JPS63297574A - Electroless copper plating bath - Google Patents
Electroless copper plating bathInfo
- Publication number
- JPS63297574A JPS63297574A JP13514687A JP13514687A JPS63297574A JP S63297574 A JPS63297574 A JP S63297574A JP 13514687 A JP13514687 A JP 13514687A JP 13514687 A JP13514687 A JP 13514687A JP S63297574 A JPS63297574 A JP S63297574A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- plating bath
- plating solution
- electroless copper
- copper 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.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 32
- 239000010949 copper Substances 0.000 title claims abstract description 32
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims abstract description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 26
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002932 luster Substances 0.000 abstract description 4
- JTPLPDIKCDKODU-UHFFFAOYSA-N acetic acid;2-(2-aminoethylamino)ethanol Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCO JTPLPDIKCDKODU-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001465 metallisation Methods 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、めっきの析出速度を早め、かつ、光沢のある
めっきの得られる無電解銅めっき液に関するものである
。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an electroless copper plating solution that accelerates the deposition rate of plating and provides glossy plating.
従来の技術
近年、無電解鋼めっきは、印刷配線板の製造やプラスチ
ックの金属化の分野で広く利用されている。BACKGROUND OF THE INVENTION In recent years, electroless steel plating has been widely used in the production of printed wiring boards and the metallization of plastics.
無電解銅めっき液は、銅塩、ＳＶ４の錯化剤、水酸化ア
ルカリおよび還元剤としてホルムアルデヒドやほう素化
水素等からなる水溶液よりなる。このような公知のめっ
き液から得られる析出銅は、一般に暗赤色を呈し、かつ
、電気銅めっきに比べて析出速度が比較的に遅く濃度を
高めたり、温度を高くして析出速度を早くするとめっき
液が不安定となる欠点があった。このようなめっき液を
改良する方法として、特公昭５６−５０４号公報には、
ぶつ化炭素系界面活性剤をめっき液に添加することが述
べられている。The electroless copper plating solution is an aqueous solution containing a copper salt, an SV4 complexing agent, an alkali hydroxide, and a reducing agent such as formaldehyde or hydrogen boron. Deposited copper obtained from such known plating solutions generally exhibits a dark red color and has a relatively slow deposition rate compared to electrolytic copper plating.If the concentration is increased or the temperature is increased to increase the deposition rate, There was a drawback that the plating solution was unstable. As a method for improving such plating solutions, Japanese Patent Publication No. 56-504 describes
It is mentioned that a carbonaceous surfactant is added to the plating solution.
発明が解決しようとする問題点
しかしながら、前記の方法は、めっき液の析出速度をか
なり遅くする傾向があるという問題点を有していた０本
発明は、上記の問題点に鑑みて、めっき銅の光沢に優れ
、かつ、析出速度の大きい無電解銅めっき液を提供する
ものである。Problems to be Solved by the Invention However, the above-mentioned method had a problem in that the deposition rate of the plating solution tended to be considerably slow. The purpose of the present invention is to provide an electroless copper plating solution that has excellent gloss and a high deposition rate.
問題点を解決するための手段
本発明は、上記のような欠点のない無電解銅めっき液を
提供することを意図するものであって、銅塩とその錯化
剤、水酸化アルカリおよび銅の還元剤の水溶液よりなる
従来のめっき液に、ヒドロキシエチルエチレンジアミン
三酢酸（ＨＥＤＴＡ）を含めてなることを特徴とするめ
っき液である。Means for Solving the Problems The present invention is intended to provide an electroless copper plating solution that does not have the above-mentioned drawbacks, and which consists of a copper salt, a complexing agent thereof, an alkali hydroxide, and a copper plating solution. This plating solution is characterized by containing hydroxyethylethylenediaminetriacetic acid (HEDTA) in a conventional plating solution consisting of an aqueous solution of a reducing agent.
銅塩には硫酸銅、硝酸銅、酢酸銅などの銅イオン源がい
ずれも使用可能であり、その濃度範囲は、０．００７〜
０．１５モル／ｌが有効である。銅の錯化剤には酒石酸
、若しくはその塩、あるいはエチレンジアミンテトラ酢
酸（ＥＤＴＡ） 、若しくはその塩などが用いられるが
、なかでもＥＤＴＡは常温から１００℃付近の比較的に
広い温度範囲で有効に使用できる点できわめて優れてい
る。 ＩＩ化剤の使用量は、錯イオンを十分に錯体化す
るに足る量以上であればよいが、場合によっては銅の５
〜６倍程度を用いることがある。水酸化アリカリは、め
っき液のｐＨを！ｌ］１！ｆｆするために用いるもので
そＯｐＨ域は、１１．５〜１３．０が適当である。還元
剤としては、ホルムルデヒドあるいはその代替としてバ
ラホルムアルデヒド等が０．０３〜０．７５モル／ｌの
濃度範囲が好ましい。Any copper ion source such as copper sulfate, copper nitrate, or copper acetate can be used as the copper salt, and the concentration range is 0.007 to
0.15 mol/l is effective. Tartaric acid or its salts, ethylenediaminetetraacetic acid (EDTA) or its salts are used as copper complexing agents, but EDTA is especially effective in a relatively wide temperature range from room temperature to around 100°C. It's extremely good at what it can do. The amount of the II-forming agent to be used may be at least an amount sufficient to sufficiently complex the complex ion, but in some cases, the amount of the
~6 times may be used. Alkaline hydroxide adjusts the pH of the plating solution! l]1! The appropriate OpH range for the one used for ff is 11.5 to 13.0. As the reducing agent, formaldehyde or a substitute thereof such as paraformaldehyde is preferably used in a concentration range of 0.03 to 0.75 mol/l.
本発明において、添加剤として使用するヒドロキシエチ
ルエチレンジアミン三酢＃（ＨＥＤＴＡ）は、０．０２
〜２．１ｇ／ｆにわたって使用できるが、あまり多くす
ると、めっき液が不安定になり、少なすぎると効果が不
十分となることからその濃度範囲は、０．１〜０．８ｇ
／ｊ！で銅の錯化剤であるＥＤＴＡに対してモル比で１
／１００〜Ｂ／１００の範囲である。このようなめっき
液の操作のさいの最適温度は５０〜８５℃である。In the present invention, hydroxyethylethylenediamine triacetate # (HEDTA) used as an additive is 0.02
It can be used up to 2.1g/f, but if it is too much, the plating solution will become unstable, and if it is too little, the effect will be insufficient, so the concentration range is 0.1 to 0.8g.
/j! The molar ratio is 1 to EDTA, which is a copper complexing agent.
It is in the range of /100 to B/100. The optimum temperature for operating such a plating solution is 50-85°C.
作用
本発明の無電解銅めっき液は、上記の添加剤の添加によ
って、銅の析出反応に微妙に影響することになり、めっ
き液の析出速度が大きくなり、がっ、めっき銅の色もき
わめて良好な銅光沢を存するものが得られるようになる
。Effect The addition of the above-mentioned additives to the electroless copper plating solution of the present invention subtly affects the copper precipitation reaction, increasing the deposition rate of the plating solution and greatly changing the color of the plated copper. A product with good copper luster can now be obtained.
実施例
本発明の銅めっき液は、次表に示すような特性を有する
ことが実験的に確認された。同表において、使用された
めっき基本液の組成は、硫酸銅０．０３７５モル／１．
ＥＤＴＡ０．０４モル／１．苛性ソーダ０．０３５モル
／ｌ、ホルムアルデヒド０．１２モル／１である。EXAMPLE It was experimentally confirmed that the copper plating solution of the present invention had the characteristics shown in the following table. In the same table, the composition of the base plating solution used is copper sulfate 0.0375 mol/1.
EDTA0.04 mol/1. The concentrations are 0.035 mol/l of caustic soda and 0.12 mol/1 of formaldehyde.
（以下余白）
上表において、実施例１ないし９は、本発明の添加剤を
用いた本発明の無電解銅めっき液の実施例である。比較
例１ないし５は、いずれも本発明の添加剤を欠除してい
る。(The following is a blank space) In the above table, Examples 1 to 9 are examples of the electroless copper plating solution of the present invention using the additive of the present invention. Comparative Examples 1 to 5 all lack the additive of the present invention.
発明の効果
本発明の無電解銅めっき液は、従来の銅めっき液に比較
して、析出速度が２０％以上も大きく、かつ、析出銅の
銅光沢に優れためっき銅が得られるものであり、プリン
ト配線板やプラスチックの金属化のさいの生産性に大き
く役立つとともに、外観にも優れたものが得られること
になり付加価値が大きい。Effects of the Invention The electroless copper plating solution of the present invention has a deposition rate that is 20% or more higher than that of conventional copper plating solutions, and provides plated copper with excellent copper luster in the deposited copper. This not only greatly improves productivity in the production of printed wiring boards and plastic metallization, but also provides products with excellent appearance, which has great added value.
Claims (3)
還元剤からなる水溶液に、ヒドロキシエチルエチレンジ
アミン三酢酸（ＨＥＤＴＡ）を含めてなることを特徴と
する無電解銅めっき液。(1) An electroless copper plating solution comprising hydroxyethylethylenediaminetriacetic acid (HEDTA) in an aqueous solution consisting of a copper salt, a complexing agent thereof, an alkali hydroxide, and a reducing agent for the copper salt.
の錯化剤に対してモル比で１／１００〜８／１００の範
囲である特許請求の範囲第（１）項記載の無電解銅めっ
き液。(2) The electroless copper plating solution according to claim (1), wherein the molar ratio of hydroxyethylethylenediaminetriacetic acid to the copper complexing agent is in the range of 1/100 to 8/100.
特許請求の範囲第（１）項記載の無電解銅めっき液。(3) The electroless copper plating solution according to claim (1), wherein the operating temperature of the plating solution is in the range of 50 to 85°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13514687A JPS63297574A (en) | 1987-05-29 | 1987-05-29 | Electroless copper plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13514687A JPS63297574A (en) | 1987-05-29 | 1987-05-29 | Electroless copper plating bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63297574A true JPS63297574A (en) | 1988-12-05 |
Family
ID=15144885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13514687A Pending JPS63297574A (en) | 1987-05-29 | 1987-05-29 | Electroless copper plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63297574A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5925693A (en) * | 1994-07-08 | 1999-07-20 | The Gillette Company | Aqueous correction fluids |
| JP2016516902A (en) * | 2013-03-27 | 2016-06-09 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ | Electroless copper plating solution |
-
1987
- 1987-05-29 JP JP13514687A patent/JPS63297574A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5925693A (en) * | 1994-07-08 | 1999-07-20 | The Gillette Company | Aqueous correction fluids |
| JP2016516902A (en) * | 2013-03-27 | 2016-06-09 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ | Electroless copper plating solution |
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