JPS6119784A - Copper colloid catalyst solution for electroless plating and its preparation - Google Patents
Copper colloid catalyst solution for electroless plating and its preparationInfo
- Publication number
- JPS6119784A JPS6119784A JP14003184A JP14003184A JPS6119784A JP S6119784 A JPS6119784 A JP S6119784A JP 14003184 A JP14003184 A JP 14003184A JP 14003184 A JP14003184 A JP 14003184A JP S6119784 A JPS6119784 A JP S6119784A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- solution
- electroless plating
- gelatin
- polyethylene glycol
- 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
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】
（技術分野）
本発明は無電解めっき用銅コロイド触媒液およびその製
造方法に関し、％に電気絶縁物質、特にプラスチ、りを
活性化して無電解めりきＫよる金属被覆工程の準備を行
なうための銅コロイド触媒液に関するものである。Detailed Description of the Invention (Technical Field) The present invention relates to a copper colloidal catalyst solution for electroless plating and a method for producing the same, and relates to a metal coating by electroless plating K by activating an electrically insulating material, particularly plasti, and a method for producing the same. This invention relates to a copper colloidal catalyst solution for preparing a process.
（従来技術）
一般に電子工業においてはプラスチックを無電解めっき
により金属被覆し、導電化することが広く行なわれてい
る。例えばプリント配線板の製造においては銅張りエポ
キシ樹脂積層板の表面の所望の位置に貫通孔を形成した
後、貫通孔壁に無電解めっき用触媒を吸着させ、次いで
無電解銅めっき等の無電解めっきによシ貫通孔壁面に金
属被覆を行ない貫通孔壁面を導電化することが行なわれ
ている。無電解めっき用触媒としてはパラジウム金属が
一般に使用されておシバラジウム金属の貫通孔壁面への
形成は貫通孔壁面を塩化第一錫と塩化パラジウムの混合
コロイド水溶液に接触させた後水洗する。該貫通孔壁面
へはパラジウム金属と錫化合物が同時に吸着する。無電
解めっきの触媒となるためにはパラジウム金属と同時に
吸着した錫化合物を塩酸水溶液あるいはホウフッ化水素
酸溶液に浸漬して除去しパラジウム金属が露出するよう
にしなければならない。しかし上記酸水溶液に浸漬する
際錫化合物の除去と同時にパラジウム金属も除去される
場合がある。特に銅張ジェポキシ樹脂積層板の貫通孔壁
のガラス表面からはパラジウム金属が除去され易くしば
しば貫通孔壁への無電解銅めっき析出不良の原因となっ
ていた。(Prior Art) Generally, in the electronics industry, it is widely practiced to coat plastics with metals by electroless plating to make them conductive. For example, in the production of printed wiring boards, after forming through holes at desired positions on the surface of a copper-clad epoxy resin laminate, a catalyst for electroless plating is adsorbed on the walls of the through holes, and then electroless plating such as electroless copper plating is performed. The wall surfaces of the through holes are coated with metal by plating to make the walls of the through holes electrically conductive. Palladium metal is generally used as a catalyst for electroless plating, and the formation of cibaradium metal on the walls of the through-holes is carried out by bringing the walls of the through-holes into contact with a mixed colloidal aqueous solution of stannous chloride and palladium chloride, and then washing with water. Palladium metal and a tin compound are simultaneously adsorbed onto the wall surface of the through hole. In order to serve as a catalyst for electroless plating, the tin compound adsorbed at the same time as the palladium metal must be removed by immersion in an aqueous hydrochloric acid solution or a fluoroboric acid solution to expose the palladium metal. However, when immersing in the above acid aqueous solution, palladium metal may also be removed at the same time as the tin compound is removed. In particular, palladium metal is easily removed from the glass surface of the through-hole walls of copper-clad epoxy resin laminates, often causing poor electroless copper plating deposition on the through-hole walls.
（発明の目的）
本発明の目的は上記従来の無電解めっき用触媒液の欠点
を除去した新規な無電解めっき用触媒液およびその製造
方法を提供することにある。(Object of the Invention) An object of the present invention is to provide a novel catalyst solution for electroless plating that eliminates the drawbacks of the conventional catalyst solution for electroless plating, and a method for producing the same.
（発明の構成）
本発明の無電解めっき用触媒溶液は銅金属粒子の濃度が
０．３ ｔ ／ １以上と銅金属粒子１ｆ当りゼラチン
０．８を以上と平均分子量２００〜６００のポリエチレ
ングリコールを含むｐＨ２〜４の銅コロイド水溶液から
成り銅コロイド水溶液は２価の銅イオンと平均分子量２
００〜６００のポリエチレングリコールと２価の銅イオ
ン１を当り上記ポリエチレングリコールの存在下でアル
カリ熟成した０．８ｇ以上のゼラチンを含むｐＨ１〜２
、液ｓ４０〜７０℃の水溶液に２価の銅イオン１ｇ当り
１．２１以上のジメチルアミンポランを添加し、２価の
銅イオンを金属銅に還元した後、平均分子量２００〜６
００のポリエチレングリコールを添加し、該水溶液のｐ
Ｈを２〜４に調整することから製造される。(Structure of the Invention) The catalyst solution for electroless plating of the present invention has a concentration of copper metal particles of 0.3 t/1 or more, gelatin of 0.8 or more per 1f of copper metal particles, and polyethylene glycol with an average molecular weight of 200 to 600. The copper colloid aqueous solution has a pH of 2 to 4 and contains divalent copper ions and an average molecular weight of 2.
00-600 polyethylene glycol and 1 divalent copper ion, pH 1-2 containing 0.8 g or more of gelatin that has been alkali-ripened in the presence of the above polyethylene glycol.
, Add 1.21 or more dimethylamine poran per 1 g of divalent copper ions to an aqueous solution at 40 to 70°C to reduce the divalent copper ions to metallic copper, and then reduce the average molecular weight to 200 to 6.
00 polyethylene glycol is added, and the p of the aqueous solution is
It is manufactured by adjusting H to 2 to 4.
本発明の銅コロイド触媒液においてアルカリ熟成したゼ
ラチンを使用すると銅コロイドの吸着性及び安定性が著
しく向上することを見い出した。It has been found that when alkali-ripened gelatin is used in the copper colloid catalyst solution of the present invention, the adsorption and stability of copper colloids are significantly improved.
銅コロイド触媒溶液中のゼラチン濃度は銅金属粒子１を
当り０．８ｇ以上が必要であり、ゼラチンの濃度が０．
８９より減少すると銅金属粒子が凝集沈殿する。また本
発明の銅コロイド触媒液の製造において２価の銅イオン
源としては硫酸銅あるい清水酸化第二銅が使用でき、水
溶液のｐＨ調整には硫酸および水酸化ナトリウムあるい
は水酸化カリウムが使用される。２価の銅イオンをジメ
チルアミンポランで還元する際水素ガスの発生に伴ない
発泡するが、水溶液中の泡立ちを減少させ２価の銅イオ
ン還元反応を均一にするためにブチルアルコール等の消
泡性のあるアルコールを使用しても良い。本発明の平均
分子量２００〜６００のポリエチレングリコールは２価
の銅イオンのジメチルアミンポランによる還元速度をコ
ントロールし、微小銅金属粒子の生成に寄与し、その添
加量は２価の銅イオン１ｆ当り１〜２０ｆが適当である
。ポリエチレングリコールは、ゼラチンのアルカリ熟成
の際添加されるが、この場合ポリエチレングリコールは
ゼラチンのアルカリ熟成度（変性度）をコントロールす
る。アルカリ熟成したゼラチンを使用すると生成した銅
コロイドの吸着性がさらに銅コロイドの吸着性はポリエ
チレングリコール（平均分子量２００〜６００）の添加
により向上する−ことがわかった。ジメチルアミンポラ
ンによす還元された２価の銅イオンは銅金属粒子となり
、ゼラチンにより保護されコロイド粒子（銅コロイド）
を形成する。銅コロイドはｐＨ４以下で安定でありｐＨ
が４を超えると銅コロイドは凝集沈殿してしまう。銅コ
ロイドの銅張りエポキシ樹脂積層板の貫通孔壁への吸着
は銅コロイド触媒液のｐＨが２〜４で秀れそおり、また
該貫通孔壁に吸着した銅コロイドのゼラチン保護膜（銅
金属粒子を保護している膜）は水洗により容易に除去さ
れ、銅金属粒子が該貫通孔壁に残り、無電解めっき用触
媒として働く。なお銅コロイド触媒液中の銅金属粒子の
濃度は０．３ｆ／ｌ以上が適当であり、０．３ｆ／ｌよ
りも減少すると銅コロイドの吸着性が著しく減少する。The gelatin concentration in the copper colloid catalyst solution needs to be 0.8 g or more per copper metal particle, and the gelatin concentration is 0.8 g or more per copper metal particle.
When it decreases below 89, copper metal particles coagulate and precipitate. In addition, in the production of the copper colloidal catalyst solution of the present invention, copper sulfate or cupric oxide of clean water can be used as a divalent copper ion source, and sulfuric acid and sodium hydroxide or potassium hydroxide can be used to adjust the pH of the aqueous solution. Ru. When divalent copper ions are reduced with dimethylamine poran, foaming occurs due to the generation of hydrogen gas, but antifoaming such as butyl alcohol is used to reduce foaming in the aqueous solution and make the divalent copper ion reduction reaction uniform. You may also use alcohol. The polyethylene glycol of the present invention having an average molecular weight of 200 to 600 controls the rate of reduction of divalent copper ions by dimethylamine porane and contributes to the production of minute copper metal particles, and the amount added is 1f per 1f of divalent copper ions. ~20f is appropriate. Polyethylene glycol is added during alkaline ripening of gelatin, and in this case polyethylene glycol controls the alkaline ripening degree (denaturation degree) of gelatin. It has been found that when alkali-ripened gelatin is used, the adsorption of copper colloid produced is further improved by the addition of polyethylene glycol (average molecular weight 200 to 600). Divalent copper ions reduced by dimethylamine poran become copper metal particles, which are protected by gelatin and become colloidal particles (copper colloid).
form. Copper colloid is stable at pH 4 or below;
If it exceeds 4, the copper colloid will coagulate and precipitate. The adsorption of copper colloid to the through-hole walls of a copper-clad epoxy resin laminate is likely to be excellent when the pH of the copper colloid catalyst solution is 2 to 4. The film protecting the particles is easily removed by washing with water, and the copper metal particles remain on the walls of the through-holes, acting as catalysts for electroless plating. Note that the concentration of copper metal particles in the copper colloid catalyst liquid is suitably 0.3 f/l or more, and if it decreases below 0.3 f/l, the adsorption of copper colloid will be significantly reduced.
（実施例） 以下、本発明を実施例により詳細に説明する。(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例−１
ゼラチン１０２と平均分子量２００のポリエチレングリ
コール５ｆを約７００ｎｌの純水に溶解し液馬６０℃に
保持しながら２８重量−の水酸化ナトリウムを１５ｍ１
添加し、約１０分間アルカリ熟成した。次いで６０重量
％の硫酸水溶液を１５ｒｒｌ添加し、アルカリ熟成した
ゼラチン水溶液のｐＨを１．８に調整した後、硫酸銅（
ＣｕＳＯａ ・５Ｈ２０）を２４．９９溶解させた。次
に濃度１００ｆ／１のジメチルアミンボラン水溶液を１
００ｍＪＩ添加し、液温６０℃で銅イオンを完全に金属
銅に還元した。Example-1 Gelatin 102 and polyethylene glycol 5F with an average molecular weight of 200 were dissolved in approximately 700 nl of pure water, and while the solution was maintained at 60°C, 28 wt. of sodium hydroxide was added to 15 ml.
and alkali aging for about 10 minutes. Next, 15rrl of a 60% by weight sulfuric acid aqueous solution was added to adjust the pH of the alkali-ripened gelatin aqueous solution to 1.8, and then copper sulfate (
CuSOa 5H20) was dissolved at 24.99%. Next, add 1 dimethylamine borane aqueous solution with a concentration of 100 f/1.
00 mJI was added, and the copper ions were completely reduced to metallic copper at a liquid temperature of 60°C.
なお消泡剤としてブチルアルコールを２０ｍ１添加した
。次罠これらの水溶液の温度金室温まで冷却し、水溶液
の全量を純水を加えて１ｇとし銅コロイド触媒液の濃縮
液を製造した。本液中の銅金属粒子の濃度は６．３ｔ／
１．ゼラチンの濃度は１０ｆ ／ １、平均分子量２０
０のポリエチレングリコールの濃度は５０ ｆ ／ （
１である。Note that 20 ml of butyl alcohol was added as an antifoaming agent. Next, these aqueous solutions were cooled to room temperature, and the total amount of the aqueous solutions was made up to 1 g by adding pure water to produce a concentrated solution of copper colloidal catalyst solution. The concentration of copper metal particles in this liquid is 6.3t/
1. The concentration of gelatin is 10f/1, the average molecular weight is 20
The concentration of polyethylene glycol at 0 is 50 f/(
It is 1.
実施例−２
実施例−１における平均分子量２００のポリエチレング
リコールの代わりに平均分子量４００および６００ ｏ
２ 種のポリエチレングリコールを使用し、実施例−
１と同様な操作により２種の銅コロイド触媒液の濃縮液
を製造した。Example-2 Polyethylene glycol with an average molecular weight of 400 and 600 o was used instead of the polyethylene glycol with an average molecular weight of 200 in Example-1.
Example using two types of polyethylene glycol-
Concentrated liquids of two types of copper colloidal catalyst liquids were produced by the same operation as in Example 1.
実施例−３
実施例−１および実施例−２で製造した銅コロイド触媒
液と、それらの１０倍希釈液を準備し、硫酸水溶液でそ
れぞれの銅コロイド触媒液のｐＨを３．０に調整した。Example-3 The copper colloidal catalyst liquids produced in Example-1 and Example-2 and their 10-fold dilutions were prepared, and the pH of each copper colloidal catalyst liquid was adjusted to 3.0 with an aqueous sulfuric acid solution. .
これらの銅コロイド触媒液に貫通孔の形成された銅張り
エポキシ樹脂積層板を液温４０℃で１分間浸漬後、１分
間流水水洗し、次いで液温２５℃、ｐＨ＝ １３の無電
解銅めっき液に約１０分間浸漬し、貫通孔壁への無電解
銅めりきの析出性を調べた。A copper-clad epoxy resin laminate with through-holes formed in these copper colloidal catalyst solutions was immersed for 1 minute at a solution temperature of 40°C, rinsed with running water for 1 minute, and then electroless copper plated at a solution temperature of 25°C and pH = 13. The sample was immersed in the liquid for about 10 minutes, and the precipitation of electroless copper plating on the wall of the through hole was examined.
（発明の効果）
以上１本発明によυ貫通孔壁の断面観察により全ての試
料の貫通孔壁への無電解銅めっきの被覆は完全であるこ
とが確認され本発明の実用性が立証された。(Effects of the Invention) According to the above-described 1. cross-sectional observation of the through-hole walls of the present invention, it was confirmed that the electroless copper plating on the through-hole walls of all samples was completely coated, thus proving the practicality of the present invention. Ta.
＼、＼ 皿 ゛）＼\, \ Plate゛)＼
Claims (2)
子１ｇ当りゼラチン０．８ｇ以上と平均分子量２００〜
６００のポリエチレングリコールを含むｐＨ２〜４の水
溶液から成る無電解めっき用銅コロイド触媒液。(1) The concentration of copper metal particles is 0.3 g/l or more, the gelatin is 0.8 g or more per 1 g of copper metal particles, and the average molecular weight is 200 or more.
A copper colloidal catalyst solution for electroless plating consisting of an aqueous solution containing 600% polyethylene glycol and having a pH of 2 to 4.
リエチレングリコールと２価の銅イオン１ｇ当り前記ポ
リエチレングリコールの存在下でアルカリ熟成した０．
８ｇ以上のゼラチンを含むｐＨ１〜２、液温４０〜７０
℃の水溶液に２価の銅イオン１ｇ当り１．２ｇ以上のジ
メチルアミンボランを添加し、２価の銅イオンを金属銅
に還元した後、該水溶液のｐＨを２〜４に調整する工程
から成る無電解めっき用銅コロイド触媒液の製造方法。(2) Divalent copper ions and polyethylene glycol with an average molecular weight of 200 to 600, and 0.00% per gram of divalent copper ions and alkali-ripened in the presence of the polyethylene glycol.
Contains 8g or more of gelatin, pH 1-2, liquid temperature 40-70
It consists of the step of adding 1.2 g or more of dimethylamine borane per 1 g of divalent copper ions to an aqueous solution at °C to reduce the divalent copper ions to metallic copper, and then adjusting the pH of the aqueous solution to 2 to 4. A method for producing a copper colloidal catalyst liquid for electroless plating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14003184A JPS6119784A (en) | 1984-07-06 | 1984-07-06 | Copper colloid catalyst solution for electroless plating and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14003184A JPS6119784A (en) | 1984-07-06 | 1984-07-06 | Copper colloid catalyst solution for electroless plating and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6119784A true JPS6119784A (en) | 1986-01-28 |
Family
ID=15259344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14003184A Pending JPS6119784A (en) | 1984-07-06 | 1984-07-06 | Copper colloid catalyst solution for electroless plating and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6119784A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02104375A (en) * | 1988-10-14 | 1990-04-17 | Rusoo Kk | Ball preventive device of golf practice range and net device unit used thereto |
| JPH0347377A (en) * | 1989-07-14 | 1991-02-28 | Mitsui Constr Co Ltd | Chimney security curtain |
| US10071419B2 (en) * | 2008-08-29 | 2018-09-11 | Ishihara Sangyo Kaisha, Ltd. | Metallic copper dispersion, process for producing the metallic copper dispersion, electrode, wiring pattern, and coating film formed using the metallic copper dispersion, decorative article and antimicrobial article with the coating film formed thereon, and processes for producing the decorative article and the antimicrobial article |
-
1984
- 1984-07-06 JP JP14003184A patent/JPS6119784A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02104375A (en) * | 1988-10-14 | 1990-04-17 | Rusoo Kk | Ball preventive device of golf practice range and net device unit used thereto |
| JPH0347377A (en) * | 1989-07-14 | 1991-02-28 | Mitsui Constr Co Ltd | Chimney security curtain |
| US10071419B2 (en) * | 2008-08-29 | 2018-09-11 | Ishihara Sangyo Kaisha, Ltd. | Metallic copper dispersion, process for producing the metallic copper dispersion, electrode, wiring pattern, and coating film formed using the metallic copper dispersion, decorative article and antimicrobial article with the coating film formed thereon, and processes for producing the decorative article and the antimicrobial article |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| SU747437A3 (en) | Solution for activation of non-metallic surface prior to chemical metallization | |
| JPH0397873A (en) | Process for coating plastic product | |
| JP6444664B2 (en) | Electroless metallization of dielectrics with alkali-stable pyrazine derivative-containing catalysts | |
| EP2818242B1 (en) | Method for electroless metallization using catalysts containing allantoin | |
| JP2015063755A (en) | Electroless metallization of dielectric by pyrimidine derivative containing catalyst stable to alkali | |
| US9918389B2 (en) | Electroless metallization of dielectrics with alkaline stable pyrazine derivative containing catalysts | |
| US4244739A (en) | Catalytic solution for the electroless deposition of metals | |
| JP3890542B2 (en) | Method for manufacturing printed wiring board | |
| EP0191433B1 (en) | Process for manufacturing a concentrate of a palladium-tin colloidal catalyst | |
| US3674550A (en) | Method of electroless deposition of a substrate and sensitizing solution therefor | |
| JPS6119784A (en) | Copper colloid catalyst solution for electroless plating and its preparation | |
| JPS6123764A (en) | Copper colloidal catalytic solution for electroless plating and its manufacture | |
| JPS6123762A (en) | Copper colloidal catalytic solution for electroless plating and its manufacture | |
| CA2023846A1 (en) | Process for the direct metallization of a non-conducting substrate | |
| JPS6119783A (en) | Copper colloid catalyst solution for electroless plating and its preparation | |
| JPS6123763A (en) | Copper colloidal catalytic solution for electroless plating | |
| JP3093259B2 (en) | Complex compounds having oligomer or polymer properties | |
| JPS637380A (en) | Catalytic solution of copper colloid for electroless plating and its production | |
| JPS6119782A (en) | Copper colloid catalyst solution | |
| GB2253415A (en) | Selective process for printed circuit board manufacturing employing noble metal oxide catalyst. | |
| JPS6123765A (en) | Copper colloidal catalytic solution for electroless plating and its manufacture | |
| JPS61139672A (en) | Production of colloidal copper catalyst solution for electroless plating | |
| JPS634074A (en) | Catalytic solution of copper colloid for electroless plating and its production | |
| JPS62290879A (en) | Catalytic solution of copper colloid for electroless plating and its production | |
| JPS62263972A (en) | Colloidal solution for copper catalyst for electroless plating and its production |