JPH0696791B2 - Purification method of pretreatment liquid for silver plating - Google Patents
Purification method of pretreatment liquid for silver platingInfo
- Publication number
- JPH0696791B2 JPH0696791B2 JP1285940A JP28594089A JPH0696791B2 JP H0696791 B2 JPH0696791 B2 JP H0696791B2 JP 1285940 A JP1285940 A JP 1285940A JP 28594089 A JP28594089 A JP 28594089A JP H0696791 B2 JPH0696791 B2 JP H0696791B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- pretreatment liquid
- pretreatment
- precipitation
- liquid
- 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 - Lifetime
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- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、銅合金等の基材表面、例えばリードフレーム
に銀めっきを施す場合に使用した銀の置換析出防止のた
めの前処理液の浄化方法、更に詳しくは該前処理液に溶
存するCuイオンを除去する浄化方法に関する。TECHNICAL FIELD The present invention relates to a method for purifying a pretreatment liquid for preventing substitutional precipitation of silver used when silver plating is applied to the surface of a base material such as a copper alloy, for example, a lead frame. More specifically, it relates to a purification method for removing Cu ions dissolved in the pretreatment liquid.
従来技術 近年、銀より卑なる金属、例えば銅、銅合金等の素材か
ら成る電子部品材料、例えばリードフレームなどに銀め
っきを施す場合、密着性の良好なめっき皮膜を得るた
め、先ず上記基材の銅ストライクめっき処理を行った
後、高速銀めっきを行うことが一般的である。2. Description of the Related Art In recent years, when an electronic component material made of a material less base than silver, for example, a material such as copper or a copper alloy, such as a lead frame, is plated with silver, in order to obtain a plating film with good adhesion, first, the above-mentioned base material is used. It is common to perform high-speed silver plating after performing the copper strike plating process of.
しかし、この高速銀めっきに用いられる銀めっき液は、
銀濃度が非常に高いため、このような銀濃度の高いめっ
き液に、銀より卑な金属、例えば銅、銅合金などから成
る基材を浸漬すると、直ちに銀が大量に置換析出してし
まい、その結果銀めっきの密着性が損なわれるようにな
る。However, the silver plating solution used for this high-speed silver plating is
Since the silver concentration is very high, when a base material made of a metal less base than silver, such as copper or a copper alloy, is immersed in a plating solution having such a high silver concentration, a large amount of silver is immediately displaced and deposited, As a result, the adhesiveness of silver plating will be impaired.
したがって、最近では、このような銀の置換析出を防止
するための前処理が、前述した銅ストライクめっき処理
を行い、次いで水洗した後の基材に行われるようになっ
た。Therefore, recently, a pretreatment for preventing such substitutional precipitation of silver has come to be performed on the substrate after the above-mentioned copper strike plating treatment and subsequent water washing.
すなわち、上記銀めっきを密着性の良好な皮膜が形成さ
れるように行うためには、銅ストライクめっき、水洗の
後に銀の置換析出防止のための前処理を行うことが必須
となっている。That is, in order to carry out the above silver plating so that a film having good adhesion is formed, it is essential to carry out a pretreatment for preventing substitution precipitation of silver after copper strike plating and washing with water.
因に、この銀の置換析出防止のための前処理は、銀の置
換析出防止剤、例えば2-チオバルビツル酸、チオカルボ
ン酸などを含有する液に短時間浸漬することにより行わ
れる。Incidentally, the pretreatment for preventing the substitutional precipitation of silver is performed by immersing it in a liquid containing a substitutional precipitation inhibitor of silver, such as 2-thiobarbituric acid or thiocarboxylic acid, for a short time.
しかして、このような銀の置換析出防止剤を含有する前
処理液は、その前工程で行われる銅ストライクのめっき
液から持ちこまれるシアン化合物と共に、Cuイオンが混
入し、次第に蓄積してCu化合物の沈澱物を招来するに至
り、この沈澱物が上記前処理液中の銀置換析出防止剤を
吸着して該前処理液の銀の置換析出防止の効果が著しく
損われるようになる。すなわち、銀の置換析出防止液の
寿命及びその機能は上記シアン化合物とCuイオンの該防
止液への持ち込み量により大きく影響される。Therefore, the pretreatment liquid containing such a silver substitution precipitation inhibitor is mixed with Cu ions taken from the copper strike plating liquid performed in the previous step, Cu ions are mixed, and the Cu compounds are gradually accumulated to form Cu compounds. And the silver adsorption inhibitor in the pretreatment liquid is adsorbed on the pretreatment liquid, and the effect of preventing the substitution and precipitation of silver in the pretreatment liquid is significantly impaired. That is, the life and the function of the silver substitution and precipitation prevention solution are greatly influenced by the amount of the above cyan compound and Cu ions carried into the prevention solution.
本発明者は、さきに上記前処理液に無機酸又は有機酸を
添加して酸性にした液を用いることにより、銅ストライ
クめっき工程から持ち込まれるシアン化合物、例えばKC
Nを分解してHCNとして揮発除去する方法を開発した（特
願平1-244703号）。しかし、Cuイオンについては前処理
液を酸性にしたことによっては除去できないので、その
除去が銀めっき処理における課題となっている。The present inventor has previously used a liquid acidified by adding an inorganic acid or an organic acid to the above pretreatment liquid, whereby a cyanide compound introduced from the copper strike plating step, for example, KC.
We have developed a method to decompose N and volatilize it as HCN (Japanese Patent Application No. 1-244703). However, Cu ions cannot be removed by acidifying the pretreatment solution, and therefore their removal is a problem in silver plating.
発明が解決しようとする課題 本発明は、銀より卑なる金属、例えば銅、銅合金、鉄、
鉄合金、ニッケル、ニッケル合金及びこれらをめっきし
た金属から成る基材表面に銅ストライクめっきを施し、
次いで洗滌処理した後、銀の置換析出防止剤含有液で前
処理を行った後の該前処理液を陰イオン交換樹脂で処理
することにより、溶存するCuイオンを除去することを特
徴とする。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention is a metal baser than silver, for example, copper, copper alloy, iron,
Copper strike plating is applied to the surface of the base material consisting of iron alloy, nickel, nickel alloy and metal plated with these,
Then, after the washing treatment, the pretreatment with a solution containing a substitutional precipitation inhibitor of silver is performed with an anion exchange resin to remove dissolved Cu ions.
上記銀の置換析出防止前処理液中に溶存するCuイオンの
許容濃度、すなわち、Cu化合物の沈澱が生成しない濃度
はCuとして10mg/であるので、本発明では、このCu濃
度を基準として、陰イオン交換樹脂を用いて上記前処理
液中に持ち込まれたCuイオンを除去する。なお、該処理
液中の溶存Cu濃度が10mg/を越えると、液が白濁を呈
するので陰イオン交換樹脂による処理の目安とするとよ
い。The permissible concentration of Cu ions dissolved in the pretreatment liquid for preventing substitutional precipitation of silver, that is, the concentration at which precipitation of the Cu compound does not occur is 10 mg / Cu, and therefore, in the present invention, based on this Cu concentration, Cu ions brought into the pretreatment solution are removed using an ion exchange resin. When the concentration of dissolved Cu in the treatment liquid exceeds 10 mg /, the liquid becomes cloudy, so it may be used as a standard for treatment with an anion exchange resin.
本発明ではイオン交換樹脂として陰イオン交換樹脂を用
いるものであるが、陰イオン交換樹脂のCuイオンの除去
効果を陽イオン交換樹脂を対照として対比してみる。In the present invention, an anion exchange resin is used as the ion exchange resin, but the Cu ion removing effect of the anion exchange resin will be compared with the cation exchange resin as a control.
テストは両方のイオン交換樹脂を用いて、銀置換析出防
止のための処理液中の溶存Cuイオンの除去率を次に示す
試験方法に従って行った。その結果を下記表１に示す。
銀置換析出防止のための処理液中の溶存Cuイオンの除去
率を次に示す試験方法に従って行った結果を下記表１に
示す。The test was carried out using both ion exchange resins according to the test method shown below for the removal rate of dissolved Cu ions in the treatment liquid for preventing silver displacement precipitation. The results are shown in Table 1 below.
Table 1 below shows the results of the removal rate of dissolved Cu ions in the treatment liquid for preventing silver substitution precipitation according to the following test method.
試験方法 置換析出防止用液200mlに各イオン交換樹脂10mlをそれ
ぞれ添加したものにCuイオンを徐々に10mg/の濃度に
まで添加し、30分間スターラ撹拌を行った後、各イオン
交換樹脂を分離した液のCuイオンを分析した。Test method To 200 ml of the solution for displacement and precipitation prevention, 10 ml of each ion-exchange resin was added, Cu ions were gradually added to a concentration of 10 mg /, and after stirring for 30 minutes with a stirrer, each ion-exchange resin was separated. The Cu ions in the liquid were analyzed.
試験条件 置換析出防止用液： 2,2′−ジピリジル 100mg/ pH ４ 液温度 25℃ 添加Cuイオン： K3Cu（CN）４ 100g/ Cu濃度 10g/ml イオン交換樹脂： 陽イオン交換樹脂 三菱ダイヤイオンSK-1B （R-H型） 陰イオン交換樹脂 三菱ダイヤイオンSA-10A （R-OH型） 反応時間 30分 Ag浴： HS-400 浸漬温度 65℃ 浸漬時間 15秒 表にみられるとおり、陰イオン交換樹脂を用いた場合の
Cuイオン除去率が断然に高いことが確かめられた。Test conditions Replacement precipitation prevention liquid: 2,2'-dipyridyl 100 mg / pH 4 Liquid temperature 25 ° C Added Cu ion: K 3 Cu (CN) 4 100 g / Cu concentration 10 g / ml Ion exchange resin: Cation exchange resin Mitsubishi diamond Ion SK-1B (RH type) Anion exchange resin Mitsubishi Diaion SA-10A (R-OH type) Reaction time 30 minutes Ag bath: HS-400 Immersion temperature 65 ℃ Immersion time 15 seconds As shown in the table, when using anion exchange resin
It was confirmed that the Cu ion removal rate was by far the highest.
本発明において、イオン交換樹脂を用いて置換析出防止
に用いた前処理液中に溶存するCuイオンを除去するため
の実際上の作業を行うには、陰イオン交換樹脂を、ポン
プ還流配管に取り付けたカートリッジフィルターに充填
し、これに上記前処理液をポンプ還流させて陰イオン交
換樹脂と前処理液を接触させることにより、前記作業を
効果的に行うことができる。In the present invention, an anion exchange resin is attached to the pump reflux pipe in order to perform practical work for removing Cu ions dissolved in the pretreatment liquid used for prevention of displacement and precipitation using the ion exchange resin. It is possible to effectively carry out the above-mentioned operation by filling the cartridge filter with a cartridge filter and refluxing the pretreatment liquid with the cartridge to bring the anion exchange resin into contact with the pretreatment liquid.
実施例 以下実施例により本発明を具体的に説明する。EXAMPLES The present invention will be specifically described below with reference to examples.
本例では、銀置換析出防止のための前処理液中の溶存Cu
イオンの除去効果と樹脂の吸着能力を確認する目的で、
該前処理液に陰イオン交換樹脂を添加したものにCu化合
物の溶液を徐々に添加して、前処理液中の溶存Cuイオン
の濃度を経日的に分析すると共に、そのCuイオン除去に
よる効果を、銅ストライクめっき処理した金属板（銅合
金）を樹脂処理後の処理液に浸漬した後、銀めっき溶液
に漬けてAgの析出の有無により判定した。In this example, dissolved Cu in the pretreatment liquid to prevent silver substitution precipitation
For the purpose of confirming the ion removal effect and resin adsorption capacity,
A solution of a Cu compound is gradually added to the pretreatment liquid to which an anion exchange resin has been added, and the concentration of dissolved Cu ions in the pretreatment liquid is analyzed over time, and the effect of removing the Cu ions After immersing the copper strike-plated metal plate (copper alloy) in the treatment liquid after the resin treatment, it was immersed in a silver plating solution and judged by the presence or absence of Ag precipitation.
試験方法 2,2′−ジピリジル100mg/を含有し、pH4、液温25℃の
置換析出防止用液３に、陰イオン交換樹脂（三菱ダイ
ヤイオンSA-10A OH型）30mlを投入したものにK3Cu（C
N）４溶液（Cuとして4.46g/）を20mg//20〜30分の
添加速度で徐々に添加し、60分毎に置換析出防止液の白
濁の有無、該液中のCu濃度を調べた結果を表２に示す。Test method 2,3'-dipyridyl containing 100mg /, pH4, liquid temperature 25 ℃ substitution precipitation prevention liquid 3 was charged with anion exchange resin (Mitsubishi Diaion SA-10A OH type) 30ml K 3 Cu (C
N) 4 solution (4.46 g / as Cu) was gradually added at an addition rate of 20 mg // 20 to 30 minutes, and every 60 minutes, the presence or absence of turbidity of the substitution precipitation preventing solution and the Cu concentration in the solution were examined. The results are shown in Table 2.
また、60分毎に、HS-400の銀めっき浴に、銅ストライク
めっき板を、Cuイオン除去処理した銀置換析出防止液で
前処理した後、温度65℃で15秒浸漬したものについてAg
の置換析出防止効果を調べた結果も併せて表２に示す。Further, every 60 minutes, in a silver plating bath of HS-400, a copper strike plating plate was pretreated with a silver ion-precipitation-preventing solution for removing Cu ions, and then immersed for 15 seconds at a temperature of 65 ° C.
Table 2 also shows the results of examining the effect of preventing the precipitation of substitution by.
なお、表２より、陰イオン交換樹脂30mlに対しCu 2.5g
添加した時点で液は白濁沈澱を生成し、Cu 2.4g添加の
時点では白濁しないことから、樹脂30mlに対しCu 2.4g
添加の吸着量となる。したがって、樹脂１当りCu量で
80gが銅ストライクめっき工程からの持ち込み許容量と
なる。 In addition, from Table 2, Cu 2.5 g for 30 ml of anion exchange resin
The solution produced a cloudy precipitate at the time of addition, and it did not become cloudy at the time of addition of Cu 2.4 g.
It is the amount of adsorption added. Therefore, the amount of Cu per resin is
80g is the carry-in allowable amount from the copper strike plating process.
このことは、200浴が１日で20mg/の濃度になるCuを
１日に持ち込むと仮定した場合、樹脂１の寿命は 〔80g/÷（200×20mg/）日〕＝20日／‐ROH となる。This means that the life of Resin 1 is [80 g / ÷ (200 × 20 mg /) days] = 20 days / -ROH, assuming that 200 baths bring Cu to a concentration of 20 mg / day in one day. Becomes
発明の効果 以上述べたように、本発明によると、銀の置換析出防止
のための前処理液中の溶存Cu濃度が効果的に除去される
ので、該前処理液の寿命が著しく延長され、その機能も
向上するので、銀めっき処理上有益である。Effects of the Invention As described above, according to the present invention, the concentration of dissolved Cu in the pretreatment liquid for preventing the substitutional precipitation of silver is effectively removed, so that the life of the pretreatment liquid is significantly extended, Since its function is also improved, it is useful in the silver plating process.
Claims (3)
ケル合金及びこれらをめっきしたものなどの銀より卑な
る金属から成る基材表面に銀を電気めっきするに当り、
その前処理に用いた銀の置換析出防止のための前処理液
を陰イオン交換樹脂で処理して該前処理液中に溶存する
銅（Cu）イオンを除去することを特徴とする上記前処理
液の浄化方法。1. When electroplating silver on a surface of a base material made of a metal which is baser than silver, such as copper, copper alloy, iron, iron alloy, nickel, nickel alloy and those plated with these,
The above pretreatment characterized in that the pretreatment liquid used for the pretreatment for preventing substitutional precipitation of silver is treated with an anion exchange resin to remove copper (Cu) ions dissolved in the pretreatment liquid. Liquid purification method.
に記載の前処理液の浄化方法。2. A method for removing copper ions to 10 mg / l or less.
The method for purifying the pretreatment liquid according to 1.
である請求項１に記載の前処理液の浄化方法。3. The method for purifying a pretreatment liquid according to claim 1, wherein the pretreatment liquid for preventing substitutional precipitation of silver is acidic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1285940A JPH0696791B2 (en) | 1989-11-01 | 1989-11-01 | Purification method of pretreatment liquid for silver plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1285940A JPH0696791B2 (en) | 1989-11-01 | 1989-11-01 | Purification method of pretreatment liquid for silver plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03146695A JPH03146695A (en) | 1991-06-21 |
| JPH0696791B2 true JPH0696791B2 (en) | 1994-11-30 |
Family
ID=17697953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1285940A Expired - Lifetime JPH0696791B2 (en) | 1989-11-01 | 1989-11-01 | Purification method of pretreatment liquid for silver plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0696791B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101658869B1 (en) * | 2015-08-28 | 2016-09-22 | 김도현 | Illuminating apparatus with radian heat function |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5858295A (en) * | 1981-09-30 | 1983-04-06 | Electroplating Eng Of Japan Co | Pretreating solution for silver plating, silver plating method and substrate |
| JPS63223200A (en) * | 1987-03-13 | 1988-09-16 | Nippon Mining Co Ltd | Method for regenerating gold plating solution |
-
1989
- 1989-11-01 JP JP1285940A patent/JPH0696791B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03146695A (en) | 1991-06-21 |
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