JPS61139672A - Production of colloidal copper catalyst solution for electroless plating - Google Patents
Production of colloidal copper catalyst solution for electroless platingInfo
- Publication number
- JPS61139672A JPS61139672A JP26127784A JP26127784A JPS61139672A JP S61139672 A JPS61139672 A JP S61139672A JP 26127784 A JP26127784 A JP 26127784A JP 26127784 A JP26127784 A JP 26127784A JP S61139672 A JPS61139672 A JP S61139672A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- soln
- copper
- electroless plating
- bivalent
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は無電解めっき用銅コロイド触媒液の製造方法に
関し、詳しくＩ／′ｉ電気絶縁物質、特にプラスチック
を活性化して無電解めっきによる金属被覆工程の準備を
行なうだめの銅コロイド触媒液の製造方法に関するもの
である。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a copper colloidal catalyst solution for electroless plating, and more particularly to a method for activating I/'i electrical insulating materials, particularly plastics, to produce metal by electroless plating. The present invention relates to a method for producing a copper colloidal catalyst liquid for preparation for a coating process.
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。例えば印刷配線板の製造においては、銅張りエポ
キシ初詣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
無電解鋼めっき等の無電解めっきにより貫通孔壁面に金
属被覆を施し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
般に使用されており、パ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ることにより行なう。この貫
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。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 through-holes are formed at desired positions on the surface of a copper-clad epoxy laminate, an electroless plating catalyst is adsorbed onto the walls of the through-holes, and then an electroless plating process such as electroless steel plating is performed. Electrolytic plating is used to apply a metal coating to the wall surfaces of the through holes to make them electrically conductive. Palladium metal is generally used as a catalyst for electroless plating, and the formation of palladium metal on the wall surface of the through hole is carried out by bringing the wall surface of the through hole into contact with a mixed colloidal aqueous solution of stannous chloride and palladium chloride. Palladium metal and a tin compound are simultaneously adsorbed onto the wall surface of this 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.
上述した従来のパラジウム金属を用いた無電解めっき用
触媒においては、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本除去される場合がある。特に
鋼張りエ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、シばしば貫通孔壁へ
の無電解銅めっき析出不良の原因となっていた。In the conventional electroless plating catalyst using palladium metal as described above, when immersed in an acid aqueous solution, the palladium metal itself may be removed simultaneously with the removal of the tin compound. In particular, palladium metal is easily removed from the glass surface of the through-hole wall of a steel-clad epoxy resin laminate, often causing poor electroless copper plating deposition on the through-hole wall.
本発明の目的はかかる従来の欠点を除去した新規な無電
解めっき用触媒液の製造方法を提供することにある。An object of the present invention is to provide a novel method for producing a catalyst liquid for electroless plating that eliminates such conventional drawbacks.
本発明の無電解めっき用触媒液は、２価の銅イオンと平
均分子量１，０００〜１００，０００のポリエチレンダ
レコールと２価の銅イオンと銅イオン１ｇ当り上記ポリ
エチレングリコールの存在下で酸熟成した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鋼に還元
した後、さらに液温７０・ ℃以上で所望の時間熟成し
た後、水溶液のｐＨを２〜４に調整して製造される。The catalyst solution for electroless plating of the present invention is acid-ripened in the presence of divalent copper ions, polyethylene Darecol having an average molecular weight of 1,000 to 100,000, divalent copper ions, and the above-mentioned polyethylene glycol per 1 g of copper ions. 1.2 g or more of dimethylamine borane per 1 g of divalent copper ions is added to an aqueous solution containing 0.8 g or more of gelatin at a pH of 1 to 2 and a temperature of 40 to 70°C. After reducing the aqueous solution to 70.degree. C. or higher for a desired period of time, the pH of the aqueous solution is adjusted to 2 to 4 to produce the aqueous solution.
本発明の鋼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鋼あるいは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カリウムが使
用される。本発明の平均分子１ｔｘ、ｏｏｏ〜１００，
０００のポリエチレンダレコールは２価の銅イオンのジ
メチルアミンボランによる還元速度をコントロールし、
微小鋼金属粒の生成に寄与し、その添加量は２価の銅イ
オン１ｇ当り１〜２０ｇが適当である。ジメチルアミン
ボランにより還元された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。この後、未反応のジメチルアミンボラ
ンは徐々に加水分解し銅コロイド触媒液のｐＨが上昇す
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する。よって銅イオンを
完全に金属銅イオンに還元した後、これらの水溶液の温
度を７０℃以上にし、未反応のジメチルアミンボランを
完全に加水分解させることが必要である。本発明の銅コ
ロイド触媒液の製造方法によると得られた銅コロイド触
媒液は長期間安定である。In producing the steel colloidal catalyst liquid of the present invention, sulfuric acid steel or cupric hydroxide can be used as a divalent copper ion source, and sulfuric acid and potassium hydroxide are used to adjust the pH of the aqueous solution. The average molecule of the present invention 1tx, ooo ~ 100,
000 polyethylene Darecol controls the rate of reduction of divalent copper ions by dimethylamine borane,
It contributes to the formation of micro steel metal particles, and the appropriate amount of addition is 1 to 20 g per 1 g of divalent copper ions. Divalent copper ions reduced by dimethylamine borane become copper metal particles and are protected by gelatin to form colloidal particles (copper colloid). Thereafter, unreacted dimethylamine borane is gradually hydrolyzed and the pH of the copper colloid catalyst solution increases. Copper colloid is stable at pH 4 or lower, and when pH exceeds 4, copper colloid coagulates and precipitates. Therefore, after the copper ions are completely reduced to metallic copper ions, it is necessary to raise the temperature of these aqueous solutions to 70° C. or higher to completely hydrolyze unreacted dimethylamine borane. According to the method for producing a copper colloidal catalyst liquid of the present invention, the copper colloidal catalyst liquid obtained is stable for a long period of time.
以下、本発明を実施例により詳細に説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例−１
ゼラチン１０ｇと平均分子量２０，０００のポリエチレ
ングリコール５ｇを約７００ｍｔの純水に溶解し温度６
０℃に保持しなから６０ｗｔ％硫酸水溶液を１５ｍｔ添
加し、約１０分間熟成した。次いで２８ｗｔ１水酸化ナ
トリウムを２５ｍｔ添加し、熟成し九ゼラチン水溶液の
ｐＨを１．８に調整した後、硫酸鋼（ＣｕＳＯ４−５Ｈ
２０）を２４９ｇ溶解させた。Example-1 10 g of gelatin and 5 g of polyethylene glycol with an average molecular weight of 20,000 were dissolved in about 700 mt of pure water and heated to a temperature of 6.
While maintaining the temperature at 0° C., 15 mt of a 60 wt % sulfuric acid aqueous solution was added, and the mixture was aged for about 10 minutes. Next, 25mt of 28wt1 sodium hydroxide was added and aged to adjust the pH of the gelatin aqueous solution to 1.8, and then sulfuric acid steel (CuSO4-5H
20) was dissolved in 249g.
次に濃度１００ｇ／ｌのジメチルアミンボラン水溶液を
ｔｔｓｍｔ添加し、液温６０Ｃで銅イオンを完全に金属
銅に還元した。次にこれらの水溶液の温度を７５℃にし
て２時間熟成し、未反応のジメチルアミンボランを完全
に加水分解させ、更に温度を室温まで冷却し、水溶液の
容量を純水を加えて１ｔとし、銅コロイド触媒液の濃縮
液を製造した。Next, ttsm of dimethylamine borane aqueous solution having a concentration of 100 g/l was added, and the copper ions were completely reduced to metallic copper at a liquid temperature of 60C. Next, the temperature of these aqueous solutions was raised to 75°C and aged for 2 hours to completely hydrolyze unreacted dimethylamine borane, and the temperature was further cooled to room temperature, and the volume of the aqueous solutions was made up to 1 t by adding pure water. A concentrated solution of copper colloidal catalyst solution was produced.
実施例−２
実施例−１における平均分子量２０，０００のポリエチ
レングリコールの代わりに平均分子量１，０００〜１０
，０００の範囲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 1,000 to 10 was used instead of polyethylene glycol with an average molecular weight of 20,000 in Example-1.
Concentrated solutions of two types of copper colloidal catalyst solutions were produced using polyethylene glycol in the range of .,000 and in the same manner 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、硫酸水溶液で銅コ
ロイド触媒液のｐＨを２．５に調整゛した。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
脂積層板を常温で５分間浸漬した後１分間流水で水洗し
、次いで液温２５ｔ：、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っきの析
出性を調べた。Example 3 The copper colloidal catalyst liquids produced in Examples 1 and 2 and their 10-fold dilutions were prepared, and the pH of the copper colloidal catalyst liquids was adjusted to 2.5 with an aqueous sulfuric acid solution. A copper-clad epoxy resin laminate with through-holes formed in these copper colloidal catalyst solutions was immersed for 5 minutes at room temperature, then washed with running water for 1 minute, and then immersed in an electroless copper plating solution with a solution temperature of 25 tons and a pH of 13. The sample was immersed for about 10 minutes, and the precipitation of electroless copper plating on the wall of the through hole was examined.
６一
以上、本発明により貫通孔壁の凹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。6. Above all, by observing the concave surface of the through-hole walls according to the present invention, it was confirmed that the electroless copper plating on the through-hole walls of all samples was completely covered, thus proving the practicality of the present invention.
Claims (1)
のゼラチンと０．８ｇ以上の平均分子量１，０００〜１
００，０００のポリエチレングリコールを含むｐＨ１〜
２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た後、液温４０℃から７０
℃をこえない範囲で銅イオンを金属銅に還元した後、さ
らに液温７０℃以上で所望の時間熟成した後、該水溶液
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。Divalent copper ion and 0.8g or more of gelatin per 1g of divalent copper ion and 0.8g or more of average molecular weight 1,000 to 1
pH 1~ containing 00,000 polyethylene glycol
After adding 1.2 g or more of dimethylamine borane per 1 g of divalent copper ions to the aqueous solution of 2, the liquid temperature was increased from 40°C to 70°C.
A copper colloidal catalyst for electroless plating comprising the steps of reducing copper ions to metallic copper at a temperature not exceeding 70°C, further aging at a liquid temperature of 70°C or higher for a desired period of time, and adjusting the pH of the aqueous solution to 2 to 4. Method of manufacturing liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26127784A JPS61139672A (en) | 1984-12-11 | 1984-12-11 | Production of colloidal copper catalyst solution for electroless plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26127784A JPS61139672A (en) | 1984-12-11 | 1984-12-11 | Production of colloidal copper catalyst solution for electroless plating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61139672A true JPS61139672A (en) | 1986-06-26 |
Family
ID=17359580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26127784A Pending JPS61139672A (en) | 1984-12-11 | 1984-12-11 | Production of colloidal copper catalyst solution for electroless plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61139672A (en) |
-
1984
- 1984-12-11 JP JP26127784A patent/JPS61139672A/en active Pending
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