JP2529021B2 - Cyan-based gold plating solution containing gold replacement / electrolytic corrosion inhibitor - Google Patents

Cyan-based gold plating solution containing gold replacement / electrolytic corrosion inhibitor

Info

Publication number
JP2529021B2
JP2529021B2 JP2226460A JP22646090A JP2529021B2 JP 2529021 B2 JP2529021 B2 JP 2529021B2 JP 2226460 A JP2226460 A JP 2226460A JP 22646090 A JP22646090 A JP 22646090A JP 2529021 B2 JP2529021 B2 JP 2529021B2
Authority
JP
Japan
Prior art keywords
gold
plating solution
electrolytic corrosion
cyan
gold plating
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
Application number
JP2226460A
Other languages
Japanese (ja)
Other versions
JPH04110488A (en
Inventor
明秀 船木
文雄 脇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Electroplating Engineers of Japan Ltd
Original Assignee
Electroplating Engineers of Japan Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Electroplating Engineers of Japan Ltd filed Critical Electroplating Engineers of Japan Ltd
Priority to JP2226460A priority Critical patent/JP2529021B2/en
Publication of JPH04110488A publication Critical patent/JPH04110488A/en
Application granted granted Critical
Publication of JP2529021B2 publication Critical patent/JP2529021B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Description

【発明の詳細な説明】 <産業上の利用分野> この発明は金の置換・電食防止剤を含んだシアン系の
金メッキ液に関するものである。
DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a cyan gold plating solution containing a gold replacement / electrolytic corrosion inhibitor.

<従来の技術> 従来、セラミックパッケージ等の表面処理は、金メッ
キ対象部位であるタングステン(又はモリブデン)−マ
ンガン等のメタライズ面にまずニッケルメッキを行い、
リードのロウ付けを行った後に、更にニッケルメッキを
行い、一定の平滑度を得た上で、熱処理し、最終的に金
メッキ処理を行っていた(特公昭62−43343号公報参
照)。
<Prior Art> Conventionally, for surface treatment of a ceramic package or the like, nickel plating is first performed on a metallized surface of tungsten (or molybdenum) -manganese or the like which is a target portion for gold plating,
After brazing the leads, nickel plating was further performed to obtain a certain degree of smoothness, heat treatment, and finally gold plating treatment (see Japanese Patent Publication No. 62-43343).

このようにセラミックパッケージには表面処理用とし
て高価な金が用いられるため、コストダウンを考える場
合、この金の使用量を如何に低減させるかが問題とな
る。
As described above, expensive gold is used for the surface treatment of the ceramic package. Therefore, when considering cost reduction, how to reduce the amount of gold used becomes a problem.

<発明が解決しようとする課題> ところが、セラミックパッケージのような部品には、
電解メッキのために電気導通状態とした前記メタライズ
面の他にも「金属部」が存在する。すなわち、セラミッ
クパッケージの型式等を表示するためのマーカー部がそ
れである。そのマーカー部は電解メッキを意図していな
いため電気的に非導通状態(フリーパターン)となって
いる。このマーカー部はセラミックパッケージに1ケ所
設けられており、その形態(形状・サイズ・位置)はセ
ラミックパッケージのメーカーにより異なっている。
<Problems to be solved by the invention> However, in parts such as ceramic packages,
In addition to the metallized surface that has been brought into an electrically conductive state for electrolytic plating, there are "metal parts". That is, this is the marker portion for displaying the model of the ceramic package and the like. Since the marker portion is not intended for electrolytic plating, it is electrically non-conductive (free pattern). The marker portion is provided at one place on the ceramic package, and its form (shape, size, position) differs depending on the manufacturer of the ceramic package.

このマーカー部の表面状態は、一般的にタングステン
(又はモリブテン)−マンガン面か、或いはニッケルメ
ッキ面とされている。そして、前記の金メッキ対象とし
てのメタライズ面に金メッキ処理を行う場合には、この
マーカー部にも金メッキ液が接触することになる。この
時に、マーカー部表面の金属が金メッキ液により溶かさ
れ金メッキ液中の金が置換により無電解で付着する「置
換現象」が起こることとなる。また、長時間メッキ液に
浸漬しておくと、前記置換による無電解金メッキ層の下
地であるマーカー部の溶出が更に進み、終いには前記置
換による無電解金メッキ層ごとマーカー部が大量に溶け
出してしまう「電食現象」を起こすこととなる。最悪の
場合は、マーカー部が全部溶けて無くなってしまうこと
もあり得る。
The surface state of the marker portion is generally a tungsten (or molybdenum) -manganese surface or a nickel-plated surface. When the metallized surface to be gold-plated is subjected to the gold-plating treatment, the gold-plating liquid also comes into contact with the marker portion. At this time, a "replacement phenomenon" occurs in which the metal on the surface of the marker portion is melted by the gold plating solution and the gold in the gold plating solution is electrolessly attached due to the replacement. In addition, if it is immersed in the plating solution for a long time, the marker portion, which is the base of the electroless gold plating layer due to the replacement, further elutes, and at the end, a large amount of the marker portion melts together with the electroless gold plating layer due to the replacement. This will cause the "electrolytic corrosion phenomenon" to occur. In the worst case, there is a possibility that the marker part will melt and disappear.

このようにメッキ対象でない不要部(マーカー部)に
金が置換して付着することはコスト的に不利となるだけ
でなく、マーカー部がリードの接近位置に設けられてい
るような場合はマーカー部に付着した金がリードに接触
し、セラミックパッケージの本来的な性能にも悪影響を
及ぼすおそれがある。更に、マーカー部が電食により多
く溶け出してしまっては、セラミックパッケージとして
は不良品となり出荷できなくなる。
As described above, it is not costly to replace and attach gold to unnecessary portions (marker portions) that are not to be plated, and in the case where the marker portions are provided close to the leads, the marker portion The gold attached to the lead may come into contact with the leads, and may adversely affect the original performance of the ceramic package. Furthermore, if the marker portion melts out due to electrolytic corrosion, it becomes a defective ceramic package and cannot be shipped.

このような金の置換・電食の防止を必要とする部品と
しては、セラミックパッケージに限定されず、トランジ
スタヘッダやプリント配線基板等の如きパターン金メッ
キを行うものであって、電気的に非導通のフリーパター
ンを有するもの全てが含まれる。また、そのフリーパタ
ーンがニッケル、鉄、ニッケル鉄合金、銅、銅合金など
の場合に特に置換・電食が発生しやすい。
Parts requiring such replacement of gold and prevention of electrolytic corrosion are not limited to ceramic packages, but are those that perform patterned gold plating such as transistor headers and printed wiring boards, and are electrically non-conductive. All that have free patterns are included. Further, when the free pattern is nickel, iron, nickel-iron alloy, copper, copper alloy, or the like, substitution and electrolytic corrosion are particularly likely to occur.

この発明はこのような従来の技術に着目してなされた
ものであり、電気的に非導通状態となっている金属部
(フリーパターン)に金が置換して付着したり、或いは
該金属部が電食により溶けて無くなったりすることを防
止することができる金の置換・電食防止剤を含んだシア
ン系の金メッキ液を提供せんとするものである。
The present invention has been made by paying attention to such a conventional technique. Gold replaces and adheres to a metal part (free pattern) which is in an electrically non-conductive state, or the metal part is It is intended to provide a cyan-based gold plating solution containing a gold substitution / electrolytic corrosion inhibitor that can be prevented from melting and disappearing due to electrolytic corrosion.

<課題を解決するための手段> この発明に係る金の置換・電食防止剤は一種又は二種
以上のメルカプト化合物から成るものである。このメル
カプト化合物を金メッキ液中に添加することにより、電
気的に導通されていないフリーパターンの表面にメルカ
プト化合物が保護膜を形成することとなり、フリーパタ
ーンへの置換・電食作用が防止されることとなる。
<Means for Solving the Problems> The gold substitution / electrolytic corrosion inhibitor according to the present invention comprises one or more mercapto compounds. By adding this mercapto compound to the gold plating solution, the mercapto compound forms a protective film on the surface of the free pattern that is not electrically conducted, and the substitution and electrolytic corrosion action on the free pattern are prevented. Becomes

この発明における好適なメルカプト化合物としては、
メルカプト酢酸、メルカプト安息香酸、チオリンゴ酸、
2−メルカプトベンゾチアゾール、チオグリコール酸ア
ンモニウム、2−チオウラシルなどを挙げることができ
る。これらメルカプト化合物は一種類で使用しても良い
が、二種類以上のメルカプト化合物を混合することによ
り置換・電食防止効果の更なる向上が期待できる。
Suitable mercapto compounds in the present invention include:
Mercaptoacetic acid, mercaptobenzoic acid, thiomalic acid,
2-Mercaptobenzothiazole, ammonium thioglycolate, 2-thiouracil and the like can be mentioned. These mercapto compounds may be used alone, but by mixing two or more kinds of mercapto compounds, further improvement of the substitution / electrolytic corrosion preventing effect can be expected.

そして、このメルカプト化合物は、シアン系の金メッ
キ液に少しでも含まれていれば効果がある。しかし、こ
のメルカプト化合物は、金メッキ液中に遊離シアンが存
在する場合だけ機能する。高い液温により遊離シアンが
全て飛んでしまったような金メッキ液では、たとえこの
メルカプト化合物を添加しても効果を期待することがで
きない。従って、金メッキの開始時点において、遊離シ
アンを増やすために金メッキ液に0.05〜0.1g/程度の
シアン化カリウムを別途添加したり、またメルカプト化
合物だけを別に添加したりすることにより、メッキ開始
当初の置換・電食防止効果を高めるようにすることもで
きる。
This mercapto compound is effective as long as it is contained in the cyan gold plating solution. However, this mercapto compound only works if free cyan is present in the gold plating solution. Even if this mercapto compound is added, no effect can be expected with a gold plating solution in which all the free cyan has been blown off due to the high solution temperature. Therefore, at the start of gold plating, 0.05 to 0.1 g / potassium cyanide is separately added to the gold plating solution to increase the amount of free cyan, or only the mercapto compound is added separately, so that the replacement at the beginning of plating It is also possible to enhance the effect of preventing electrolytic corrosion.

<実 施 例> 以下この発明の好適な実施例を説明する。<Examples> Hereinafter, preferred examples of the present invention will be described.

メッキサンプルとしては、金メッキ対象であるメタラ
イズ面(表面にニッケルメッキ済み)とメッキ不要部と
してのマーカー部を有するセラミックパッケージを使用
した。そして、金メッキ液としては以下の如き二種類の
メルカプト化合物(※印)を添加した金メッキ液(A)
と、この金メッキ液からメルカプト化合物を削除した通
常の金メッキ液(B)を用いて、以下のような操作条件
で金の電解メッキを3.7μmの厚さで行った。
As the plating sample, a ceramic package having a metallized surface to be gold-plated (the surface of which was nickel-plated) and a marker portion as a plating-free portion was used. And as the gold plating liquid, the following two kinds of mercapto compounds (*) are added to the gold plating liquid (A)
Using the usual gold plating solution (B) obtained by removing the mercapto compound from this gold plating solution, gold electroplating was performed to a thickness of 3.7 μm under the following operating conditions.

金メッキ液組成(A) ・シアン化金カリウム 12g/ ・クエン酸三カリウム 150g/ ※チオグリコール酸アンモニウム 0.05g/ (メルカプト化合物No.1) ※2−チオウラシル 0.2g/ (メルカプト化合物No.2) 操作条件 ・pH 6.0 ・温 度 65℃ ・電流密度 0.2A/dm2 ・時 間 30分 そして、それぞれの金メッキ液(A)(B)でメタラ
イズ面を金メッキした場合におけるマーカー部表面の状
態を5分おきに調べ、その評価を以下の表に示した。
Gold plating liquid composition (A) -Kold gold cyanide 12g / -Tripotassium citrate 150g / * Ammonium thioglycolate 0.05g / (Mercapto compound No.1) * 2-Thiouracil 0.2g / (Mercapto compound No.2) Conditions ・ pH 6.0 ・ Temperature 65 ℃ ・ Current density 0.2A / dm 2・ Time 30 minutes And the state of the marker surface when the metallized surface is gold plated with each gold plating solution (A) and (B) is 5 minutes. The results are shown in the table below.

結果は、表に示されている如く、メルカプト化合物を
添加した金メッキ液(A)の方では「置換」も「電食」
は全く認められなかった。これに対し、メルカプト化合
物を添加しない金メッキ液(B)の方では、メッキ開始
当初の5分時点では金が無電解で付着する「置換」が発
生し、そして10分を過ぎてからは、前記置換で付着した
金ごとマーカー部が大量に溶け出す「電食」の発生が確
認された。
The results show that, as shown in the table, "replacement" and "electrolytic corrosion" were observed in the gold plating solution (A) containing the mercapto compound.
Was not recognized at all. On the other hand, in the case of the gold plating solution (B) to which the mercapto compound was not added, "replacement" in which gold was electrolessly adhered at the time of 5 minutes at the beginning of plating, and after 10 minutes, It was confirmed that “electrolytic corrosion” occurred, in which a large amount of the marker portion melted together with the gold attached by the substitution.

<発明の効果> この発明に係る金の置換・電食防止剤を含んだシアン
系の金メッキ液は、以上説明した如き内容のものであっ
て、電気的に非導通状態とされた金属部に対する金の置
換及び電食を確実に防止することができる。従って、セ
ラミックパッケージのようにメッキ不要部としてのマー
カー部を有するような電子部品を金メッキする場合に好
適である。
<Effects of the Invention> The cyan gold plating solution containing the gold displacement / electrolytic corrosion inhibitor according to the present invention has the content as described above, and is suitable for the electrically non-conductive metal part. Gold replacement and electrolytic corrosion can be reliably prevented. Therefore, it is suitable for gold-plating an electronic component such as a ceramic package having a marker portion that does not require plating.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】メルカプト酢酸、メルカプト安息香酸、チ
オリンゴ酸、2−メルカプトベンゾチアゾール、チオグ
リコール酸アンモニウム、2−チオウラシルの群から選
ばれた一種又は二種以上のメルカプト化合物から成る金
の置換・電食防止剤を含んだシアン系の金メッキ液。
1. Gold substitution / electricity consisting of one or more mercapto compounds selected from the group consisting of mercaptoacetic acid, mercaptobenzoic acid, thiomalic acid, 2-mercaptobenzothiazole, ammonium thioglycolate and 2-thiouracil. Cyan-based gold plating solution containing food inhibitor.
JP2226460A 1990-08-30 1990-08-30 Cyan-based gold plating solution containing gold replacement / electrolytic corrosion inhibitor Expired - Lifetime JP2529021B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2226460A JP2529021B2 (en) 1990-08-30 1990-08-30 Cyan-based gold plating solution containing gold replacement / electrolytic corrosion inhibitor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2226460A JP2529021B2 (en) 1990-08-30 1990-08-30 Cyan-based gold plating solution containing gold replacement / electrolytic corrosion inhibitor

Publications (2)

Publication Number Publication Date
JPH04110488A JPH04110488A (en) 1992-04-10
JP2529021B2 true JP2529021B2 (en) 1996-08-28

Family

ID=16845447

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2226460A Expired - Lifetime JP2529021B2 (en) 1990-08-30 1990-08-30 Cyan-based gold plating solution containing gold replacement / electrolytic corrosion inhibitor

Country Status (1)

Country Link
JP (1) JP2529021B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10577704B2 (en) 2015-06-26 2020-03-03 Metalor Technologies Corporation Electrolytic hard gold plating solution substitution inhibitor and electrolytic hard gold plating solution including same

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6736954B2 (en) * 2001-10-02 2004-05-18 Shipley Company, L.L.C. Plating bath and method for depositing a metal layer on a substrate
JP2004176171A (en) * 2002-09-30 2004-06-24 Shinko Electric Ind Co Ltd Non-cyanogen type electrolytic solution for plating gold
JP2005256140A (en) * 2004-03-15 2005-09-22 C Uyemura & Co Ltd Gold plating bath
US8608931B2 (en) * 2009-09-25 2013-12-17 Rohm And Haas Electronic Materials Llc Anti-displacement hard gold compositions
CN104233385A (en) * 2014-10-22 2014-12-24 华文蔚 Electroplating liquid for non-cyanide plating gold by thiazole and electroplating method thereof
EP4245893A1 (en) * 2022-03-15 2023-09-20 Université de Franche-Comté Gold electroplating solution and its use for electrodepositing gold with an aged appearance

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62218594A (en) * 1986-03-19 1987-09-25 Shinko Electric Ind Co Ltd Pretreating solution for gold plating and gold plating solution

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10577704B2 (en) 2015-06-26 2020-03-03 Metalor Technologies Corporation Electrolytic hard gold plating solution substitution inhibitor and electrolytic hard gold plating solution including same

Also Published As

Publication number Publication date
JPH04110488A (en) 1992-04-10

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