JPS6123762A - Copper colloidal catalytic solution for electroless plating and its manufacture - Google Patents

Copper colloidal catalytic solution for electroless plating and its manufacture

Info

Publication number
JPS6123762A
JPS6123762A JP14181084A JP14181084A JPS6123762A JP S6123762 A JPS6123762 A JP S6123762A JP 14181084 A JP14181084 A JP 14181084A JP 14181084 A JP14181084 A JP 14181084A JP S6123762 A JPS6123762 A JP S6123762A
Authority
JP
Japan
Prior art keywords
copper
soln
electroless plating
polyethylene glycol
ion
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
Application number
JP14181084A
Other languages
Japanese (ja)
Inventor
Takao Sato
高雄 佐藤
Kenji Kobayashi
健治 小林
Shinichi Mitsui
三井　真一
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.)
NEC Corp
Original Assignee
NEC Corp
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 NEC Corp filed Critical NEC Corp
Priority to JP14181084A priority Critical patent/JPS6123762A/en
Publication of JPS6123762A publication Critical patent/JPS6123762A/en
Pending legal-status Critical Current

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

PURPOSE:To obtain a copper colloidal catalytic soln. for electroless plating in which the metals are completely deposited on plastics by means of the electroless plating by constituting the catalytic soln. of an aq. soln. of a specified pH contg. metallic copper particles, gelatin and polyethylene glycol having a specified mol.wt. in a specified concn. CONSTITUTION:A copper colloidal catalytic soln. consisting of aq. soln. having 2-4pH is obtained by contg. >=0.3g/l concn. of metallic copper particles, >=0.8g gelatin per 1g metallic copper particles and >=0.8g polyethylene glycol having 1,000-20,000 average mol.wt. In manufacturing this soln., an aq. soln. of 1-2pH and 40-70 deg.C liquid temp. is prepared in which Cu<2+> ion, >=0.8g gelatin per 1g Cu<2+>ion and >=0.8g polyethylene glycol of the above-mentioned average mol.wt. are contained. To this soln. >=1.2g dimethylamine borane per 1g Cu<2+> ion is added and the soln. is regulated to 2-4pH after reducing Cu<2+> ion to metallic copper. When using this catalytic soln., the electroless copper deposited coating for the wall having perforated holes such as the copper-lined epoxy resin laminate sheet can be completely performed.

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
造方法に係わり、詳しくは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単備
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 more particularly, it relates to a method for activating an electrically insulating material, particularly a plastic, to enable a single metal coating process by electroless plating. This invention relates to a copper colloidal catalyst liquid for carrying out this process.

（従来技術） 一般に電子工業に於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Ｏ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
。(Prior Art) In general, 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 resin laminate, an electroless plating catalyst is adsorbed onto the walls of the through-holes, and then electroless copper plating, etc. Electroless plating is used to apply a metal coating to the wall surfaces of the through holes to make them electrically conductive.

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
水溶液に接触させた後水洗する。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。しかし前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９工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やすく、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。Palladium metal is generally used as a catalyst for electroless plating, and the formation of palladium 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 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 a hydrochloric acid solution or a fluoroboric acid solution to expose the palladium metal. However, when immersing in the 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 wall of a copper-clad 9-layer poxy resin laminate, often causing poor electroless copper plating deposition on the through-hole wall.

（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 liquid for electroless plating that eliminates the drawbacks of the conventional catalyst liquid 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液は銅金属粒子の濃度が０
．３ｇ／／以上と銅金属粒子１ｇ当りゼラチ７０．８　
ｇ以上と平均分子量ｔ、ｏｏｏ〜２０，０００のポリエ
チレングリコールを０．８ｇｇ以上む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２価の銅イオン１ｇ当り０．８ｇ以上のゼラチ
ンと平均分子ｉｌｌ、０００〜２０．０００のポリエチ
レングリコールを０．８ｇｇ以上むＰＨ１〜２．かつ液
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／ボラ／を添加し２価の銅イオ
ノを金属銅に還元した後、該水溶液のＰＨ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.
．． 3g // or more and gelatin per gram of copper metal particles 70.8
It consists of an aqueous copper colloid solution with a pH of 2 to 4 containing 0.8 g or more of polyethylene glycol with an average molecular weight of t or more and an average molecular weight of t or ooo to 20,000. PH1-2.8g or more of gelatin and polyethylene glycol with average molecular weight of 000-20.000. and 1.0 g of divalent copper ion in an aqueous solution with a liquid temperature of 40 to 70°C.
It is produced by adding 2 g or more of dimethylamine/bora/ to reduce divalent copper ion to metallic copper, and then adjusting the pH of the aqueous solution to 2 to 4.

本発明の銅コロイド触媒液の製造に於いて、２価の銅イ
オン源としては、硫酸銅あるいは水酸化第２銅が使用で
き、また水溶液の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／をジメチルアミ／ボランで還元する際水素ガスの発
生に伴い発泡するが水溶液中の泡立ちを減少させ２価の
銅イオンの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よい。In the production of the copper colloidal catalyst solution of the present invention, copper sulfate or cupric hydroxide can be used as the divalent copper ion source, and sulfuric acid and sodium hydroxide or potassium hydroxide can be used to adjust the pH of the aqueous solution. is used. When divalent copper ions are reduced with dimethylamine/borane, 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 reduction reaction of divalent copper ions uniform. Alcohol may also be used.

本発明に用いる平均分子量ｔ、ｏｏｏ〜２０，０００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
アミンボラ／による還元速度をコノトロールし、微小銅
金属粒子の生成に寄与し、その添加量Ｆｉ２価の銅イオ
ン１ｇ当ａ０．８ｇ以上が適当である。ジメチルアミン
ボラ７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。銅コロイドはＰＨ，４以下で安定であ
りＰＨが４をこえると銅コロイドは凝集沈殿してしまう
。The polyethylene glycol having an average molecular weight t, ooo ~ 20,000 used in the present invention controls the rate of reduction of divalent copper ions by dimethylamine bora/, contributes to the production of minute copper metal particles, and its addition amount Fi divalent A suitable amount is 0.8 g or more of a per 1 g of copper ions. Divalent copper ions reduced by dimethylaminebora 7 become copper metal particles, which are protected by gelatin to form colloidal particles (copper colloid). Copper colloid is stable at a pH of 4 or less, and when the pH exceeds 4, copper colloid coagulates and precipitates.

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ですぐれてお
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ｏ３ｇ／／以上が適当であり、０．３′ｇ
／／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 adsorption of copper colloid to the through-hole walls of a copper-clad epoxy resin laminate is excellent when the pH of the copper colloid catalyst solution is 2 to 4, and the gelatin protective film (copper metal 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 a catalyst for electroless plating. The appropriate concentration of copper metal particles in the copper colloidal catalyst solution is o3g// or more, and 0.3'g
When it decreases by more than //, the adsorption of copper colloid decreases significantly.

（実施例） 以下本発明を実施例により詳細に説明する。(Example) The present invention will be explained in detail below with reference to Examples.

〔実施例−１〕 ゼラチンｌＯｇｔ：約７００ｍＡの純水に添加し、液温
約ｉＯ℃で完全に溶解させた。次いで硫酸銅（Ｃｕ８０
ａ　・５）１ｚＯ）　ｔ　２４．９ｇ、平均分子量ｔ、
ｏｏ。[Example-1] Gelatin lOgt: Added to pure water at about 700 mA and completely dissolved at a liquid temperature of about iO<0>C. Next, copper sulfate (Cu80
a ・5) 1zO) t 24.9g, average molecular weight t,
oo.

のポリエチレングリコールｔｌＯｇ添加し完全に溶解さ
せた後、水溶液のＰＨを硫酸水溶液で約１．８に調整し
た。次に＃度１００ｇ／Ｖのジメチルアミノボラン水溶
液を１００ｍｊ！！添加し、液温６０℃で銅イオンを完
全に金属銅に還元した。なお、消泡剤としてブチルアル
コールｔ　２０　ｍ／添加した。After adding and completely dissolving the polyethylene glycol tlOg, the pH of the aqueous solution was adjusted to about 1.8 with an aqueous sulfuric acid solution. Next, add 100mj of dimethylaminoborane aqueous solution with # degree of 100g/V! ! The copper ions were completely reduced to metallic copper at a liquid temperature of 60°C. In addition, butyl alcohol t 20 m/m was added as an antifoaming agent.

水溶液の温度を室温まで冷却し、水溶液の容量を純水を
加え−て１１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６．３ｇ／／、ゼラチ
ンの濃度は１ｏｇ／ｌ、平均分子Ｊ！：Ｌ、０００のポ
リエチレングリコールの濃度は１０ｇ／／である。The temperature of the aqueous solution was cooled to room temperature, and the volume of the aqueous solution was brought to 11 by adding pure water to produce a concentrated solution of copper colloidal catalyst solution. The concentration of copper metal particles in this solution is 6.3 g//, the concentration of gelatin is 1 og/l, and the average molecular weight is J! The concentration of polyethylene glycol in :L,000 is 10g//.

〔実施例−２〕 実施例−ＩＫ於ける平均分生量ｔ、ｏｏｏのポリエチレ
ノグリコールの代りに平均分子量２０，０００のポリエ
チレングリコールを使用し、実施例−１と同機な操作に
より銅金属粒子の濃度６．３ｇ／／、’ゼラチンの濃度
１０ｇ／／、平均分子量２０，０００のポリエチレング
リコールの濃［１０ｇ／ｉｔ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 20,000 was used instead of polyethylene glycol with an average grain size t and ooo in Example-IK, and copper metal particles were produced by the same operation as in Example-1. A concentrated solution of copper colloidal catalyst solution was prepared with a concentration of 6.3 g//' gelatin, and a concentration of polyethylene glycol of 10 g/it with an average molecular weight of 20,000.

〔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ＰＨｔ″３０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
キシ樹脂積層板金液温４０℃で約３分間浸漬した後、１
分間流水で水洗し、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
銅めっきの析出性を調べた。以上、本発明にエリ貫通孔
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
めっきの複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。[Example-3] - The copper colloidal catalyst liquids produced in Example-1 and Example-2 and their 10-fold dilutions were prepared, and the PHt of each copper colloidal catalyst liquid was adjusted to 30 with an aqueous sulfuric acid solution. After immersing copper-clad epoxy resin laminated sheet metal with through-holes in these copper colloidal catalyst solutions for about 3 minutes at a liquid temperature of 40°C,
It was washed with running water for a minute, and then immersed in an electroless copper plating solution with a liquid temperature of 25°C and a pH of 13 for about 10 minutes to examine the deposition properties of electroless copper plating on the walls of the through holes. As described above, cross-sectional observation of the through-hole walls of the present invention confirmed that the electroless copper plating on the through-hole walls of all samples was complete, thus proving the practicality of the present invention.

代理人　弁理士　　内　原　　　晋／′−，，，ｉ・、
１、戸Agent Patent Attorney Susumu Uchihara/'-,,,i・,
1. Door

Claims (2)

【特許請求の範囲】[Claims] （１）銅金属粒子の濃度が０．３ｇ／ｌ以上と銅金属粒
子１ｇ当り０．８ｇ以上のゼラチンと０．８ｇ以上の平
均分子量１，０００〜２０，０００のポリエチレングリ
コールを含むＰＨ２〜４の水溶液からなる無電解めっき
用銅コロイド触媒液。(1) PH2-4 containing copper metal particles with a concentration of 0.3 g/l or more, 0.8 g or more gelatin per 1 g of copper metal particles, and 0.8 g or more of polyethylene glycol with an average molecular weight of 1,000-20,000. A colloidal copper catalyst solution for electroless plating consisting of an aqueous solution of （２）２価の銅イオンと２価の銅イオン１ｇ当り０．８
ｇ以上のゼラチンと０．８ｇ以上の平均分子量１，００
０〜２０，０００のポリエチレングリコールを含むＰＨ
１〜２、かつ液温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
し該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銅めっき用銅コロ
イド触媒液の製造方法。(2) Divalent copper ion and 0.8 per gram of divalent copper ion
gram or more of gelatin and 0.8g or more of average molecular weight 1,00
PH containing polyethylene glycol from 0 to 20,000
1 to 2, and 1.2 g or more of dimethylamine borane per 1 g of divalent copper ions is added to an aqueous solution with a liquid temperature of 40 to 70°C to reduce the copper ions to metallic copper, and then the pH of the aqueous solution is adjusted to 2 to 70°C. 4. A method for producing a copper colloidal catalyst solution for electroless copper plating, which comprises the steps of adjusting step 4.
JP14181084A 1984-07-09 1984-07-09 Copper colloidal catalytic solution for electroless plating and its manufacture Pending JPS6123762A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP14181084A JPS6123762A (en) 1984-07-09 1984-07-09 Copper colloidal catalytic solution for electroless plating and its manufacture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP14181084A JPS6123762A (en) 1984-07-09 1984-07-09 Copper colloidal catalytic solution for electroless plating and its manufacture

Publications (1)

Publication Number Publication Date
JPS6123762A true JPS6123762A (en) 1986-02-01

Family

ID=15300654

Family Applications (1)

Application Number Title Priority Date Filing Date
JP14181084A Pending JPS6123762A (en) 1984-07-09 1984-07-09 Copper colloidal catalytic solution for electroless plating and its manufacture

Country Status (1)

Country Link
JP (1) JPS6123762A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62290879A (en) * 1986-06-11 1987-12-17 Nec Corp Catalytic solution of copper colloid for electroless plating and its production
JPS6361404U (en) * 1986-10-13 1988-04-23
WO2013073277A1 (en) * 2011-11-14 2013-05-23 石原薬品株式会社 Pretreatment solution for electroless copper plating, and electroless copper plating method
WO2015118907A1 (en) * 2014-02-07 2015-08-13 石原ケミカル株式会社 Aqueous copper colloid catalyst solution for electroless copper plating and electroless copper plating method
JP2016151056A (en) * 2015-02-19 2016-08-22 石原ケミカル株式会社 Copper colloid catalyst liquid for electroless copper plating and electroless copper plating method

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62290879A (en) * 1986-06-11 1987-12-17 Nec Corp Catalytic solution of copper colloid for electroless plating and its production
JPS6361404U (en) * 1986-10-13 1988-04-23
WO2013073277A1 (en) * 2011-11-14 2013-05-23 石原薬品株式会社 Pretreatment solution for electroless copper plating, and electroless copper plating method
WO2015118907A1 (en) * 2014-02-07 2015-08-13 石原ケミカル株式会社 Aqueous copper colloid catalyst solution for electroless copper plating and electroless copper plating method
CN105121701A (en) * 2014-02-07 2015-12-02 石原化学株式会社 Aqueous copper colloid catalyst solution for electroless copper plating and electroless copper plating method
CN105121701B (en) * 2014-02-07 2018-09-28 石原化学株式会社 Electroless copper water system copper colloid catalyst liquid and electroless copper plating method
JP2016151056A (en) * 2015-02-19 2016-08-22 石原ケミカル株式会社 Copper colloid catalyst liquid for electroless copper plating and electroless copper plating method
WO2016132786A1 (en) * 2015-02-19 2016-08-25 石原ケミカル株式会社 Copper colloid catalyst solution for electroless copper plating and electroless copper plating method

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