。(Example II) This example is an example in which a copper inhibitor is added. Example No. 2 in Table 2. Baths having compositions as shown in 1 to 7 were prepared. Each of the above release agent baths was prepared by using a sample of a lead frame made of copper in which a pad portion was subjected to partial silver plating with a thickness of 5 μm (a silver plating film was also formed on unnecessary portions around the pad portion). Then, electrolytic peeling was performed under the peeling conditions shown in Table 2. That is, pH: 8 to 12, current density: 3.0 to 5.0 A /
Electrolysis was performed at dm 2 , bath temperature: 25 ° C., stirring speed: 1.0 m / sec, and time: 30 seconds to remove unnecessary portions of silver. The sample after peeling was evaluated in the same manner as in Example I.
【００３６】［結果］電解剥離後の銀表面外観および素
材外観はともに良好であった。銀剥離膜厚は０．９〜
１．６μｍと十分な剥離性能を示した。電解剥離後のサ
ンプルを煮沸純水に１０分間浸漬した後でさえも、銀表
面外観および素材外観はともに良好であった。ボンディ
ング特性も良好であった。建浴後４２日後の試験におい
ても、全く同じ結果を得た。このことからまだ浴寿命に
は達していないことがわかる。[Results] Both the silver surface appearance and the material appearance after electrolytic peeling were good. Silver peeling film thickness is 0.9 ~
1.6 μm, sufficient peeling performance was exhibited. Even after the electrolytically stripped sample was immersed in boiling pure water for 10 minutes, both the silver surface appearance and the material appearance were good. The bonding characteristics were also good. The same results were obtained in the test 42 days after the bathing. This indicates that the bath life has not yet been reached.
【００３７】（参考例）表２の参考例Ｎｏ．１〜２に示
すように、ヒダントイン単独の浴及びヒダントインと副
成分のｐＨ緩衝剤としてピロリン酸カリウムそして銅の
インヒビターとしてベンゾトリアゾールを添加した浴を
用いて同様に銀電解剥離を行った。(Reference Example) Reference Example No. As shown in FIGS. 1 and 2, silver electrolytic stripping was similarly performed using a bath containing hydantoin alone and a bath containing potassium pyrophosphate as a pH buffer as a secondary component of hydantoin and benzotriazole as an inhibitor of copper.
【００３８】［結果］すでに述べたように、ヒダントイ
ン単独の浴の場合には銀表面外観および素材外観ともに
良好であったが、煮沸後素材外観は変色を示した。ヒダ
ントインと副成分のｐＨ緩衝剤としてピロリン酸カリウ
ムそして銅のインヒビターとしてベンゾトリアゾールを
添加した浴の場合には、銀表面外観および素材外観とも
に不良であった。ボンディング特性も不良であった。こ
れは、ヒダントイン等の本発明の剥離成分とホウ酸化合
物と銅インヒビターとの組み合わせの重要性を意味す
る。建浴後４２日後の試験においても、全く同じ結果で
あった。[Results] As described above, in the case of the bath containing only hydantoin, both the silver surface appearance and the material appearance were good, but the material appearance after boiling showed discoloration. In the case of a bath containing hydantoin and potassium pyrophosphate as a pH buffer as an accessory component and benzotriazole as an inhibitor of copper, both the silver surface appearance and the material appearance were poor. The bonding characteristics were also poor. This means the importance of the combination of the release component of the present invention such as hydantoin and the boric acid compound with the copper inhibitor. The same result was obtained in the test 42 days after the bathing.
【００３９】（比較例）表２の比較例Ｎｏ．１〜２に示
すようなコハク酸イミドを主成分とする剥離剤浴及びそ
れにｐＨ緩衝剤として四ホウ酸カリウム及び銅インヒビ
ターとしてベンゾトリアゾールを添加した浴を調製し
た。実施例と同様に銅を素材とするリードフレームのパ
ット部分に厚さ５μｍの部分銀めっきを行ったものをサ
ンプルとして、上記の剥離剤浴中に浸漬して、表２に示
す剥離条件で電解剥離を行った。すなわち、ｐＨ：９、
電流密度：３．０Ａ／ｄｍ2 、浴温：２５℃、撹拌速
度：１．０ｍ／秒、時間：３０秒で電解を行い不要部分
の銀の剥離を行った。(Comparative Example) A stripper bath containing succinimide as a main component and a bath containing potassium tetraborate as a pH buffer and benzotriazole as a copper inhibitor were prepared as shown in FIGS. A sample obtained by subjecting a pad portion of a lead frame made of copper to partial silver plating with a thickness of 5 μm in the same manner as in the example was immersed in the above-mentioned stripping agent bath and electrolyzed under the stripping conditions shown in Table 2. Peeling was performed. That is, pH: 9,
Electrolysis was performed at a current density of 3.0 A / dm 2 , a bath temperature of 25 ° C., a stirring speed of 1.0 m / sec, and a time of 30 seconds to peel off unnecessary portions of silver.
【００４０】［結果］剥離後のサンプルについて同じく
評価した。建浴初期の試験では銀表面外観および素材外
観ともに良好であった。煮沸後素材外観はコハク酸イミ
ドを主成分とする剥離剤浴では変色を示したが、それに
四ホウ酸カリウム及びベンゾトリアゾールを添加した浴
の場合には良好な外観を示した。銀剥離膜厚は、０．８
μｍであった。しかしながら、建浴後４２日後の試験に
おいては、銀表面外観、素材外観ともムラがあり不良で
あった。ボンディング特性も不良となった。また、銀剥
離膜厚は０．４μｍと著しく低下しており、既に浴寿命
を過ぎていることがわかった。[Results] The sample after peeling was evaluated in the same manner. In the initial tests of the bath, both the silver surface appearance and the material appearance were good. The material appearance after boiling showed discoloration in the release agent bath containing succinimide as a main component, but in the case of a bath to which potassium tetraborate and benzotriazole were added, good appearance was shown. The peeled silver film thickness is 0.8
μm. However, in the test 42 days after the bathing, both the silver surface appearance and the material appearance were uneven and poor. The bonding characteristics were also poor. In addition, the silver peeling film thickness was remarkably reduced to 0.4 μm, and it was found that the bath life had already passed.
【００４１】[0041]
【表２】 [Table 2]
【００４２】[0042]
【発明の効果】本発明により、銀の電解剥離剤の寿命を
従来に比べ大幅に延ばすことが可能である。また、高電
流密度での銀の剥離が可能である。ボンディング特性へ
の悪影響を防止することができる。本発明により、銅ま
たは銅合金等を被処理物とする銀の電解剥離の場合に、
電解剥離後の保管中の素材の変色あるいは腐食を防止す
ることが可能である。銀の電解剥離剤の寿命を従来に比
べ大幅に延ばし、また、高電流密度での銀の剥離を可能
としつつ、銅または銅合金等素材の変色あるいは腐食を
防止することができる。According to the present invention, the life of the silver electrolytic stripping agent can be greatly extended as compared with the conventional one. Further, silver can be peeled at a high current density. An adverse effect on the bonding characteristics can be prevented. According to the present invention, in the case of electrolytic peeling of silver using copper or a copper alloy or the like as an object to be treated,
It is possible to prevent discoloration or corrosion of the material during storage after electrolytic peeling. The service life of the silver electrolytic stripping agent can be significantly extended as compared with the conventional one, and the discoloration or corrosion of a material such as copper or a copper alloy can be prevented while silver can be separated at a high current density.
Claims (7)
５，５−ジメチルヒダントイン、シアヌル酸、６−メチ
ル−３−ピリダゾン、３−メチル−５−ピラゾロン及び
アラントインから成る群から選択される少なくとも１種
の銀の剥離成分と、（ｂ）副成分としての、ホウ酸系化
合物を含むことを特徴とする銀の電解剥離剤。(A) hydantoin as a main component;
At least one silver exfoliating component selected from the group consisting of 5,5-dimethylhydantoin, cyanuric acid, 6-methyl-3-pyridazone, 3-methyl-5-pyrazolone and allantoin; and (b) as a subcomponent An electrolytic stripping agent for silver, comprising a boric acid compound.
５，５−ジメチルヒダントイン、シアヌル酸、６−メチ
ル−３−ピリダゾン、３−メチル−５−ピラゾロン及び
アラントインから成る群から選択される少なくとも１種
の銀の剥離成分と、（ｂ）副成分としての、ホウ酸系化
合物と、更に（ｃ）界面活性剤とを含むことを特徴とす
る銀の電解剥離剤。2. (a) Hydantoin as a main component,
At least one silver exfoliating component selected from the group consisting of 5,5-dimethylhydantoin, cyanuric acid, 6-methyl-3-pyridazone, 3-methyl-5-pyrazolone and allantoin; and (b) as a subcomponent An electrolytic stripping agent for silver, comprising: a boric acid compound; and (c) a surfactant.
５，５−ジメチルヒダントイン、シアヌル酸、６−メチ
ル−３−ピリダゾン、３−メチル−５−ピラゾロン及び
アラントインから成る群から選択される少なくとも１種
の銀の剥離成分と、（ｂ）副成分としての、ホウ酸系化
合物と、（ｃ）銅のインヒビターとしての、ベンゾトリ
アゾール、ベンズイミダゾール、チオウラシル、チオバ
ルビツル酸、ベンゾチアゾール、ベンゾオキサゾール、
インダゾール、インドール、イミダゾール、イミダゾリ
ンまたはこれらの誘導体から選択された１種またはそれ
以上を更に含むことを特徴とする銀の電解剥離剤。(A) hydantoin as a main component;
At least one silver exfoliating component selected from the group consisting of 5,5-dimethylhydantoin, cyanuric acid, 6-methyl-3-pyridazone, 3-methyl-5-pyrazolone and allantoin; and (b) as a subcomponent A boric acid compound and (c) benzotriazole, benzimidazole, thiouracil, thiobarbituric acid, benzothiazole, benzoxazole as copper inhibitors;
A silver electrolytic stripping agent further comprising one or more selected from indazole, indole, imidazole, imidazoline or derivatives thereof.
５，５−ジメチルヒダントイン、シアヌル酸、６−メチ
ル−３−ピリダゾン、３−メチル−５−ピラゾロン及び
アラントインから成る群から選択される少なくとも１種
の銀の剥離成分と、（ｂ）副成分としての、ホウ酸系化
合物と、（ｃ）界面活性剤と、（ｄ）銅のインヒビター
としての、ベンゾトリアゾール、ベンズイミダゾール、
チオウラシル、チオバルビツル酸、ベンゾチアゾール、
ベンゾオキサゾール、インダゾール、インドール、イミ
ダゾール、イミダゾリンまたはこれらの誘導体から選択
された１種またはそれ以上を更に含むことを特徴とする
銀の電解剥離剤。4. (a) Hydantoin as a main component,
At least one silver exfoliating component selected from the group consisting of 5,5-dimethylhydantoin, cyanuric acid, 6-methyl-3-pyridazone, 3-methyl-5-pyrazolone and allantoin; and (b) as a subcomponent A boric acid compound, (c) a surfactant, and (d) a copper inhibitor, benzotriazole, benzimidazole,
Thiouracil, thiobarbituric acid, benzothiazole,
A silver electrolytic stripping agent further comprising one or more selected from benzoxazole, indazole, indole, imidazole, imidazoline and derivatives thereof.
濃度範囲：５〜２００ｇ／ｌ、副成分としてのホウ酸系
化合物の濃度範囲：５〜１００ｇ／ｌ、界面活性剤の濃
度範囲：０．１μｇ〜１０ｇ／ｌ、そして銅インヒビタ
ーの濃度範囲：１〜１０００ｍｇ／ｌであることを特徴
とする請求項４に記載の銀の電解剥離剤。5. A concentration range of a silver release component as a main component in a bath: 5 to 200 g / l, a concentration range of a boric acid compound as an auxiliary component: 5 to 100 g / l, and a concentration of a surfactant. The silver stripper of claim 4, wherein the range is from 0.1 µg to 10 g / l and the concentration range of the copper inhibitor is from 1 to 1000 mg / l.
処理物を、請求項１〜５のいずれか１項に記載の電解剥
離剤の浴に浸漬し、該被処理物を陽極として電解するこ
とを特徴とする、銀の電解剥離方法。6. A copper or copper alloy workpiece whose surface is silver-plated is immersed in the electrolytic stripping agent bath according to any one of claims 1 to 5, and the workpiece is used as an anode. An electrolytic stripping method for silver, comprising electrolyzing.
電流密度：０．１〜５０Ａ／ｄｍ2 及び浴温度：１０〜
６０℃の条件で攪拌下で実施することを特徴とする、請
求項６に記載の銀の電解剥離方法。7. The electrolytic peeling is performed by using a releasing agent having a pH of 7 to 14, a bath current density of 0.1 to 50 A / dm 2 and a bath temperature of 10 to 10.
The method for electrolytically stripping silver according to claim 6, wherein the method is carried out under stirring at 60 ° C.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8142304A JP2939181B2 (en) | 1995-05-31 | 1996-05-14 | Silver electrolytic peeling agent and electrolytic peeling method |
| MYPI96002021A MY114710A (en) | 1995-05-31 | 1996-05-28 | Electrolytic desilvering agents and electrolytic desilvering method |
| SG1998006213A SG74111A1 (en) | 1995-05-31 | 1996-05-30 | Electrolytic desilvering agents and electrolytic desilvering method |
| KR1019960018653A KR100251832B1 (en) | 1995-05-31 | 1996-05-30 | Electrolytic desilvering agents and electrolytic desilvering method |
| GB9611400A GB2301599B (en) | 1995-05-31 | 1996-05-31 | Electrolytic desilvering agents and electrolytic desilvering method |
| GB9823380A GB2333780A (en) | 1995-05-31 | 1996-05-31 | Electrolytic desilvering agent |
| TW085107251A TW338072B (en) | 1996-05-14 | 1996-06-14 | Lectrolytic desilvering agents and electrolytic desilvering method |
| HK98109430A HK1008687A1 (en) | 1995-05-31 | 1998-07-28 | Electrolytic desilvering agents and electrolytic desilvering method |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-155462 | 1995-05-31 | ||
| JP15546295 | 1995-05-31 | ||
| JP7-155461 | 1995-05-31 | ||
| JP15546195 | 1995-05-31 | ||
| JP8142304A JP2939181B2 (en) | 1995-05-31 | 1996-05-14 | Silver electrolytic peeling agent and electrolytic peeling method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0949100A JPH0949100A (en) | 1997-02-18 |
| JP2939181B2 true JP2939181B2 (en) | 1999-08-25 |
Family
ID=27318421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8142304A Expired - Fee Related JP2939181B2 (en) | 1995-05-31 | 1996-05-14 | Silver electrolytic peeling agent and electrolytic peeling method |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP2939181B2 (en) |
| KR (1) | KR100251832B1 (en) |
| GB (1) | GB2301599B (en) |
| HK (1) | HK1008687A1 (en) |
| MY (1) | MY114710A (en) |
| SG (1) | SG74111A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100322499B1 (en) * | 1999-06-29 | 2002-02-07 | 김 무 | Method for Stripping an unnecessary Silver Plating In Manufacturing a Lead-Frame |
| KR100429389B1 (en) * | 2001-07-23 | 2004-04-29 | 유니온스페셜티 (주) | Electrolytic Removing Agent for Silver and Process for Electrolytic Removing of Silver |
| CN109880161A (en) * | 2019-02-26 | 2019-06-14 | 张坤 | A kind of Compositional type copper resistant agent and its preparation and verification method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1162504A (en) * | 1980-11-25 | 1984-02-21 | Mobuyuki Oda | Treating tin plated steel sheet with composition containing titanium or zirconium compounds |
| JPH05311485A (en) * | 1991-12-25 | 1993-11-22 | Nikko Kinzoku Kk | Hole sealing treatment of noble metal plate material |
| JP2603800B2 (en) * | 1994-03-08 | 1997-04-23 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Silver electrolytic stripping solution and electrolytic stripping method using the same |
-
1996
- 1996-05-14 JP JP8142304A patent/JP2939181B2/en not_active Expired - Fee Related
- 1996-05-28 MY MYPI96002021A patent/MY114710A/en unknown
- 1996-05-30 KR KR1019960018653A patent/KR100251832B1/en not_active IP Right Cessation
- 1996-05-30 SG SG1998006213A patent/SG74111A1/en unknown
- 1996-05-31 GB GB9611400A patent/GB2301599B/en not_active Expired - Fee Related
-
1998
- 1998-07-28 HK HK98109430A patent/HK1008687A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| GB2301599A (en) | 1996-12-11 |
| HK1008687A1 (en) | 1999-05-14 |
| MY114710A (en) | 2002-12-31 |
| KR960041426A (en) | 1996-12-19 |
| GB9611400D0 (en) | 1996-08-07 |
| JPH0949100A (en) | 1997-02-18 |
| KR100251832B1 (en) | 2000-04-15 |
| SG74111A1 (en) | 2000-07-18 |
| GB2301599B (en) | 1999-11-10 |
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