JPH06272077A - Gold plating bath and production of gold plated article using the same - Google Patents
Gold plating bath and production of gold plated article using the sameInfo
- Publication number
- JPH06272077A JPH06272077A JP8113893A JP8113893A JPH06272077A JP H06272077 A JPH06272077 A JP H06272077A JP 8113893 A JP8113893 A JP 8113893A JP 8113893 A JP8113893 A JP 8113893A JP H06272077 A JPH06272077 A JP H06272077A
- Authority
- JP
- Japan
- Prior art keywords
- gold
- plating bath
- gold plating
- pinhole
- production
- 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000010931 gold Substances 0.000 title claims abstract description 22
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 22
- 238000007747 plating Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 19
- 229920000209 Hexadimethrine bromide Polymers 0.000 claims description 8
- -1 polyalkylimine (PAI) Polymers 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229920000083 poly(allylamine) Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はピンホールが少なくて耐
蝕性に優れた析出皮膜を得ることができる金めっき浴及
びそれを用いた金めっき品の製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gold plating bath capable of obtaining a deposited film having few pinholes and excellent corrosion resistance, and a method for producing a gold plated product using the same.
【０００２】[0002]
【従来の技術】金めっき浴、特に硬質金めっき浴は、接
点、コネクター、プリント基板の如き優れた耐磨耗性と
耐蝕性が要求される電子部品に対して用いられる。しか
しながら、金めっきの場合は、金濃度を低下させ且つ電
流密度を高くしたとしても、析出皮膜に多くのピンホー
ルが大量に発生し、厳密な意味での耐蝕性が劣化するこ
とが知られている（表面技術協会第８１回講演大会要旨
集Ｐ１７４参照）。2. Description of the Related Art Gold plating baths, especially hard gold plating baths, are used for electronic parts such as contacts, connectors and printed circuit boards which are required to have excellent wear resistance and corrosion resistance. However, in the case of gold plating, it is known that even if the gold concentration is decreased and the current density is increased, a large number of pinholes are generated in the deposited film, and the corrosion resistance in a strict sense deteriorates. (Refer to P174 for the 81st lecture meeting of Surface Technology Association).
【０００３】[0003]
【発明が解決しようとする課題】そこで、従来より、良
好な光沢外観ならびに電気的・機械的な特性を与え、更
に耐蝕性に対し問題となる析出皮膜のピンホールを減少
せしめる為の添加剤の開発が試みられているが、今まで
のところはピンホール減少に関して十分に満足のいく性
能を示す添加剤の提案はされていない。Therefore, conventionally, an additive for imparting a good glossy appearance and electrical / mechanical properties and further reducing the pinholes of the deposited film, which is a problem for corrosion resistance, has been proposed. Although development is being attempted, so far no additives have been proposed that exhibit sufficiently satisfactory performance in terms of pinhole reduction.
【０００４】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、ピンホールの少ない良好なめっ
き膜を得るため、金への良好な連続的配位が期待できる
アミン類高分子界面活性剤の添加剤や長鎖アルキル系化
合物の封止剤による検討を加えることにより、満足のい
くピンホール減少剤を得ようとするものである。The present invention was made by paying attention to such a conventional technique, and in order to obtain a good plated film with few pinholes, an amine polymer which is expected to have good continuous coordination with gold. By adding a surfactant as an additive and a long-chain alkyl-based compound as a sealant, it is intended to obtain a satisfactory pinhole reducing agent.
【０００５】[0005]
【課題を解決するための手段】この発明に係る金めっき
浴は、上記の目的を達成するために、主鎖にＮＨX +基
をもつ高分子を、ピンホール減少剤として、めっき浴中
に０．１〜１０００ｐｐｍ（好ましくは１〜１００ｐｐ
ｍ）含有しているものである。In order to achieve the above-mentioned object, a gold plating bath according to the present invention uses a polymer having an NH X + group in its main chain as a pinhole reducing agent in the plating bath. 0.1 to 1000 ppm (preferably 1 to 100 pp
m) It is contained.
【０００６】主鎖にＮＨX + 基をもつ高分子として、好
適なものは、エトキシ化（８０％）ポリエチレンイミン
（ＰＥＩＥ）、ポリアルキルイミン（ＰＡＩ）、ポリエ
チレンイミン（ＰＥＩ）、ポリブレン（ＰＢ）の４種類
である。すなわち、例えばエトキシ化（８０％）ポリエ
チレンイミン（ＰＥＩＥ）のように、主鎖にＮＨX +基
をもつものでなければならない。尚、金めっき浴のｐＨ
は３．０〜５．０の範囲が望ましい。Suitable polymers having NH x + groups in the main chain are preferably ethoxylated (80%) polyethyleneimine (PEIE), polyalkylimine (PAI), polyethyleneimine (PEI), polybrene (PB). There are four types. That is, it must have NH x + groups in the backbone, for example, ethoxylated (80%) polyethyleneimine (PEIE). The pH of the gold plating bath
Is preferably in the range of 3.0 to 5.0.
【０００７】[0007]
【実施例】 〔めっき浴組成〕 ・ＫＡｕ（ＣＮ）2 ２．９ｇ／ｄｍ3 ・Ｃ5 Ｈ8 Ｏ7 １００ｇ／ｄｍ3 ・ＣｏＳＯ4 ・７Ｈ2 Ｏ １ｇ／ｄｍ3 Examples [Plating bath composition] KAu (CN) 2 2.9 g / dm 3 · C 5 H 8 O 7 100 g / dm 3 · CoSO 4 · 7H 2 O 1 g / dm 3
【０００８】 〔操作条件〕 ・ｐＨ ３．８ ・温度 ４０℃ ・電流密度 ２．０Ａ／ｄｍ2 ・めっき厚み ０．３μｍ[Operating conditions] -pH 3.8-Temperature 40 ° C-Current density 2.0 A / dm 2 -Plating thickness 0.3 μm
【０００９】〔有孔度測定〕上記の組成・条件の金めっ
き浴に、以下の添加剤をピンホール減少剤として添加
し、それぞれの相対有孔度（無添加のときを１００とし
たときの有孔度の値）を図１に示した。[Measurement of Porosity] To the gold plating bath having the above composition and conditions, the following additives were added as pinhole reducing agents, and their relative porosities (when no addition was taken as 100) The porosity value) is shown in FIG.
【００１０】エトキシ化（８０％）ポリエチレンイミ
ン（ＰＥＩＥ）Ethoxylated (80%) polyethyleneimine (PEIE)
【化１】 ポリアルキルイミン（ＰＡＩ）[Chemical 1] Polyalkylimine (PAI)
【化２】 ポリエチレンイミン（ＰＥＩ）[Chemical 2] Polyethyleneimine (PEI)
【化３】 ポリブレン（ＰＢ）[Chemical 3] Polybrene (PB)
【化４】 ポリアリルアミン（ＰＡＡ）[Chemical 4] Polyallylamine (PAA)
【化５】 ２−ビニルピリジン−スチレン−共重合体（ＰＶＰ
Ｓ）[Chemical 5] 2-Vinylpyridine-styrene-copolymer (PVP
S)
【化６】 塩化１−ラウリルピリジニウム（ＬＰＣ）〔参照例〕[Chemical 6] 1-laurylpyridinium chloride (LPC) [Reference example]
【化７】 [Chemical 7]
【００１１】この電気的有孔度測定は、金析出被膜が形
成されたテストピースを５％硫酸水溶液に浸漬し、地下
金属（銅）が金析出被膜のピンホールを介して溶液中に
溶出する量を電流量として測定したものである。従っ
て、この測定電流量が大きいほど有孔度（金析出被膜の
ピンホール数）は大きい。また、析出物はすべて良好な
光沢外観と電気的・機械的特性を有していた。In this electrical porosity measurement, the test piece on which the gold deposition film is formed is immersed in a 5% sulfuric acid aqueous solution, and the underground metal (copper) is eluted into the solution through the pin hole of the gold deposition film. The amount is measured as the amount of current. Therefore, the larger the measured current amount, the larger the porosity (the number of pinholes in the gold deposition film). All the deposits had good gloss appearance and electrical / mechanical properties.
【００１２】ピンホール防止剤添加の効果：この図１の
グラフからもわかるように、エトキシ化（８０％）ポ
リエチレンイミン（ＰＥＩＥ）、ポリアルキルイミン
（ＰＡＩ）は、低濃度でもピンホール防止性能が高く、
次いでポリエチレンイミン（ＰＥＩ）、ポリブレン
（ＰＢ）の順に効果があることがわかる。ポリアリル
アミン（ＰＡＡ）、２−ビニルピリジン−スチレン−
共重合体（ＰＶＰＳ）、及び塩化１−ラウリルピリジ
ニウム（ＬＰＣ）〔参照例〕を添加したもののめっき面
は、ブランクと比較して有孔度は減少していなかったた
め、図１にはデータを記載していない。ピンホール防止
効果のあった添加剤はいずれも高分子の主鎖にＮＨX +
基をもつものであり、側鎖にＮＨX + 基があるものはあ
まり効果がなかった。 Effect of Addition of Pinhole Inhibitor: As can be seen from the graph of FIG. 1, ethoxylated (80%) polyethyleneimine (PEIE) and polyalkylimine (PAI) have pinhole prevention performance even at low concentrations. high,
Next, it can be seen that polyethyleneimine (PEI) and polybrene (PB) are effective in this order. Polyallylamine (PAA), 2-vinylpyridine-styrene-
The porosity of the plated surface of the composition to which the copolymer (PVPS) and 1-laurylpyridinium chloride (LPC) [Reference Example] were added did not decrease as compared with the blank, so the data is shown in FIG. 1. I haven't. The additives that had the effect of preventing pinholes were all NH X + in the main chain of the polymer.
Those having a group and having an NH x + group in the side chain had little effect.
【００１３】析出効率：ピンホール防止効果のあったも
のに関して、析出効率と添加濃度との関係を図２に示し
た。有孔度を抑えるために添加濃度を高くすると析出効
率は低下する傾向を示すが、エトキシ化（８０％）ポ
リエチレンイミン（ＰＥＩＥ）は、ピンホール防止効果
が高いわりには、析出効率の低下が少なく、好適な添加
剤といえる。 Deposition efficiency: FIG. 2 shows the relationship between the deposition efficiency and the addition concentration for those having a pinhole prevention effect. Although the precipitation efficiency tends to decrease when the addition concentration is increased to suppress the porosity, ethoxylated (80%) polyethyleneimine (PEIE) has a high effect of preventing pinholes, but the decrease of the precipitation efficiency is small. It can be said that it is a suitable additive.
【００１４】ＡＦＭ観察：ここで、「ＡＦＭ」とは、原
子間力顕微鏡（Atomic Force Microscope ）のことであ
り、ＡＦＭは探針の先端の原子と観察試料の原子間に働
く微小な斥力を利用して、試料表面をなぞることによっ
て表面形状を観測するものである。そして、この実施例
ではピンホール防止効果をもつものに関してＡＦＭ像を
得、それに対応する相対的な表面高さヒストグラム（図
１で有孔度が大きく下がった点での濃度における）のデ
ータをとって検討したところ、有孔度の小さいめっき面
では結晶粒が小さく、全体的に平滑であることが判明し
た。また、ヒストグラムも添加剤無しのブランクと比べ
て、狭い分布となることも判明した。以上より、浴添加
剤によって結晶粒を微細化し、めっき面を平滑化するこ
とによりピンホールが防止されると考えられる。 AFM observation: Here, “AFM” is an atomic force microscope, and the AFM uses a minute repulsive force that acts between atoms at the tip of a probe and atoms at an observation sample. Then, the surface shape is observed by tracing the surface of the sample. Then, in this embodiment, an AFM image of an object having a pinhole prevention effect was obtained, and data of a corresponding relative surface height histogram (in the density at the point where the porosity greatly decreased in FIG. 1) was obtained. As a result, it was found that crystal grains were small on the plated surface having a small porosity and were smooth as a whole. It was also found that the histogram also had a narrower distribution than the blank without additives. From the above, it is considered that pinholes are prevented by refining the crystal grains by the bath additive and smoothing the plated surface.
【００１５】[0015]
【発明の効果】この発明に係る金めっき浴及びそれを用
いた金めっき品の製造方法は、以上説明してきた如き内
容のものであって、本発明のピンホール減少剤を添加す
ることにより、析出皮膜のピンホールを減少せしめて耐
蝕性を向上させると共に、析出皮膜に良好な光沢外観と
電気的・機械的特性を与えることができる。The gold plating bath and the method for producing a gold plated article using the same according to the present invention have the contents described above, and by adding the pinhole reducing agent of the present invention, It is possible to reduce the pinholes of the deposited film to improve the corrosion resistance and to give the deposited film a good gloss appearance and electrical / mechanical properties.
【図１】ピンホール減少剤として添加した時の相対有孔
度（無添加のときを１００としたときの有孔度の値）を
表すグラフである。FIG. 1 is a graph showing a relative porosity when added as a pinhole reducing agent (a value of porosity when 100 without addition).
【図２】ピンホール減少剤の添加濃度と析出効率との関
係を示すグラフである。FIG. 2 is a graph showing the relationship between the addition concentration of a pinhole reducing agent and the deposition efficiency.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鴨川 智明 千葉県野田市山崎2641東京理科大学理工学 部工業化学科内 (72)発明者 大谷 豊 千葉県野田市山崎2641東京理科大学理工学 部工業化学科内 (72)発明者 鎗田 聡明 神奈川県相模原市渕野辺３−10−13−901 (72)発明者 葛島 俊夫 神奈川県平塚市真土1061 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomoaki Kamogawa 2641 Yamazaki, Noda, Chiba Prefecture, Department of Industrial Chemistry, Faculty of Science and Engineering, Tokyo University of Science (72) Yutaka Otani 2641 Yamazaki, Noda, Chiba Prefecture, Department of Industrial Chemistry, Faculty of Science and Engineering, Tokyo University of Science (72) Inventor Satoshi Yuchida 3-10-13-901 Fuchinobe, Sagamihara-shi, Kanagawa Prefecture (72) Toshio Kuzushima 1061 Manado, Hiratsuka-shi, Kanagawa Prefecture
Claims (4)
ホール減少剤として、めっき浴中に０．１〜１０００ｐ
ｐｍ含有していることを特徴とする金めっき浴。1. A polymer having an NH X + group in its main chain as a pinhole reducing agent is added to a plating bath in an amount of 0.1 to 1000 p.
A gold plating bath containing pm.
キシ化（８０％）ポリエチレンイミン（ＰＥＩＥ）、ポ
リアルキルイミン（ＰＡＩ）、ポリエチレンイミン（Ｐ
ＥＩ）、ポリブレン（ＰＢ）、の少なくとも１種である
請求項１記載の金めっき浴。2. A polymer having an NH x + group in the main chain is ethoxylated (80%) polyethyleneimine (PEIE), polyalkylimine (PAI), polyethyleneimine (P).
The gold plating bath according to claim 1, which is at least one of EI) and polybrene (PB).
て、被めっき品の表面に金めっき処理を行うことを特徴
とする金めっき品の製造方法。3. A method of manufacturing a gold-plated product, which comprises subjecting the surface of a product to be plated to gold plating using the gold-plating bath according to claim 1.
で用いる請求項３記載の金めっき品の製造方法。4. The method for producing a gold-plated product according to claim 3, wherein the gold-plating bath is used under conditions of pH 3.0 to 5.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8113893A JPH06272077A (en) | 1993-03-17 | 1993-03-17 | Gold plating bath and production of gold plated article using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8113893A JPH06272077A (en) | 1993-03-17 | 1993-03-17 | Gold plating bath and production of gold plated article using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06272077A true JPH06272077A (en) | 1994-09-27 |
Family
ID=13738046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8113893A Pending JPH06272077A (en) | 1993-03-17 | 1993-03-17 | Gold plating bath and production of gold plated article using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06272077A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009168691A (en) * | 2008-01-17 | 2009-07-30 | Sumitomo Electric Ind Ltd | Evaluation method of pinhole |
| JP2009168692A (en) * | 2008-01-17 | 2009-07-30 | Sumitomo Electric Ind Ltd | Evaluation method of pinhole |
| CN103201788A (en) * | 2010-11-01 | 2013-07-10 | 三菱电机株式会社 | Drawing device and drawing method |
| CN106521575A (en) * | 2016-11-15 | 2017-03-22 | 惠州市力道电子材料有限公司 | Electroplating liquid of cyanide-free soft gold plating and electroplating method of electroplating liquid |
| CN106757200A (en) * | 2016-11-15 | 2017-05-31 | 惠州市力道电子材料有限公司 | The electroplate liquid and its electro-plating method of a kind of hard gold of non-cyanide plating |
-
1993
- 1993-03-17 JP JP8113893A patent/JPH06272077A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009168691A (en) * | 2008-01-17 | 2009-07-30 | Sumitomo Electric Ind Ltd | Evaluation method of pinhole |
| JP2009168692A (en) * | 2008-01-17 | 2009-07-30 | Sumitomo Electric Ind Ltd | Evaluation method of pinhole |
| CN103201788A (en) * | 2010-11-01 | 2013-07-10 | 三菱电机株式会社 | Drawing device and drawing method |
| CN106521575A (en) * | 2016-11-15 | 2017-03-22 | 惠州市力道电子材料有限公司 | Electroplating liquid of cyanide-free soft gold plating and electroplating method of electroplating liquid |
| CN106757200A (en) * | 2016-11-15 | 2017-05-31 | 惠州市力道电子材料有限公司 | The electroplate liquid and its electro-plating method of a kind of hard gold of non-cyanide plating |
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