KR101807696B1 - Aqueous copper colloid catalyst solution and electroless copper plating method for the electroless copper plating - Google Patents

Aqueous copper colloid catalyst solution and electroless copper plating method for the electroless copper plating Download PDF

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KR101807696B1
KR101807696B1 KR1020177013993A KR20177013993A KR101807696B1 KR 101807696 B1 KR101807696 B1 KR 101807696B1 KR 1020177013993 A KR1020177013993 A KR 1020177013993A KR 20177013993 A KR20177013993 A KR 20177013993A KR 101807696 B1 KR101807696 B1 KR 101807696B1
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copper
acid
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에이 우치다
카오루 타나카
아이 카와바타
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이시하라 케미칼 가부시키가이샤
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Abstract

계면활성제의 함유액에 비도전성 기판을 침지하여 예비 흡착촉진처리를 한 후, (A)가용성 구리염과 (B)환원제와 (C)콜로이드 안정제를 함유하며, 상기 성분(A)와 (C)의 함유 중량비율을 특정화하고, 계면활성제를 함유하지 않거나 혹은 소량으로 억제한 무전해 구리도금용 수계 구리 콜로이드 촉매액으로 비도전성 기판에 촉매를 부여하고, 무전해 구리도금을 실시함에 따라, 촉매액의 경시안정성이 양호하다. 또한 흡착촉진 예비처리에 의하여, 촉매 활성을 증강시킨 후, 촉매 부여하고 무전해 도금을 하므로, 석출되는 구리피막의 균일성과 석출 불균일의 발생 방지에 뛰어나다.(A), (B), (C), and (C) a colloidal stabilizer, wherein the components (A) and (C) are mixed with a surfactant, By adding a catalyst to a non-conductive substrate using an aqueous copper colloid catalyst solution for electroless copper plating containing no surfactant or a small amount of surfactant and performing electroless copper plating, The stability with time is good. Further, since the catalytic activity is enhanced by the adsorption promoting preliminary treatment, the catalyst is provided and the electroless plating is performed, which is excellent in the uniformity of the deposited copper film and prevention of occurrence of uneven deposition.

Description

무전해 구리도금용 수계 구리 콜로이드 촉매액 및 무전해 구리도금 방법{AQUEOUS COPPER COLLOID CATALYST SOLUTION AND ELECTROLESS COPPER PLATING METHOD FOR THE ELECTROLESS COPPER PLATING}FIELD OF THE INVENTION [0001] The present invention relates to a copper-colloidal catalyst solution and an electroless copper plating method for an electroless copper plating,

본 발명은, 비도전성 기판에 무전해 구리도금을 실시할 때, 전처리로서의 촉매 부여를 하기 위한 수계 구리 콜로이드 촉매액 및 당해 무전해 구리도금 방법에 관하며, 구리 촉매액의 경시 안정성이 우수함과 더불어, 양호한 균일성 및 얼룩(불균일함) 없는 외관의 구리 피막을 형성할 수 있는 방법을 제공한다.The present invention relates to an aqueous copper colloid catalyst solution for imparting a catalyst as a pretreatment when electroless copper plating is performed on a non-conductive substrate and the electroless copper plating method, and furthermore, the stability of the copper catalyst solution with respect to time is excellent, , A method of forming a copper film having an outer appearance with good uniformity and unevenness (unevenness).

구리 또는 구리 합금기판을 비롯하여, 특히 유리 에폭시 수지, 유리 폴리이미드 수지, 에폭시 수지, 폴리이미드 수지, 폴리카보네이트 수지, ABS 수지, PET 수지 등의 수지기판, 유리 기판, 세라믹 기판 등의 비도전성 기판 상에 무전해 구리도금을 실시하기 위하여, 먼저 기판 상에 팔라듐, 은, 백금 등의 귀금속을 흡착시켜 이것을 촉매핵으로 한 후, 이 촉매핵을 통해 무전 해 구리도금액으로 기판 상에 구리 피막을 석출시키는 방식이 일반적이다.A resin substrate such as a glass epoxy resin, a glass polyimide resin, an epoxy resin, a polyimide resin, a polycarbonate resin, an ABS resin, and a PET resin, a non-conductive substrate such as a glass substrate and a ceramic substrate In order to perform electroless copper plating, a noble metal such as palladium, silver, or platinum is first adsorbed on a substrate, which is used as a catalyst nucleus, and a copper film is deposited on the substrate with the electroless copper plating solution through the catalyst nucleus .

한편, 귀금속 촉매를 사용하지 않고, 가격이 저렴한 구리, 니켈, 코발트 등의 특정 금속을 사용한 촉매부여 방식도 있으며, 당해 특정 금속의 촉매액에서는 가용성 금속염을 환원제로 처리하여 금속 콜로이드 입자를 생성시키고, 이를 촉매핵으로 하는 것이 기본 원리이다.On the other hand, there is a catalyst addition method using a specific metal such as copper, nickel, cobalt or the like, which is inexpensive and does not use a noble metal catalyst. In the catalyst solution of the specific metal, the soluble metal salt is treated with a reducing agent to produce metal colloid particles, The basic principle is to use this as a catalyst nucleus.

이 중 수계 구리 콜로이드 촉매액의 종래기술을 들면 다음과 같다.Among them, the conventional aqueous copper colloid catalyst solution is as follows.

(1) 특허문헌 1(일본공개특허 1990-093076호 공보, SANKO 특수금속)(1) Patent Document 1 (Japanese Patent Application Laid-Open No. 1990-093076, SANKO Special Metals)

가용성 구리염과, 분산제와, 착화제를 첨가하고 환원제로 환원처리 한 후에 안정제를 첨가하여 무전해 구리도금용의 미세한 구리 촉매액을 제조한다.A soluble copper salt, a dispersant, and a complexing agent are added, a reduction treatment is performed with a reducing agent, and a stabilizer is added to prepare a fine copper catalyst solution for electroless copper plating.

상기 분산제는 젤라틴, 노니온성 계면활성제이고, 착화제는 디카르복시산, 옥시카르복시산 등이며, 환원제는 수소화붕소나트륨, 디메틸아민보란 등이다. 안정제는 차아인산나트륨, 디메틸아민보란 등이다.The dispersant is gelatin or a nonionic surfactant. The complexing agent is a dicarboxylic acid, an oxycarboxylic acid or the like. The reducing agent is sodium borohydride, dimethylamine borane or the like. The stabilizer is sodium hypophosphite and dimethylamine borane.

또한, 실시예 4(4페이지 좌상란)에서는, 황산구리와 젤라틴과 수소화붕소나트륨과 차아인산염을 함유하는 촉매액에 피도금물을 침지한 후, 무전해 구리도금을 실시하였다.Further, in Example 4 (upper left column on page 4), electroless copper plating was carried out after dipping the substrate in a catalyst solution containing copper sulfate, gelatin, sodium borohydride and hypophosphite.

(2) 특허문헌 2(일본공개특허 1998-229280호 공보, 오쿠노 제약)(2) Patent Document 2 (Japanese Patent Application Laid-Open No. 1998-229280, Okuno Pharmaceutical)

구리염과 아니온성 계면활성제와 환원제로 이루어지는 무전해 도금용 촉매를 피도금물에 부여하고, 무전해 구리도금을 실시한 후, 전기 구리도금을 실시한다(청구항 1~2 단락 42).An electroless plating catalyst composed of a copper salt, an anionic surfactant and a reducing agent is applied to the object to be plated, electroless copper plating is performed, and then electroplating is performed (Claims 1 and 2).

구리 촉매액의 구체예인 제조예 2(단락 52)에서, 촉매액은 황산구리 및 암모니아에 의한 구리착체와 아니온성 계면활성제 및 수소화붕소나트륨(환원제)을 포함한다.In Production Example 2 (paragraph 52), which is a specific example of the copper catalyst solution, the catalyst solution contains a copper complex with copper sulfate and ammonia, an anionic surfactant and sodium borohydride (reducing agent).

(3) 특허문헌 3(일본공개특허 1995-197266호 공보 일본 LeaRonal)(3) Patent Document 3 (Japanese Patent Application Laid-Open No. 1995-197266, LeaRonal, Japan)

기판에 산화구리(I) 콜로이드 촉매용액에 의한 촉매부여 후, 구리염과 환원제 및 착화제를 포함하는 용액에 침지하여, 구리를 기판에 직접 도금(direct plating)하는 것이며, 상기 촉매부여 후의 용액에는 착화제나 환원제를 포함하나, 상기 촉매용액의 조성은 불분명하다.(I) colloid catalyst solution on the substrate, the copper is immersed in a solution containing a copper salt, a reducing agent and a complexing agent to directly coat copper on the substrate, A complexing agent and a reducing agent, but the composition of the catalyst solution is unclear.

(4) 특허문헌 4(일본공개특허 2011-225929호 공보, 칸토가쿠인대학)(4) Patent Document 4 (Japanese Patent Application Laid-Open No. 2011-225929, Kanto Gakuin University)

제일구리염과 차아인산염과 염소이온을 포함(청구항 1), 혹은 추가로 유기 또는 무기 환원제(아민보란 류, 수소화붕소화합물, 개미산 등)를 포함하는 촉매용액을 제조하는 방법(청구항 1~3), 및 피도금물을 계면활성제(카티온성, 아니온성, 카티온성, 노니온성; 단락 56)를 포함하는 컨디셔닝제로 전처리하고, 촉매용액에서 촉매 처리한 후, 무전해 도금을 하는 방법(청구항 8~9)이 개시되었다.A method for producing a catalyst solution comprising a cuprous salt, a hypophosphite and a chlorine ion (Claim 1) or further comprising an organic or inorganic reducing agent (amine borane, boron hydride compound, formic acid, etc.) (Claims 1 to 3) , And a method of pretreating the material to be plated with a conditioning agent including a surfactant (cationic, anionic, cationic, nonionic, paragraph 56), carrying out a catalytic treatment in the catalyst solution, 9).

상기 무전해 도금의 종류는 구리, 니켈, 금 등이며 무전해 구리도금이 바람직하다(단락 70).The type of electroless plating is copper, nickel, gold, etc., and electroless copper plating is preferable (paragraph 70).

또한, 상기 컨디셔닝제에 있어서는, 특히 카티온성 계면활성제를 사용하면, 피도금물에 흡착된 계면활성제의 친수기가 마이너스로 대전하여, 상기 제일구리이온이 흡착하기 쉽고, 균일하게 구리 이온이 흡착된 촉매화 피도금물을 얻을 수 있음이 기재되었다(단락 58).In addition, in the above-mentioned conditioning agent, in particular, when a cationic surfactant is used, the hydrophilic group of the surfactant adsorbed on the object to be plated is negatively charged, the copper ion is easily adsorbed, It has been described that it is possible to obtain fugitive material (paragraph 58).

(5) 특허문헌 5(일본 공표특허 2013-522476호 공보; Enthone Inc.)(5) Patent Document 5 (Japanese Published Patent Application No. 2013-522476; Enthone Inc.)

귀금속/금속-콜로이드(예를 들어, 팔라듐/주석 콜로이드 용액)을 포함하는 활성화제 용액으로 비도전성 기판을 처리하고, 이어서 구리염 등의 금속염 용액과 당해 금속이온의 착화제와 환원제를 포함하는 도전체 용액에 접촉시킨 후, 무전해 도금 및 전기도금을 실시하는 비도전성 기판의 직접 금속화법이 기재되었다(단락 1, 13).A non-conductive substrate is treated with an activator solution comprising a noble metal / metal-colloid (e.g., palladium / tin colloid solution) and then a solution containing a metal salt solution such as a copper salt and a complexing agent of the metal ion with a reducing agent A direct metallization of a non-conductive substrate is carried out in which electroless plating and electroplating are performed after contact with a sieving solution (paragraphs 1 and 13).

상기 도전체 용액의 금속염은 활성화제 용액의 금속으로 환원되어, 예를 들어, 활성화제 용액의 2가 주석(산화성 카티온)은 도전체 용액의 2가 구리이온 (환원성 카티온)에 작용하고, 주석은 4가로 산화됨에 따라 2가 구리이온은 환원되어 금속구리가 된다(단락 24, 29).The metal salt of the conductor solution is reduced to the metal of the activator solution, for example, the divalent tin (oxidizing cation) of the activator solution acts on the divalent copper ion (reducing cation) of the conductor solution, As tin is oxidized 4 times, divalent copper ions are reduced to metal copper (paragraphs 24 and 29).

실시예 1에서는, ABS 플라스틱 기판을 팔라듐-주석계 콜로이드를 함유하는 활성화제 분산액에서 활성화 처리한 후, 주석산(착화제)과 차아인산염(또는 차아인산염 및 하이드록시메틸설포네이트; 환원제)과 구리염 및 리튬염 등을 포함하는 도전체 용액으로 처리하는 것이 기재되었다(단락 65, 단락 66의 표1).In Example 1, the ABS plastic substrate was activated in a dispersion of an activator containing a palladium-tin colloid, and then treated with a mixture of tartaric acid (complexing agent), hypophosphite (or hypophosphite and hydroxymethylsulfonate; reducing agent) And a lithium salt or the like (paragraph 65, Table 1 in paragraph 66).

일본 특개평 2-093076호 공보Japanese Patent Laid-Open No. 2-093076 일본 특개평 10-229280호 공보Japanese Patent Application Laid-Open No. 10-229280 일본 특개평 7-197266호 공보Japanese Patent Application Laid-Open No. 7-197266 일본 특개 2011-225929호 공보Japanese Patent Application Laid-Open No. 2011-225929 일본 특표 2013-522476호 공보Japan Specification Sheet 2013-522476

그러나, 상기 수계 촉매액에서는, 가용성 금속염을 환원제로 처리하여 금속의 미세입자를 생성하는 것을 기본 원리로 하고 있으나, 상기 특허문헌의 촉매액을 비롯하여, 경시 안정성에 문제가 있는 것이 많아, 촉매부여와 무전해 도금 작업의 연속성을 장시간에 걸쳐 원활하게 확보하기가 쉽지 않다는 것이 현실정이다.However, in the above-mentioned aqueous catalyst solution, the basic principle is that the soluble metal salt is treated with a reducing agent to produce fine particles of metal. However, since there are many problems with respect to stability over time including the catalyst solution of the patent documents, It is a reality that it is not easy to secure continuity of the electroless plating work for a long time smoothly.

또한 비도전성 기판을 구리 촉매액으로 촉매 부여한 후, 무전해 도금을 실시해도, 석출이 곤란하거나 부분적으로 피막 석출이 안 되는 도금 부족의 발생이나, 도금 피막에 얼룩이 발생하거나, 또는 균일성이 떨어지는 등의 문제가 있다.Further, even when the electroless plating is performed after the non-conductive substrate is subjected to catalytic treatment with the copper catalyst liquid, it is difficult to precipitate or undergo partial plating precipitation, to cause plating defects, to cause unevenness in the plating film, There is a problem of.

본 발명은, 수계 구리 촉매액의 경시 안정성을 향상시킴과 더불어, 촉매 부여한 비도전성 기판에 무전해 구리도금을 실시하여, 균일하며 얼룩이 없는 구리피막을 얻는 것을 기술적 과제로 한다.SUMMARY OF THE INVENTION It is a technical object of the present invention to improve the stability of the aqueous copper catalyst solution with the elapse of time and to conduct electroless copper plating on the catalyst-imparted non-conductive substrate to obtain a uniform and uneven copper film.

본 발명자들은 예를 들어, 특허문헌 1에서는 구리의 환원상태를 유지하기 위하여 안정제를 사용하는 점에서, 우선 구리염에 대하여 착화 기능을 갖는 성분을 촉매액에 함유시키는 등으로, 콜로이드 입자의 안정화에 착상하였다.The inventors of the present invention have found that, for example, in Patent Document 1, stabilizers are used in order to maintain a reduced state of copper. In order to stabilize the colloid particles by first adding a component having a complexing function to the copper salt in the catalyst liquid, .

그리고 구리 촉매액에, 구리염을 안정시키는 옥시카르복시산류, 아미노카르복시산류 등의 콜로이드 안정제를 함유시킴과 더불어, 구리염과 안정제의 혼합비율을 조정함으로써 경시 안정성을 개선할 수 있는 점, 이어서 계면활성제의 존재는 경시 안정성에 악영향을 주므로, 첨가해도 그 함유량은 극히 소량에 머물러야 하는 점, 또한 소정의 수용성 폴리머의 존재는 경시 안정성에 크게 기여하는 점 등의 지견을 얻었다.It is also possible to add a colloidal stabilizer such as an oxycarboxylic acid or an aminocarboxylic acid to stabilize the copper salt in the copper catalyst liquid and to improve the stability with the elapse of time by adjusting the mixing ratio of the copper salt and the stabilizer, The presence of the water-soluble polymer adversely affects the stability over time, so that even when added, the content thereof should be kept to a very small amount, and the presence of the predetermined water-soluble polymer contributes greatly to the stability over time.

또한, 이러한 지견에 따라, 기판을 구리 촉매액으로 촉매 부여하기 전에, 계면활성제로 이루어지는 흡착 촉진제 함유액에 침지한다는 예비처리를 가중적으로 실시하면, 촉매 부여 시에 촉매활성이 높아져 무전해 도금으로 얻어지는 석출 피막의 균일성과, 피막의 외관 얼룩 발생 방지에 우수하다는 점을 새로이 발견하여 본 발명을 완성하였다.According to this finding, if the preliminary treatment of immersing the substrate in a solution containing an adsorption promoter made of a surfactant is carried out before the catalyst is added with the copper catalyst liquid, the catalytic activity at the time of catalyst application becomes high, The present invention has been completed on the basis that it is excellent in the uniformity of the obtained precipitation film and in preventing appearance stain of the film.

즉, 본 발명 1은, 무전해 구리도금을 실시할 비도전성 기판에 접촉시켜 촉매 부여를 하기 위한 수계 구리 콜로이드 촉매액에 있어서,That is, the present invention 1 is an aqueous copper colloid catalyst solution for bringing a catalyst into contact with a non-conductive substrate to be subjected to electroless copper plating,

(A) 가용성 구리염과,(A) a soluble copper salt,

(B) 환원제와,(B) a reducing agent,

(C) 모노카르복시산류, 옥시카르복시산류, 아미노카르복시산류, 폴리카르복시산류로 이루어지는 군에서 선택된 콜로이드 안정제의 적어도 한 종류를 함유하며, 상기 성분 (A)와 (C)의 함유 몰 비율을 A:C = １：0.03 ~ 1:35로 함과 더불어,(C) at least one kind of colloidal stabilizer selected from the group consisting of monocarboxylic acids, oxycarboxylic acids, aminocarboxylic acids and polycarboxylic acids, wherein the molar ratio of the components (A) and (C) = 1: 0.03 to 1:35,

계면활성제를 함유하지 않거나, 혹은 계면활성제의 함유량을 950mg/L 이하로 하는 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액이다.Wherein the surfactant-free water-based copper-colloidal catalyst solution contains no surfactant or the content of the surfactant is 950 mg / L or less.

본 발명 2는, 무전해 구리도금을 실시할 비도전성 기판에 접촉시켜 촉매 부여를 하기 위한 수계 구리 콜로이드 촉매액에 있어서,The present invention 2 is an aqueous copper colloid catalyst solution for bringing a catalyst into contact with a non-conductive substrate to be subjected to electroless copper plating,

(A) 가용성 구리염과,(A) a soluble copper salt,

(B) 환원제와,(B) a reducing agent,

(C) 모노카르복시산류, 옥시카르복시산류, 아미노카르복시산류, 폴리카르복시산류로 이루어지는 군에서 선택된 콜로이드 안정제 중 적어도 한 종류를 함유하며, 상기 성분 (A)와 (C)의 함유 몰비율을 A:C = １：0.03 ~ 1:35로 함과 더불어,(C) a colloidal stabilizer selected from the group consisting of monocarboxylic acids, oxycarboxylic acids, aminocarboxylic acids and polycarboxylic acids, wherein the molar ratio of the components (A) and (C) is A: C = 1: 0.03 to 1:35,

합성계 수용성 폴리머를 함유하는 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액이다.Soluble copper-colloidal catalyst solution for electroless copper plating.

본 발명 3은, 상기 본 발명 2에서 합성계 수용성 폴리머가 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리비닐피롤리돈, 폴리비닐알콜, 폴리아크릴아마이드, 폴리에틸렌이민에서 선택된 적어도 한 종류인 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액이다.The present invention 3 is an electroluminescent material characterized in that the synthetic water-soluble polymer is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide and polyethyleneimine, It is a water-based copper colloid catalyst liquid for plating.

본 발명 4는, 상기 본 발명 1~3 중 어느 하나에 있어서, 환원제(B)가 수소화붕소화합물, 아민보란류, 차아인산류, 알데히드류, 아스코르빈산류, 하이드라진류, 다가페놀류, 다가나프톨류, 페놀술폰산류, 나프톨술폰산류, 술핀산(sulfinic acid)류로 이루어지는 군에서 선택된 적어도 한 종류인 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액이다.A fourth aspect of the present invention is the fourth aspect of the present invention, wherein the reducing agent (B) is at least one selected from the group consisting of a borohydride compound, an amine borane, a hypophosphorous acid, an aldehyde, an ascorbic acid, a hydrazine, a polyhydric phenol, Is at least one member selected from the group consisting of sulfuric acid, sulfuric acid, sulfuric acid, sulfuric acid, sulfuric acid, sulfuric acid, sulfuric acid, phenolsulfonic acids, naphtholsulfonic acids and sulfinic acids.

본 발명 5는, 상기 본 발명 1~4 중 어느 하나에 있어서, 모노카르복시 산류(C)가, 개미산, 아세트산, 프로피온산, 부티르산, 발레르산, 카프로산, 카프릴산, 카프린산, 라우르산, 미리스트산, 팔미트산, 스테아린산 및 이들의 염으로 이루어진 군에서 선택된 적어도 한 종류인 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액이다.A fifth aspect of the present invention is the fifth aspect of the present invention, wherein in the first to fourth inventions, the monocarboxylic acids (C) are at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, , Myristic acid, palmitic acid, stearic acid, and salts thereof. The electrolytic copper-colloidal catalyst solution for electroless copper plating is an aqueous copper colloid catalyst solution.

본 발명 6은, 상기 본 발명 1~5 중 어느 하나에 있어서, 옥시카르복시산(C)이, 구연산, 주석산, 사과산, 글루콘산, 글루코헵탄(Glucoheptonic acid), 글리콜산, 젖산, 트리옥시부티르산, 아스코르빈산, 이소구연산, 타르트론산, 글리세린산, 하이드록시부티르산, 로이신산, 시트라말산(citramalic acid)및 이들의 염으로 이루어진 군에서 선택된 적어도 한 종류인 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액이다.A sixth aspect of the present invention relates to any one of the first to fifth aspects of the present invention, wherein the oxycarboxylic acid (C) is at least one selected from the group consisting of citric acid, tartaric acid, malic acid, gluconic acid, glucoheptonic acid, glycolic acid, lactic acid, trioxybutyric acid, Wherein the aqueous copper hydroxide for electroless copper plating is at least one selected from the group consisting of citric acid, cornic acid, iso citric acid, tartronic acid, glyceric acid, hydroxybutyric acid, leucine acid, citramalic acid, Colloidal catalyst solution.

본 발명 7은, 상기 본 발명 1~6 중 어느 하나에 있어서, 아미노카르복시산류(C)가 하이드록시에틸 에틸렌디아민트리아세트산, 디에틸렌트리아민펜타아세트산, 트리에틸렌테트라민헥사아세트산, 에틸렌디아민테트라아세트산, 에틸렌디아민테트라프로피온산, 니트릴로트리아세트산, 이미노디아세트산, 하이드록시에틸 이미노디아세트산, 이미노디프로피온산, 1,3-프로판디아민테트라아세트산, 1,3-디아미노-2-하이드록시프로판테트라아세트산, 글리콜에테르 디아민테트라아세트산, 메타페닐렌 디아민테트라아세트산, 1,2-디아미노시클로헥산-N,N,N',N'-테트라아세트산, 디아미노프로피온산, 글루타민산, 디카르복시메틸글루타민산, 오르니틴, 시스테인, N,N-비스(2-하이드록시에틸)글리신, (S,S)-에틸렌디아민숙신산 및 이들의 염으로 이루어진 군에서 선택된 적어도 한 종류인 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액이다.In the present invention 7, the aminocarboxylic acids (C) are preferably selected from the group consisting of hydroxyethylethylenediamine triacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, ethylenediaminetetraacetic acid , Ethylenediaminetetrapropionic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, iminodipropionic acid, 1,3-propanediamine tetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol N, N ', N'-tetraacetic acid, diaminopropionic acid, glutamic acid, dicarboxymethylglutamic acid, ornithine, cysteine, N, N-bis (2-hydroxyethyl) glycine, (S, S) -ethylenediamine succinic acid and salts thereof At least one kind of copper-colloidal catalyst solution for electroless copper plating.

본 발명 8은, 상기 본 발명 1~7 중 어느 하나에 있어서, 폴리카르복시산류(C)가, 숙신산, 글루타르산, 말론산, 아디프산, 옥살산, 말레인산, 시트라콘산, 이타콘산, 메사콘산 및 이들의 염으로 이루어진 군에서 선택된 적어도 한 종류인 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액이다.In the present invention 8, in any one of the inventions 1 to 7, the polycarboxylic acids (C) are selected from the group consisting of succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesa And at least one member selected from the group consisting of hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid,

본 발명 9는, (a) 노니온계 계면활성제, 카티온계 계면활성제, 아니온계 계면활성제, 양성 계면활성제로 이루어진 군에서 선택된 흡착촉진제의 적어도 하나의 함유액에 비도전성 기판을 침지하는 흡착촉진공정(전처리 공정)과,(9) An adsorption promoting step ((a)) of immersing a non-conductive substrate in a liquid containing at least one adsorbent selected from the group consisting of a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant Preprocessing step)

(b) 상기 본 발명 1~8 중 어느 하나의 수계 구리 콜로이드 촉매액에 비도전성 기판을 침지하여, 기판 표면상에 구리 콜로이드 입자를 흡착시키는 촉매부여공정과,(b) a catalyst imparting step of immersing the non-conductive substrate in the aqueous copper colloid catalyst solution of any of the above inventions 1 to 8 to adsorb copper colloid particles on the surface of the substrate,

(c) 흡착 처리된 상기 기판 상에 무전해 구리도금액을 사용하여 구리피막을 형성하는 무전해 도금공정으로 이루어지는 것을 특징으로 하는 무전해 구리도금 방법이다.(c) an electroless copper plating process for forming a copper film on the substrate subjected to the adsorption treatment using an electroless copper plating solution.

본 발명 10은, 공정(a)의 흡착촉진제가, 카티온계 계면활성제 및/또는 양성 계면활성제인 것을 특징으로 하는 무전해 구리도금 방법이다.The present invention 10 is an electroless copper plating method characterized in that the adsorption promoter of the step (a) is a cationic surfactant and / or an amphoteric surfactant.

본 발명의 구리 콜로이드 촉매액에서는, 구리염에 착화작용을 하는 콜로이드 안정제를 함유하여, 해당 안정제와 구리염의 비율을 특정화함과 더불어, 폴리에틸렌글리콜, 폴리비닐피롤리돈, 폴리비닐알코올 등의 소정의 수용성 폴리머를 함유하거나, 혹은, 역으로 계면활성제를 함유하지 않거나, 극히 소량만 함유함으로써 액의 경시안정성을 현저히 향상시킬 수 있다.In the copper-colloidal catalyst solution of the present invention, a colloidal stabilizer capable of acting as a complex in the copper salt is contained to specify the ratio of the stabilizer to the copper salt, and a predetermined amount of a stabilizer such as polyethylene glycol, polyvinyl pyrrolidone and polyvinyl alcohol It is possible to remarkably improve the stability with time of the liquid by containing the water-soluble polymer or, conversely, containing no surfactant or containing only a very small amount.

더불어, 상기 특허문헌 1의 금속체 함유액(즉 촉매액)에서는, 구리염의 착화작용을 하는 성분의 함유는 없다. 또한 특허문헌 1의 실시예 4(4 페이지 좌상란~우상란)의 촉매액에서는, 분산제로서 젤라틴 1000mg/L를 함유하거나, 혹은, 상기 특허문헌 2 제조예 2(단락 52)의 촉매액에서는, 아니온성 계면활성제를 1000mg/L 함유하고 있어, 모두 본 발명 1의 촉매액에서의 계면활성제 규정량의 상한을 초과하였다.In addition, in the metal-containing liquid (i.e., the catalyst liquid) of Patent Document 1, there is no ingredient for complexing the copper salt. In the catalyst liquid of Example 4 of Patent Document 1 (upper left column to upper right column of page 4), 1000 mg / L of gelatin was dispersed as the dispersing agent or in the catalyst solution of Production Example 2 (paragraph 52) of Patent Document 2, And 1000 mg / L of the surfactant, all exceeding the upper limit of the specified amount of the surfactant in the catalyst solution of the present invention 1.

본 발명에서는, 비도전성 기판에 상기 구리 콜로이드 촉매를 부여한 후, 무전해 구리도금을 하는 것을 기본 원리로 하되, 이 촉매 부여의 전처리, 혹은 예비처리로서, 비도전성 기판을 계면활성제 함유액에 침지하는 흡착촉진처리를 추가시켜, 당해 흡착촉진공정, 촉매부여공정 및 무전해 구리도금 공정을 순차 실시함으로써, 촉매부여 시의 촉매 활성을 강화시켜 무전해 도금에 의해 석출되는 구리피막의 균일성을 개선하며, 피막의 불균일 발생을 양호하게 방지할 수 있다.In the present invention, the copper-colloidal catalyst is applied to a non-conductive substrate and then electroless copper plating is performed. As a pretreatment or pretreatment of the catalyst application, the non-conductive substrate is immersed in a surfactant- By carrying out the adsorption promoting step, the catalyst imparting step and the electroless copper plating step in succession by adding the adsorption promoting treatment, the catalytic activity at the time of catalyst addition is enhanced to improve the uniformity of the copper film deposited by electroless plating , It is possible to satisfactorily prevent occurrence of unevenness of the coating film.

본 발명은 첫째로, 비도전성 기판에 접촉시켜 촉매 부여를 실시하기 위한 수계 구리 콜로이드 촉매액으로서, (A) 가용성 구리염과 (B) 환원제 및 (C) 콜로이드 안정제를 함유하며, 상기 성분 (A)와 (C)의 함유 몰 비율을 특정화하여, 계면활성제를 함유하지 않거나, 또는 극히 소량만 함유하는 무전해 구리도금용 수계 구리 콜로이드 촉매액이고, 둘째로, 계면활성제의 함유를 배제 혹은 소정량 이하로 억제하는 제 1 발명에 갈음하여, 합성계 수용성 폴리머를 함유하는 수계 구리 콜로이드 촉매액이며, 셋째로, 상기 제 1 또는 제 2 촉매액을 이용한 무전해 구리도금 방법이고, 미리 비도전성 기판을 계면활성제 함유액에서 흡착촉진 처리한 후, 이어서 상기 촉매액에 의해 촉매 부여한 후 무전해 구리도금을 실시하는 방법이다.(A) a soluble copper salt, (B) a reducing agent, and (C) a colloidal stabilizer, wherein the component (A) is a copper colloid, ) And (C), and is a water-based copper colloid catalyst liquid for electroless copper plating which contains no surfactant or contains only a very small amount. Second, the content of the surfactant is excluded or a predetermined amount Aqueous copper-colloid catalyst solution containing a synthetic water-soluble polymer, and third, an electroless copper plating method using the first or second catalyst solution, wherein the non-conductive substrate is pre- Containing solution, followed by catalyst addition by the catalyst solution, and electroless copper plating is carried out.

상기 비도전성 기판은, 유리에폭시 수지, 유리폴리이미드 수지, 에폭시 수지, 폴리이미드 수지, 폴리카보네이트 수지, ABS 수지, PET 수지 등의 수지기판을 비롯하여, 유리기판, 세라믹기판 등을 말한다.The non-conductive substrate refers to a resin substrate such as a glass epoxy resin, a glass polyimide resin, an epoxy resin, a polyimide resin, a polycarbonate resin, an ABS resin or a PET resin, and also a glass substrate or a ceramic substrate.

상기 본 발명 1의 수계 구리 콜로이드 촉매액의 기본 구성은, (A) 가용성 구리염과, (B) 환원제와, (C) 콜로이드 안정제이다.The basic composition of the aqueous copper colloid catalyst solution of the present invention 1 is (A) a soluble copper salt, (B) a reducing agent, and (C) a colloidal stabilizer.

상기 가용성 구리염(A)은, 수용액 중에서 제 1 또는 제 2 구리이온을 발생시키는 가용성 염이라면 임의의 염을 사용할 수 있으며, 특별한 제한은 없고, 난용성 염도 배제하지 않는다. 구체적으로는, 황산구리, 산화구리, 염화구리, 피롤린산 구리, 탄산 구리, 또는 아세트산 구리, 옥살산 구리 및 구연산 구리 등의 카르복시산 구리염, 또는 메탄술폰산 구리 및 하이드록시 에탄술폰산 구리 등의 유기 술폰산 구리염 등을 들 수 있으며, 황산 구리, 구연산 구리, 메탄술폰산 구리가 바람직하다.The soluble copper salt (A) can be any salt as long as it is a soluble salt for generating the first or second copper ion in an aqueous solution. There is no particular limitation, and the poorly soluble salt is not excluded. Specifically, there may be mentioned copper sulfate salts such as copper sulfate, copper oxide, copper chloride, copper pyrophosphate, copper carbonate, copper carboxylate such as copper acetate, copper oxalate and copper citrate, or organic sulfonate copper salts such as copper methanesulfonate and copper hydroxyethanesulfonate And copper sulfate, copper citrate, and copper methanesulfonate are preferable.

상기 환원제(B)로는, 수소화붕소화합물, 아민보란류, 차아인산류, 알데히드류, 아스코르빈산류, 하이드라진류, 다가페놀류, 다가나프톨류, 페놀술폰산류, 나프톨술폰산류, 술핀산(sulfinic acid)류 등을 들 수 있다. 알데히드류는 포름알데히드, 글리옥실산 또는 그 염 등이며, 다가페놀류는 카테콜, 하이드로퀴논, 레졸신(resorcine), 피로갈롤, 플로로글루신, 갈릭산 등이고, 페놀술폰산류는 페놀술폰산, 크레졸술폰산 또는 그 염 등이다.Examples of the reducing agent (B) include a borohydride compound, an amine borane, a hypophosphorous acid, an aldehyde, an ascorbic acid, a hydrazine, a polyhydric phenol, a divalent phenol, a phenol sulfonic acid, a naphthosulfonic acid, a sulfinic acid ), And the like. The aldehydes include formaldehyde, glyoxylic acid and salts thereof, and the polyhydric phenols include catechol, hydroquinone, resorcine, pyrogallol, fluoroglucine and gallic acid. The phenolsulfonic acids include phenolsulfonic acid, Sulfonic acid or a salt thereof.

상기 콜로이드 안정제(C)는 도금욕 중에서 구리 착체를 형성하는 화합물이며, 촉매액의 경시 안정성을 담보하는 기능을 수행하는 것이다.The colloidal stabilizer (C) is a compound which forms a copper complex in a plating bath, and performs the function of securing the stability of the catalyst solution with respect to time.

당해 콜로이드 안정제(C)는, 모노카르복시산류, 옥시카르복시산류, 아미노카르복시산류, 폴리카르복시산류로 이루어지는 군에서 선택된다.The colloidal stabilizer (C) is selected from the group consisting of monocarboxylic acids, oxycarboxylic acids, aminocarboxylic acids and polycarboxylic acids.

상기 모노카르복시산류로는, 개미산, 아세트산, 프로피온산, 부티르산, 발레르산, 카프로산, 카프릴산, 카프린산, 라우르산, 미리스트산, 팔미트산, 스테아린산 및 이들의 염 등을 들 수 있다.
상기 옥시카르복시산류로는, 구연산, 주석산, 사과산, 글루콘산, 글루코헵탄, 글리콜산, 젖산, 트리옥시부티르산, 아스코르빈산, 이소구연산, 타르트론산, 글리세린산, 하이드록시부티르산, 로이신산, 시트라말산 및 이들의 염 등을 들 수 있다.Examples of the monocarboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, have.
The oxycarboxylic acids include citric acid, tartaric acid, malic acid, gluconic acid, glucoheptane, glycolic acid, lactic acid, trioxybutyric acid, ascorbic acid, isocitric acid, tartronic acid, glyceric acid, hydroxybutyric acid, Malic acid and salts thereof.

상기 아미노카르복시산류로는, 에틸렌디아민테트라아세트산(EDTA), 하이드록시에틸 에틸렌디아민트리아세트산(HEDTA), 디에틸렌트리아민펜타아세트산(DTPA), 트리에틸렌테트라민헥사아세트산(TTHA), 에틸렌디아민테트라프로피온산, 니트릴로트리아세트산(NTA), 이미노디아세트산(IDA), 이미노디프로피온산(IDP), 하이드록시에틸 이미노디아세트산, 1,3-프로판디아민테트라아세트산, 1,3-디아미노-2-하이드록시프로판테트라아세트산, 글리콜에테르 디아민테트라아세트산, 메타페닐렌 디아민테트라아세트산, 1,2-디아미노시클로헥산-N,N,N',N'-테트라아세트산, 디아미노프로피온산, 글루타민산, 디카르복시메틸글루타민산, 오르니틴, 시스테인, N,N-비스(2-하이드록시에틸)글리신, (S,S)-에틸렌디아민숙신산 및 이들의 염 등을 들 수 있다.Examples of the aminocarboxylic acids include ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), ethylenediaminetetrapropionic acid , Nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), hydroxyethyliminodiacetic acid, 1,3-propanediamine tetraacetic acid, 1,3-diamino- N, N ', N'-tetraacetic acid, diaminopropionic acid, glutamic acid, dicarboxymethylglutamic acid, dicarboxylic acid, acetic acid, Tin, cysteine, N, N-bis (2-hydroxyethyl) glycine, (S, S) -ethylenediamine succinic acid and salts thereof.

상기 폴리카르복시산류로는, 숙신산, 글루타르산, 말론산, 아디프산, 옥살산, 말레인산, 시트라콘산, 이타콘산, 메사콘산 및 이들의 염 등을 들 수 있다.Examples of the polycarboxylic acids include succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid and salts thereof.

본 발명의 구리 콜로이드 촉매액은 수계이므로, 액의 용매는 물 및/또는 친수성 알코올로 제한되며, 유기용매(친유성 알코올 포함) 단독 사용은 배제된다.Since the copper colloid catalyst solution of the present invention is aqueous, the solvent of the solution is limited to water and / or hydrophilic alcohol, and the use of an organic solvent (including oleophilic alcohol) alone is excluded.

또, 당해 촉매액에 대해서는, 중성 부근에서는 촉매활성이 저하되기 쉬우므로, 액의 pH는 중성 영역을 제외한 산성 쪽 또는 알칼리 쪽이 바람직하며, 구체적으로는 pH1~6 및 pH8~12가 적합하고, 바람직하게는 pH2~5 및 pH8~11이다.The pH of the solution is preferably acidic or alkaline, except for the neutral region. Specifically, the pH of the solution is preferably from pH 1 to 6 and pH 8 to 12, Preferably pH 2-5 and pH 8-11.

수계 구리 콜로이드 촉매액에 있어서, 상기 가용성 구리염 (A)는 단독 사용 또는 병용이 가능하며, 그 함유량은 0.005~１몰/L, 바람직하게는 0.05~0.5몰/L, 보다 바람직하게는 0.04~0.2몰/L이다.The content of the soluble copper salt (A) in the aqueous copper colloid catalyst solution can be used alone or in combination, and the content thereof is 0.005 to 1 mol / L, preferably 0.05 to 0.5 mol / L, more preferably 0.04 to 0.5 mol / 0.2 mol / L.

상기 환원제 (B)는 단독 사용 또는 병용이 가능하며, 그 함유량은 0.005~１몰/L, 바람직하게는 0.05~0.5몰/L이다. 환원제의 함유량이 적정량보다 적으면 구리염의 환원작용이 저하되며, 역으로 지나치게 많으면 무전해 도금으로 석출되는 구리피막의 균질성이 저하될 우려가 있다.The reducing agent (B) can be used alone or in combination, and its content is 0.005 to 1 mol / L, preferably 0.05 to 0.5 mol / L. If the content of the reducing agent is less than the proper amount, the reducing action of the copper salt is lowered, and if it is excessively large, the homogeneity of the copper film deposited by electroless plating may be deteriorated.

상기 콜로이드 안정제 (C)는 단독 사용 또는 병용이 가능하며, 그 함유량은 0.005~2몰/L, 바람직하게는 0.05~1.5몰/L이다.The colloidal stabilizer (C) can be used alone or in combination, and its content is 0.005 to 2 mol / L, preferably 0.05 to 1.5 mol / L.

또한, 수계 콜로이드 촉매액에서, 상기 (A)와 (C)의 함유 몰 비율은 A:C=1:0.03~1:35이며, 바람직하게는 A:C=1:0.5~1:24이다. 콜로이드 안정제 (C)의 상대적 함유율이 지나치게 적으면 촉매액의 경시 안정성이 저하되며, 나아가 무전해 도금으로 얻어지는 구리피막에 석출 불량이 발생하는 요인이 된다. 역으로, 콜로이드 안정제 (C)의 함유율이 지나치게 많아도, 촉매액의 경시 안정성을 훼손시켜, 얻어지는 구리피막의 질을 저하시키게 된다(후술하는 시험예 참조).In the aqueous colloidal catalyst solution, the molar ratio of A to C is 1: 0.03 to 1:35, and A: C is 1: 0.5 to 1: 24. If the relative content of the colloidal stabilizer (C) is too low, the stability of the catalyst solution with the elapse of time tends to deteriorate, and furthermore, the precipitation failure occurs in the copper film obtained by electroless plating. Conversely, if the content of the colloidal stabilizer (C) is too high, the stability of the catalyst solution with time is deteriorated, and the quality of the obtained copper coating film is lowered (see test examples described later).

수계 콜로이드 촉매액에서, 상기 (A)와 (B)의 함유 몰비율은 A:B=1:0.05~1:6이며, 바람직하게는A:B=1:0.1~1:5이다.In the aqueous colloidal catalyst solution, the molar ratio of the components (A) and (B) is 1: 0.05 to 1: 6, preferably 1: 0.1 to 1: 5.

당해 촉매액 제조 시에 있어, 환원제로부터 구리이온으로 전자를 원활하게 공여하므로, 환원제 용액을 가용성 구리염(및 콜로이드 안정제) 함유 용액에 시간을 들여 천천히 적하시켜 제조하는 것을 기본으로 한다. 예를 들어, 5~50℃(바람직하게는 10~40℃)의 환원제 용액을 구리염 용액에 적하하고, 20~1200분간(바람직하게는 30~300분간) 교반하여, 촉매액을 제조한다. 촉매액 제조에 있어서는, 가용성 구리염 용액을 환원제 액에 적하하는 것을 배제하지 않는다.In the preparation of the catalyst liquid, electrons are smoothly supplied from the reducing agent to the copper ion, so that the reducing agent solution is slowly added dropwise to the soluble copper salt (and colloid stabilizer) -containing solution over a period of time. For example, a reducing agent solution of 5 to 50 캜 (preferably 10 to 40 캜) is dropped into a copper salt solution and stirred for 20 to 1,200 minutes (preferably 30 to 300 minutes) to prepare a catalyst solution. In the preparation of the catalyst liquid, it is not excluded to drop the soluble copper salt solution into the reducing agent solution.

본 발명의 촉매액에 있어서, 환원제 작용에 의하여 가용성 구리염에서 생성되는 구리 콜로이드 입자는 적합한 평균 입경이 1~250nm, 바람직하게는 1~120nm, 보다 바람직하게는 1~100nm의 미세 입자이다.In the catalyst solution of the present invention, the copper colloid particles produced in the soluble copper salt by the action of the reducing agent are fine particles having an appropriate average particle diameter of 1 to 250 nm, preferably 1 to 120 nm, more preferably 1 to 100 nm.

구리 콜로이드 입자의 평균 입경이 250nm 이하가 되면, 촉매액에 비도전성 기판을 침지할 경우, 콜로이드 입자가 기판의 미세한 요철면의 홈으로 들어가 조밀하게 흡착되거나, 혹은 홈에 유지되는 등의 앵커 효과에 의하여 기판 표면에 구리 콜로이드 핵의 부여가 촉진되는 것으로 추정된다. 역으로, 평균 입경이 250nm보다 커지면, 응집, 침전 혹은 분리 등으로 인하여, 안정된 구리 콜로이드를 얻기 어려울뿐더러, 앵커 효과도 기대할 수 없으므로, 구리 콜로이드 입자가 기판 표면에 부분적으로 밖에 부여할 수 없거나, 부여 불량이 될 우려가 있다.When the average particle size of the copper colloidal particles is 250 nm or less, when the non-conductive substrate is immersed in the catalyst liquid, the colloidal particles enter the grooves of the fine uneven surface of the substrate and are densely adsorbed or held in the grooves. It is presumed that the application of copper colloid nuclei to the substrate surface is promoted. Conversely, if the average particle diameter is larger than 250 nm, it is difficult to obtain stable copper colloid due to coagulation, sedimentation or separation, and an anchor effect can not be expected. Therefore, copper colloid particles can only partially be imparted to the substrate surface There is a risk of failure.

본 발명 1의 수계 구리 콜로이드 촉매액에서는, 계면활성제를 함유하지 않거나 혹은 계면활성제의 함유량을 950mg/L 이하로 억제할 필요가 있다.In the aqueous copper colloid catalyst solution of the present invention 1, it is necessary to contain no surfactant or to suppress the content of the surfactant to 950 mg / L or less.

촉매액에 계면활성제를 함유시키면 촉매 활성이 저하될 우려가 있어, 계면활성제는 첨가하지 않는 것이 바람직하다. 단, 함유량이 950mg/L 이하의 극히 소량일 경우에는 그다지 촉매 활성 저하에 악영향은 없으며, 바람직하게는 700mg/L 이하이다.When the surfactant is contained in the catalyst liquid, there is a possibility that the catalytic activity is lowered, and it is preferable that no surfactant is added. However, when the content is an extremely small amount of 950 mg / L or less, there is no adverse effect on catalyst activity lowering, and it is preferably 700 mg / L or less.

상기 계면활성제는 노니온계, 양성(兩性), 카티온계 혹은 아니온계의 각종 계면활성제를 의미하며, 특히, 양성, 카티온계, 아니온계 혹은 저분자 노니온계 계면활성제는 바람직하지 못하다.The surfactant refers to various nonionic, amphoteric, cationic or anionic surfactants. In particular, positive, cationic, anionic or low molecular weight nonionic surfactants are not preferred.

상기 노니온계 계면활성제로는, C1~C20 알칸올, 페놀, 나프톨, 비스페놀류, (폴리) C1~C25 알킬페놀, (폴리)아릴알킬페놀, C1~C25 알킬나프톨, C1~C25 알콕실화인산(염), 소르비탄에스테르, 폴리알킬렌글리콜, C1~C22 지방족 아민, C1~C22 지방족 아마이드 등에 에틸렌 옥사이드(EO) 및/또는 프로필렌 옥사이드(PO)를 2~300몰 부가 축합시킨 것 등을 들 수 있다.Examples of the nonionic surfactant include C 1 -C 20 alkanol, phenol, naphthol, bisphenols, (poly) C 1 -C 25 alkylphenol, (poly) arylalkylphenol, C 1 -C 25 alkylnaphthol, C (EO) and / or propylene oxide (PO) to 1 to C 25 alkoxylated phosphates (salts), sorbitan esters, polyalkylene glycols, C 1 to C 22 aliphatic amines, C 1 to C 22 aliphatic amides, 2 to 300 mols of the condensation product.

상기 카티온계 계면활성제로는, 제 4급 암모늄염, 혹은 피리디늄염 등을 들 수 있으며, 구체적으로는, 라우릴트리메틸암모늄염, 스테아릴트리메틸암모늄염, 라우릴디메틸에틸암모늄염, 옥타데실디메틸에틸암모늄염, 디메틸벤질라우릴암모늄염, 세틸디메틸벤질암모늄염, 옥타데실디메틸벤질암모늄염, 트리메틸벤질암모늄염, 트리에틸벤질암모늄염, 디메틸디페닐암모늄염, 벤질디메틸디페닐암모늄염, 헥사데실피리디늄염, 라우릴피리디늄염, 도데실피리디늄염, 스테아릴아민아세테이트, 라우릴아민아세테이트, 옥타데실아민아세테이트 등을 들 수 있다.Examples of the cationic surfactant include quaternary ammonium salts and pyridinium salts. Specific examples thereof include lauryltrimethylammonium salt, stearyltrimethylammonium salt, lauryldimethylethylammonium salt, octadecyldimethylethylammonium salt, dimethyl There may be mentioned, for example, benzylamine, benzylamine, benzylamine, benzylamine, benzylamine, ethylbenzylamine, benzylamine, benzylamine, Stearylamine acetate, laurylamine acetate, octadecylamine acetate, and the like.

상기 아니온계 계면활성제로는, 알킬황산염, 폴리옥시에틸렌알킬에테르황산염, 폴리옥시에틸렌알킬페닐에테르황산염, 알킬벤질술폰산염, {(모노, 디, 트리)알킬}나프탈렌술폰산염 등을 들 수 있다. 또, 에틸렌옥사이드 및/또는 프로필렌옥사이드와 알킬아민 또는 디아민과의 축합 생성물의 황산화, 혹은 술폰산화 부가물도 사용할 수 있다.Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzyl sulfonates, and {(mono, di (tri) alkyl} naphthalenesulfonates. Also, sulfated or sulfonated adducts of condensation products of ethylene oxide and / or propylene oxide with alkyl amines or diamines can be used.

본 발명 2의 수계 구리 콜로이드 촉매액은, 본 발명 1의 같은 촉매액의 기본 조성과 같으며, (A) 가용성 구리염과, (B) 환원제와, (C) 콜로이드 안정제를 필수 성분으로 하고, 성분 (A)와 (C)의 혼합비율 요건도 본 발명 1과 동일하다.The aqueous copper colloid catalyst liquid of the present invention 2 is the same as the basic composition of the same catalyst liquid of the present invention 1 and contains (A) a soluble copper salt, (B) a reducing agent and (C) a colloid stabilizer as essential components, The mixing ratio requirements of the components (A) and (C) are also the same as those of the first invention.

본 발명 2의 촉매액에서는, 계면활성제의 함유를 0으로 배제하나, 극히 소량 이하로 억제하는 본 발명 1의 요건에 갈음하여, 합성계 수용성 폴리머를 함유하는 것을 특징으로 한다.The catalyst liquid of the present invention 2 is characterized by containing a synthetic water-soluble polymer in lieu of the requirements of the present invention 1 in which the content of the surfactant is suppressed to 0 but is suppressed to an extremely small amount or less.

당해 합성계 수용성 폴리머를 촉매액에 함유하면 콜로이드 입자의 분산성이 향상되며, 이로써 무전해 구리도금 시, 우수한 균일성과 얼룩 없는 구리 피막의 석출에 기여한다.When the synthetic water-soluble polymer is contained in the catalyst liquid, the dispersibility of the colloidal particles is improved, thereby contributing to excellent uniformity and precipitation of uneven copper film upon electroless copper plating.

상기 합성계 수용성 폴리머란, 젤라틴, 전분 등의 천연 유래 수용성 폴리머를 배제하는 의미이다.The synthetic water-soluble polymer is meant to exclude a naturally occurring water-soluble polymer such as gelatin and starch.

본 발명 2의 촉매액 함유 대상인 합성계 수용성 폴리머는, 본 발명 1의 촉매액의 함유 배제 또는 억제 대상인 계면활성제와의 관계로, 그 속하는 성분에 일부 중복될 가능성도 생각할 수 있으나, 본 발명에서 양자는 별개의 개념이다.The synthetic water-soluble polymer as the object of the present invention 2 containing the catalyst liquid may partially overlap the components thereof due to the presence or absence of the catalyst liquid of the present invention 1 or the surfactant to be inhibited. However, It is a separate concept.

본 발명 2의 촉매액에서는, 수용성 폴리머 이외의 성분 함유에 대해서는 요건으로 취하지 않으므로, 예를 들어 계면활성제의 함유 유무는 불문하여, 함유하거나 혹은 함유하지 않아도 되나, 기본적으로 본 발명 1과의 관계에서, 계면활성제는 함유하지 않는 것이 바람직하다.In the catalyst liquid of the present invention 2, it is not necessary to contain components other than the water-soluble polymer, and therefore it may or may not be contained in the catalyst liquid regardless of the presence or absence of the surfactant. , And it is preferable that it does not contain a surfactant.

상기 합성계 수용성 폴리머로는, 본 발명 3에 나타내는 바와 같이, 폴리에틸렌글리콜(PEG), 폴리프로필렌글리콜(PPG), 폴리비닐피롤리돈(PVP), 폴리비닐알코올(PVA), 폴리아크릴아마이드(PAM), 폴리에틸렌이민(PEI), 폴리아크릴산염 등을 들 수 있으며, 특히, 고분자량의 PEG, PVP, PVA 등이 바람직하다.(PEG), polypropylene glycol (PPG), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylamide (PAM), and the like are used as the synthetic water- , Polyethyleneimine (PEI), and polyacrylic acid salt. Particularly, PEG, PVP and PVA having high molecular weight are preferable.

합성계 수용성 폴리머는 단일 사용 또는 병용이 가능하며, 그 촉매액에 대한 함유량은 0.05~100g/L이고, 바람직하게는 0.5~50g/L, 보다 바람직하게는 1.0~30g/L이다.The synthetic water-soluble polymer may be used singly or in combination, and the content thereof in the catalyst liquid is 0.05 to 100 g / L, preferably 0.5 to 50 g / L, more preferably 1.0 to 30 g / L.

본 발명 9는, 상기 수계 구리 콜로이드 촉매액을 이용한 무전해 도금방법이며, 다음의 3가지 공정을 순차 조합시켜 이루어진다.The present invention 9 is an electroless plating method using the aqueous copper colloid catalyst solution, and the following three steps are sequentially combined.

(a) 흡착 촉진공정(a) Adsorption promotion process

(b) 촉매 부여공정(b) Catalyst application step

(c) 무전해 구리도금 공정(c) Electroless copper plating process

상기 흡착 촉진공정(a)은, 이른바 (b)의 촉매 부여의 전처리(예비처리) 공정이며, 노니온계 계면활성제, 카티온계 계면활성제, 아니온계 계면활성제, 양성 계면활성제로 이루어지는 군에서 선택된 흡착촉진제 중 적어도 한 종류의 함유액에 비도전성 기판을 침지하는 공정으로, 기판을 계면활성제 함유액에 접촉시킴으로써 기판 표면의 젖음성을 높이고 촉매 활성을 증강시켜, 다음 공정에서의 구리 콜로이드 촉매의 흡착을 촉진하는 것이다.The adsorption promoting step (a) is a pretreatment (pretreatment) step of so-called catalyst addition (b) and is an adsorption promoter selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants A step of immersing a non-conductive substrate in a liquid containing at least one kind of a surfactant, wherein the substrate is brought into contact with a surfactant-containing liquid to increase the wettability of the substrate surface and to enhance the catalytic activity and promote the adsorption of the copper- will be.

흡착 촉진공정에서는, 비도전성 기판을 계면활성제 함유액에 접촉시키는 것이 필요하므로, 액에 침지시키는 것이 기본이나, 함유액을 기판에 분무하거나, 브러시로 도포하는 등으로도 문제 없다.In the adsorption promoting step, it is necessary to bring the non-conductive substrate into contact with the surfactant-containing liquid, so it is essential to immerse the substrate in the liquid, but there is no problem even if the liquid is sprayed onto the substrate or applied with a brush.

본 발명 10에 나타내는 바와 같이, 흡착을 촉진하는 견지에서, 정전하를 띤 카티온계나 양성계 계면활성제가 적합하며, 특히 카티온계 계면활성제가 보다 바람직하다. 또, 카티온계 계면활성제에 소량의 노니온계 계면활성제를 병용하면, 흡착 촉진 효과가 더욱 증대된다.As shown in the present invention 10, from the viewpoint of promoting adsorption, a cationic surfactant with a positive charge and a positive surfactant are suitable, and a cationic surfactant is particularly preferable. When a cationic surfactant is used in combination with a small amount of a nonionic surfactant, the adsorption promoting effect is further increased.

본 발명 1 또는 2의 촉매액에 있어서, 가용성 구리염에 환원제를 작용시켜 생성하는 구리 콜로이드 입자는 제타 전위(zeta potential)가 마이너스이므로, 예를 들어 비도전성 기판을 카티온성 계면활성제로 접촉 처리하면, 기판이 플러스 전하를 띠기 쉬워, 다음 공정에서의 구리 콜로이드 입자의 기판 흡착 효율이 증대한다.In the catalyst solution of the present invention 1 or 2, since the zeta potential of the copper colloid particles produced by reacting the soluble copper salt with the reducing agent is negative, for example, when the non-conductive substrate is treated with the cationic surfactant , The substrate tends to have a positive charge, and the substrate adsorption efficiency of the copper colloid particles in the next step increases.

계면활성제의 구체예는, 상기 본 발명 1의 촉매액에서 배제 또는 억제 대상으로서 서술한 계면활성제의 설명과 같다.The specific examples of the surfactant are the same as the description of the surfactant described as an object to be excluded or inhibited in the catalyst solution of the first invention.

계면활성제의 함유량은, 0.05~100g/L이고, 바람직하게는 0.5~50g/L이다. 계면활성제 함유액의 온도는 15~70℃ 정도, 침지시간은 0.5~20분간 정도가 바람직하다.The content of the surfactant is 0.05 to 100 g / L, preferably 0.5 to 50 g / L. The temperature of the surfactant-containing liquid is preferably about 15 to 70 DEG C, and the immersion time is preferably about 0.5 to 20 minutes.

흡착 촉진 처리를 마친 비도전성 기판은 순물로 세정한 후, 건조 혹은 건조 처리 없이 다음의 촉매 부여 공정(b)으로 이행한다.After the non-conductive substrate having undergone the adsorption promoting treatment is cleaned with the pure substance, the process proceeds to the next catalyst application step (b) without drying or drying treatment.

촉매 부여 공정에서는, 상기 수계 구리 콜로이드 촉매액에 비도전성 기판을 침지하고, 기판 표면 상에 구리 콜로이드 입자를 흡착시킨다.In the catalyst imparting step, the non-conductive substrate is immersed in the aqueous copper colloid catalyst solution, and the copper colloid particles are adsorbed on the surface of the substrate.

당해 촉매액의 온도는 10~70℃ 정도, 침지시간은 0.1~20분 정도이며, 침지처리 시에는, 기판을 촉매액에 정치상태로 침지하면 충분하나, 교반이나 요동 처리를 실시해도 된다.The temperature of the catalyst liquid is about 10 to 70 DEG C and the immersion time is about 0.1 to 20 minutes. In the immersion treatment, it is sufficient to immerse the substrate in the catalyst liquid in the stationary state, but stirring or rocking treatment may be performed.

촉매액에 침지 처리한 비도전성 기판은, 순물로 세정한 후, 건조 혹은 건조 처리 없이 무전해 구리도금 공정(c)으로 이행한다.The non-conductive substrate immersed in the catalyst liquid is cleaned with a pure substance, and then the process proceeds to the electroless copper plating process (c) without drying or drying process.

무전해 구리도금은, 종래와 마찬가지로 처리하면 되며, 특별한 제약은 없다. 무전해 구리도금액의 액 온도는 일반적으로 15~70℃, 바람직하게는20~60℃이다.Electroless copper plating can be performed in the same manner as in the conventional method, and there is no particular limitation. The solution temperature of the electroless copper plating solution is generally from 15 to 70 캜, preferably from 20 to 60 캜.

구리도금액의 교반에서는, 공기교반, 급속 액류교반, 교반날에 의한 기계교반 등을 사용할 수 있다.For the stirring of the copper plating solution, air agitation, rapid liquid agitation, mechanical agitation by a stirring blade, and the like can be used.

무전해 구리도금액의 조성에 특별한 제한은 없으며, 공지된 구리도금액을 사용할 수 있다.The composition of the electroless copper plating solution is not particularly limited, and a known copper plating solution can be used.

무전해 구리도금액은, 기본적으로 가용성 구리염과, 환원제와, 착화제를 함유하거나, 혹은, 계면활성제나 pH조정제 등의 각종 첨가제 또는 산을 추가로 함유할 수 있다.The electroless copper plating solution may basically contain a soluble copper salt, a reducing agent and a complexing agent, or may further contain various additives such as a surfactant and a pH adjusting agent or an acid.

가용성 구리염에 대해서는, 상기 구리 콜로이드 촉매액에서 서술한 바와 같다.The soluble copper salt is as described above for the copper colloid catalyst solution.

무전해 구리도금액에 함유되는 환원제에 대해서도, 상기 구리 콜로이드 촉매액에서 서술한 바와 같이, 포름알데히드(포르말린수)를 비롯하여, 차아인산류, 아인산류, 아민보란류, 수소화붕소류, 글리옥실산 등이며, 포르말린수가 바람직하다.As for the reducing agent contained in the electroless copper plating solution, as described in the copper colloid catalyst solution, it is possible to use formaldehyde (formalin water) as well as hypophosphoric acids, phosphorous acids, amine borane, hydrogenated boron, And the formalin number is preferable.

무전해 구리도금액에 함유되는 착화제에 대해서는, 상기 구리 콜로이드 촉매액에서 서술한 콜로이드 안정제와 공통되는 부분도 있으며, 구체적으로는, 에틸렌디아민테트라아세트산(EDTA), 디에틸렌트리아민펜타아세트산(DTPA), 트리에틸렌테트라민헥사아세트산(TTHA), 하이드록시에틸 에틸렌디아민트리아세트산(HEDTA), 니트릴로트리아세트산(NTA), 이미노디아세트산(IDA) 등의 아미노카르복시산류, 에틸렌디아민, 테트라메틸렌디아민, 헥사메틸렌디아민, 디에틸렌트리아민, 테트라에틸렌펜타민, 펜타에틸렌헥사민 등의 폴리아민류, 모노에탄올아민, 디에탄올아민, 트리에탄올아민 등의 아미노알코올류, 구연산, 타르타르산, 젖산, 사과산 등의 옥시카르복시산류, 티오글루콜산, 글리신 등이다.The complexing agent contained in the electroless copper plating solution has a portion which is common to the colloidal stabilizer described in the copper colloid catalyst solution. Specifically, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA ), Aminocarboxylic acids such as triethylenetetraminehexaacetic acid (TTHA), hydroxyethylethylenediamine triacetic acid (HEDTA), nitrilotriacetic acid (NTA) and iminodiacetic acid (IDA), ethylenediamine, tetramethylenediamine, Polyamines such as methylene diamine, diethylenetriamine, tetraethylenepentamine and pentaethylenehexamine, aminoalcohols such as monoethanolamine, diethanolamine and triethanolamine, oxycarboxylic acids such as citric acid, tartaric acid, lactic acid and malic acid , Thioglycolic acid, glycine, and the like.

무전해 구리도금액에는, 액 베이스성분으로 유기산 및 무기산, 혹은 그 염을 함유할 수 있다.The electroless copper plating solution may contain an organic acid, an inorganic acid, or a salt thereof as a liquid base component.

상기 무기산으로는, 황산, 피롤린산, 붕불산 등을 들 수 있다. 또, 유기산으로는, 글리콜산이나 타르타르산 등의 옥시카르복시산, 메탄술폰산이나 2-하이드록시에탄술폰산 등의 유기술폰산 등을 들 수 있다.Examples of the inorganic acid include sulfuric acid, pyroluric acid, and borofluoric acid. Examples of the organic acid include oxycarboxylic acids such as glycolic acid and tartaric acid, and organic sulfonic acids such as methanesulfonic acid and 2-hydroxyethanesulfonic acid.

(실시예)(Example)

이하, 본 발명의 흡착촉진제 함유액, 구리 콜로이드 촉매액, 및 무전해 구리도금액의 제조를 포함하는 무전해 구리도금 방법의 실시예를 서술함과 더불어, 구리 콜로이드 촉매액의 경시 안정성 시험예, 상기 실시예에서 얻어진 석출 구리피막의 외관평가 시험예를 차례로 설명한다.Examples of the electroless copper plating method including the production of the adsorption promoting agent-containing liquid, the copper colloid catalyst solution, and the electroless copper plating solution of the present invention are described below. In addition, examples of the stability test of the copper colloid catalyst solution, The appearance evaluation test examples of the precipitated copper film obtained in the above examples will be described in turn.

여기서, 본 발명은 하기의 실시예, 시험예로 제한되는 것이 아니며, 본 발명의 기술적 사상의 범위 내에서 임의의 변형을 이룰 수 있음은 물론이다.Here, the present invention is not limited to the following examples and test examples, and it goes without saying that certain modifications can be made within the scope of the technical idea of the present invention.

<무전해 구리도금 방법의 실시예>&Lt; Embodiment of Electroless Copper Plating Method >

하기 실시예 1~18 중, 실시예 7은 구리 콜로이드 촉매액에 극히 소량의 계면활성제를 포함하는 예, 실시예 1~4, 실시예 8~12 및 실시예 18은 촉매액에 계면활성제를 포함하지 않는 예, 실시예 5~6, 실시예 9 및 실시예 13~17은 촉매액에 합성계 수용성 폴리머를 함유하는 예이다.In Examples 1 to 18, Example 7 shows that the copper colloid catalyst solution contains a very small amount of surfactant, Examples 1 to 4, Examples 8 to 12, and Example 18 each contain a surfactant in the catalyst solution Examples 5 to 6, Example 9 and Examples 13 to 17 are examples in which a synthetic water-soluble polymer is contained in the catalyst liquid.

실시예 1은 촉매액에 콜로이드 안정제로서 구연산을 사용하고, 환원제로서 수소화붕소나트륨을 사용한 예이다. 이하, 실시예 1을 기초로, 실시예 2는 콜로이드 안정제의 함유량을 저감한 예, 실시예 3은 콜로이드 안정제 함유량을 증량한 예, 실시예 4는 환원제 함유량을 저감한 예, 실시예 8은 콜로이드 안정제의 종류와 함유량을 변경한 예, 실시예 9는 환원제의 종류와 촉매액의 액 온도를 변경한 예이다. 또, 실시예 9를 기초로, 실시예 10~11, 15는 가용성 구리염을 변경한 예, 실시예 12는 콜로이드 안정제를 변경한 예이다.Example 1 is an example in which citric acid is used as a colloidal stabilizer in the catalyst solution and sodium borohydride is used as a reducing agent. In Example 2, the content of the colloidal stabilizer is reduced. In Example 3, the content of the colloidal stabilizer is increased. In Example 4, the content of the reducing agent is reduced. In Example 8, Examples in which the type and content of the stabilizer are changed, Example 9 is an example in which the kind of the reducing agent and the liquid temperature of the catalyst liquid are changed. On the basis of Example 9, Examples 10 to 11 and 15 are examples in which the soluble copper salt is changed, and Example 12 is an example in which the colloidal stabilizer is changed.

실시예 7은 전술한 바와 같이, 실시예 1을 기초로, 노니온계 계면활성제를 극히 소량 함유하며, 콜로이드 안정제의 종류와 촉매액의 pH를 변경한 예이다.Example 7 is an example in which an extremely small amount of a nonionic surfactant is used and the kind of the colloidal stabilizer and the pH of the catalyst liquid are changed based on Example 1 as described above.

그리고, 실시예 1을 기초로, 실시예 5는 촉매액에 폴리비닐피롤리돈(PVP)을 함유한 예, 실시예 6은 마찬가지로 폴리에틸렌글리콜(PEG)을 함유한 예, 실시예 9와 실시예 14는 PVP(평균 분자량을 변경)를 함유한 예, 실시예 13은 폴리에틸렌이민(PEI)을 함유한 예, 실시예 15는 폴리아크릴아마이드(PAM)를 함유한 예이다.On the basis of Example 1, Example 5 is an example in which polyvinylpyrrolidone (PVP) is contained in the catalyst solution, Example 6 contains polyethylene glycol (PEG) in the same manner, Example 9 and Example 14 is an example containing PVP (changing the average molecular weight), Example 13 is an example containing polyethyleneimine (PEI), and Example 15 is an example containing polyacrylamide (PAM).

실시예 1~15는 촉매액의 pH가 산성인 예이나, 실시예 16~18은 촉매액의 pH가 알칼리성인 예이다. 더불어, pH 조정에는 10~20% 정도의 황산, 혹은 수산화나트륨을 사용하였다.In Examples 1 to 15, the pH of the catalyst liquid is acidic, while in Examples 16 to 18, the pH of the catalyst liquid is alkaline. In addition, about 10 to 20% of sulfuric acid or sodium hydroxide was used for pH adjustment.

한편, 하기 비교예 1~6 중, 비교예 1은 촉매액에 콜로이드 안정제를 함유하지 않는 대조예, 비교예 2는 촉매액에서 구리염에 대한 콜로이드 안정제의 상대 함유비율이 본 발명 1~2 규정량의 하한보다 낮은 예, 비교예 3은 동 함유비율이 본 발명 1~2 규정량의 상한을 초과하는 예, 비교예 4는, 촉매액에 계면활성제를 본 발명 1의 억제 규정량을 초과하여 함유한 예, 비교예 5는 마찬가지로 촉매액에 계면활성제를 비교예 4보다 많이 함유한 예, 비교예 6은 흡착 촉진 공정 없이, 바로 촉매 부여 공정에서 무전해 도금공정을 실시한 대조예이다.On the other hand, in Comparative Examples 1 to 6 of the following Comparative Examples 1 to 6, the relative content ratios of the colloidal stabilizer to the copper salt in the catalyst solution in the catalyst solution and the catalyst solution in Comparative Example 2, In Comparative Example 3, the content of copper exceeds the upper limit of the amount specified in the present invention 1 to 2. In Comparative Example 4, the amount of the surfactant in the catalyst solution exceeds the inhibiting amount specified in the present invention 1 And Comparative Example 5 is an example in which the catalyst solution contains more surfactant than Comparative Example 4, and Comparative Example 6 is a control example in which the electroless plating process is performed in the catalyst addition process immediately without the adsorption promoting process.

또한, 서두에서 서술한 특허문헌 1의 실시예 4에서는 촉매액에 분산제로서 젤라틴을 함유하나, 비교예 7은 촉매액에 본 발명 2에서 규정하는 합성계가 아닌, 천연 유래의 수용성 폴리머인 젤라틴을 함유한 것으로, 이른바 상기 특허문헌 1의 준거예이다.In Example 4 of Patent Document 1 described in the opening paragraph, gelatin was contained as a dispersant in the catalyst liquid, whereas Comparative Example 7 contained gelatin, which is a water-soluble polymer derived from a naturally occurring, , Which is a reference example of the so-called Patent Document 1.

(1) 실시예 1(1) Example 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

다음과 같은 조성으로 흡착촉진제 함유액을 제조하였다.An adsorption accelerator-containing liquid was prepared with the following composition.

[흡착촉진제 함유액]     [Adsorption accelerator-containing liquid]

디아릴아민폴리머의 4급 암모늄염--------5g/L  Quaternary ammonium salt of diarylamine polymer -------- 5 g / L

폴리옥시알킬렌 분기 데실에테르---------1g/L  Polyoxyalkylene branched decyl ether --------- 1 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리용액]     [Copper solution]

황산구리(Cu2 +로서)-------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------- 0.2 mol / L

구연산-----------------------------0.6몰/L  Citric acid ----------------------------- 0.6 mol / L

[환원제 용액]     [Reducing agent solution]

수소화붕소나트륨---------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 조정한 25℃의 상기 구리용액에 환원제 용액을 적하하고 45분 교반하여, 수계 구리 콜로이드 촉매액을 제조하였다.The reducing agent solution was added dropwise to the copper solution at 25 ° C adjusted to pH 4.0 and stirred for 45 minutes to prepare an aqueous copper colloid catalyst solution.

상기 촉매액의 각 성분 몰비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:3, 구리염:환원제=1:1Copper salt: colloid stabilizer = 1: 3, copper salt: reducing agent = 1: 1

생성된 구리 콜로이드 입자의 평균 입경은 약 10nm였다.The average diameter of the copper colloidal particles produced was about 10 nm.

(c) 무전해 구리도금액의 제조(c) Preparation of electroless copper plating solution

다음의 조성으로 무전해 구리도금액을 건욕하였다. 당해 도금액은 하기 수산화나트륨으로 pH 조정하였다.The electroless copper plating solution was humidified by the following composition. The pH of the plating solution was adjusted with sodium hydroxide shown below.

[무전해 구리도금액]     [Electroless copper amount amount]

황산구리 오수화물(Cu2 +로서)------------2.0g/LCopper sulfate pentahydrate (as Cu 2 + ) ------------ 2.0 g / L

포름알데히드------------------------5.0 g/L  Formaldehyde ------------------------ 5.0 g / L

EDTA----------------------------30.0 g/L  EDTA ---------------------------- 30.0 g / L

수산화나트륨------------------------9.6 g/L  Sodium hydroxide ------------------------ 9.6 g / L

잔여-----------------------------순물  Residual -----------------------------

pH(20℃)--------------------------12.8  pH (20 &lt; 0 &gt; C) - 12.8

(d) 무전해 구리도금의 처리조건(d) Treatment conditions of electroless copper plating

우선, 비도전성 기판인 유리-에폭시 수지기판(파나소닉전공(주)제의 FR-4, 판 두께: 1.0mm)을 시료기판으로 하였다.First, a glass-epoxy resin substrate (FR-4 manufactured by Panasonic Electric Works Co., Ltd., thickness: 1.0 mm) serving as a non-conductive substrate was used as a sample substrate.

그리고, 상기 (a)의 흡착촉진제를 이용하여 시료기판에 흡착촉진 처리를 한 후, 상기 (b)의 촉매액에 침지하여 촉매 부여 처리한 후, 상기 (c)의 도금액에서 무전해 구리도금을 실시하였다.After the adsorption promoting treatment is applied to the sample substrate using the adsorption promoter of (a), the substrate is immersed in the catalyst solution of (b) to perform a catalyst imparting treatment, and electroless copper plating is performed in the plating solution of (c) Respectively.

구체적으로는, 상기 흡착촉진제 함유액에 상기 시료기판을 50℃, 2분의 조건으로 침지하고, 순물로 세정하였다. 이어서, 흡착촉진처리(전처리)를 실시한 시료기판을 상기 구리 콜로이드 촉매액에 25℃, 10분의 조건으로 침지하고, 순물로 세정하였다. 그 후, 촉매 부여를 실시한 시료기판을 상기 무전해 구리도금액에 침지하여 50℃, 10분의 조건으로 무전해 도금을 실시하고, 시료기판 상에 구리 피막을 형성한 후 순물로 세정하고 건조하였다.Specifically, the sample substrate was immersed in the adsorption-promoting agent-containing liquid at 50 DEG C for 2 minutes and washed with a pure substance. Subsequently, the sample substrate subjected to the adsorption promoting treatment (pretreatment) was immersed in the copper colloid catalyst solution at 25 DEG C for 10 minutes and washed with the pure substance. Thereafter, the sample substrate to which the catalyst was applied was immersed in the electroless copper plating solution and subjected to electroless plating at 50 DEG C for 10 minutes. A copper film was formed on the sample substrate, followed by washing with pure substance and drying .

(2) 실시예 2(실시예 1의 콜로이드 안정제를 저감한 예)(2) Example 2 (Example of reducing the colloidal stabilizer of Example 1)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:0.2, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 0.2, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

라우릴디메틸벤질암모늄클로라이드--------------5g/L  Lauryldimethylbenzylammonium chloride -------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산----------------------------------0.04몰/L  Citric acid ---------------------------------- 0.04 mol / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨--------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 15nm였다.The average diameter of the copper colloid particles produced was about 15 nm.

(3) 실시예 3(실시예 1의 콜로이드 안정제를 증가시킨 예)(3) Example 3 (Example in which the colloidal stabilizer of Example 1 is increased)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:15, 구리염:환원제=1:1Copper salt: colloid stabilizer = 1: 15, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

라우릴디메틸아미노아세트산베타인--------------5g/L  Lauryldimethylaminoacetic acid betaine -------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산-----------------------------------3.0몰/L  Citric acid ----------------------------------- 3.0 moles / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨--------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 12nm였다.The average diameter of the copper colloid particles produced was about 12 nm.

(4) 실시예 4(실시예 1의 환원제를 저감한 예)(4) Example 4 (Reduction of reducing agent of Example 1)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:0.5Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 0.5

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염---------------5g/L  Quaternary ammonium salt of diarylamine polymer --------------- 5 g / L

폴리옥시알킬렌 분기데실에테르-----------------1g/L  Polyoxyalkylene branched decyl ether ----------------- 1 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산----------------------------------0.8몰/L  Citric acid ---------------------------------- 0.8 mol / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨--------------------------0.01몰/L  Sodium borohydride -------------------------- 0.01 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 25nm였다.The average diameter of the copper colloid particles produced was about 25 nm.

(5) 실시예 5(실시예 1의 환원제를 증가한 예)(5) Example 5 (Example in which the reducing agent of Example 1 is increased)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:2.25Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 2.25

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염---------------5g/L  Quaternary ammonium salt of diarylamine polymer --------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산----------------------------------0.8몰/L  Citric acid ---------------------------------- 0.8 mol / L

폴리비닐피롤리돈(평균 분자량 40,000)----------2.0g/L  Polyvinylpyrrolidone (average molecular weight: 40,000) - 2.0 g / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨--------------------------0.45몰/L  Sodium borohydride 0.45 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 8nm였다.The average diameter of the copper colloidal particles produced was about 8 nm.

(6) 실시예 6(실시예 1의 콜로이드 안정제, 환원제를 저감한 예, 교반시간을 연장한 예)(6) Example 6 (colloidal stabilizer of Example 1, reduction example reduced, stirring time extended)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액(단, 교반시간은 제외)이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption-promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, a copper colloid catalyst solution (except for stirring time) or a method of producing electroless copper- The processing conditions of the process were the same as those in Example 1.

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:3, 구리염:환원제=1:0.5Copper salt: Colloidal stabilizer = 1: 3, Copper salt: Reducing agent = 1: 0.5

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

라우릴디메틸벤질암모늄클로라이드---------------5g/L  Lauryldimethylbenzylammonium chloride --------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산-----------------------------------0.6몰/L  Citric acid ----------------------------------- 0.6 mol / L

폴리에틸렌글리콜(평균 분자량 10,000)-----------1.0g/L  Polyethylene glycol (average molecular weight 10,000) ----------- 1.0 g / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨------------------------ --0.01몰/L  Sodium borohydride ------------------------ - 0.01 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 60분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C of pH 4.0 and stirred for 60 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 30nm였다.The average diameter of the copper colloid particles produced was about 30 nm.

(7) 실시예 7(실시예 1의 콜로이드 안정제의 변경, 양의 변경, pH 변경,촉매액에 계면활성제 첨가예)(7) Example 7 (modification of colloidal stabilizer of Example 1, change of amount, change of pH, addition of surfactant to catalyst solution)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액(단, pH 조건은 제외)이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption-promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, a copper colloid catalyst solution (except for the pH condition) and the method of producing the electroless copper- The processing conditions of the process were the same as those in Example 1.

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:3.5, 구리염:환원제=1:1Copper salt: colloid stabilizer = 1: 3.5, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

라우릴디메틸아미노아세트산베타인---------------5g/L  Lauryldimethylaminoacetic acid betaine --------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

글루콘산---------------------------------0.7몰/L  Gluconic acid --------------------------------- 0.7 mol / L

폴리옥시에틸렌-스틸렌화페닐에테르(EO10몰)------0.2g/L  Polyoxyethylene-styrenated phenyl ether (EO 10 moles) ------ 0.2 g / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨------------------------ --0.2몰/L  Sodium borohydride ------------------------ - 0.2 mol / L

pH3.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 3.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 17nm였다.The average diameter of the copper colloid particles produced was about 17 nm.

(8) 실시예 8(실시예 1의 콜로이드 안정제 변경, 양의 변경예)(8) Example 8 (Example of changing the amount of colloidal stabilizer in Example 1)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액(단, 교반시간은 제외)이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption-promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, a copper colloid catalyst solution (except for stirring time) or a method of producing electroless copper- The processing conditions of the process were the same as those in Example 1.

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:3, 구리염:환원제=1:1Copper salt: colloid stabilizer = 1: 3, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

라우릴디메틸벤질암모늄클로라이드---------------5g/L  Lauryldimethylbenzylammonium chloride --------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

글리콜산---------------------------------0.6몰/L  Glycolic acid --------------------------------- 0.6 mol / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨------------------------ --0.2몰/L  Sodium borohydride ------------------------ - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 90분 교반하였다.The reducing agent solution was added dropwise to a copper solution having a pH of 4.0 at 25 占 폚 and stirred for 90 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 15nm였다.The average diameter of the copper colloid particles produced was about 15 nm.

(9) 실시예 9(실시예 1의 환원제 변경, 도금욕 온도 변경예)(9) Example 9 (Change of reducing agent in Example 1, change in plating bath temperature)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액(단, 구리용액의 액 온도 조건 제외)이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption-promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the copper colloid catalyst solution (except for the solution temperature condition of the copper solution) and the preparation of the electroless copper plating solution The method and the treatment conditions of each step were the same as those of Example 1.

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:3, 구리염:환원제=1:0.5Copper salt: Colloidal stabilizer = 1: 3, Copper salt: Reducing agent = 1: 0.5

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염---------------5g/L  Quaternary ammonium salt of diarylamine polymer --------------- 5 g / L

폴리옥시알킬렌 분기데실에테르-----------------1g/L  Polyoxyalkylene branched decyl ether ----------------- 1 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산-----------------------------------0.6몰/L  Citric acid ----------------------------------- 0.6 mol / L

폴리비닐피롤리돈(분자량 300,000)--------------1.0g/L  Polyvinylpyrrolidone (molecular weight 300,000) -------------- 1.0 g / L

[환원제 용액]      [Reducing agent solution]

디메틸아민보란----------------------------0.1몰/L  Dimethylamine borane 0.1 mol / L

pH4.0으로 한 35℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to the copper solution at 35 DEG C adjusted to pH 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 45nm였다.The average diameter of the copper colloid particles produced was about 45 nm.

(10) 실시예 10(실시예 9의 가용성 구리염 변경예)(10) Example 10 (Example of soluble copper salt modification of Example 9)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액(단, pH와 구리용액의 액 온도 조건 제외)이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the copper colloid catalyst solution (except for the pH and the solution temperature condition of the copper solution) and the electroless copper solution amount And the processing conditions of each step were the same as those in Example 1. [

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:0.5Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 0.5

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

라우릴디메틸벤질암모늄클로라이드---------------5g/L  Lauryldimethylbenzylammonium chloride --------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

메탄술폰산구리(Cu2 +로서)--------------------0.2몰/LCopper methanesulfonate (as Cu 2 + ) - 0.2 mol / L

구연산-----------------------------------0.8몰/L  Citric acid ----------------------------------- 0.8 mol / L

[환원제 용액]      [Reducing agent solution]

디메틸아민보란----------------------------0.1몰/L  Dimethylamine borane 0.1 mol / L

pH3.0으로 한 35℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution having a pH of 3.0 at 35 DEG C and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 16nm였다.The average diameter of the copper colloid particles produced was about 16 nm.

(11) 실시예 11(실시예 9의 가용성 구리염 변경예)(11) Example 11 (Example of soluble copper salt modification of Example 9)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액(단, pH와 구리용액의 액 온도 조건 제외)이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the copper colloid catalyst solution (except for the pH and the solution temperature condition of the copper solution) and the electroless copper solution amount And the processing conditions of each step were the same as those in Example 1. [

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:3.5, 구리염:환원제=1:0.75Copper salt: colloidal stabilizer = 1: 3.5, copper salt: reducing agent = 1: 0.75

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염---------------5g/L  Quaternary ammonium salt of diarylamine polymer --------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

구연산구리 2.5수화물(Cu2 +로서)----------------0.2몰/LCopper citrate 2.5 Hydrate (as Cu 2 + ) ---------------- 0.2 mol / L

구연산-----------------------------------0.7몰/L  Citric acid ----------------------------------- 0.7 mol / L

[환원제 용액]      [Reducing agent solution]

디메틸아민보란----------------------------0.15몰/L  Dimethylamine borane 0.15 mol / L &lt; RTI ID = 0.0 &gt;

pH5.0으로 한 35℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution having a pH of 5.0 at 35 占 폚 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 14nm였다.The average diameter of the copper colloid particles produced was about 14 nm.

(12) 실시예 12(실시예 9의 콜로이드 안정제 변경예)(12) Example 12 (Example of modification of colloidal stabilizer of Example 9)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액(단, 구리용액의 액 온도 조건 제외)이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption-promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the copper colloid catalyst solution (except for the solution temperature condition of the copper solution) and the preparation of the electroless copper plating solution The method and the treatment conditions of each step were the same as those of Example 1.

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:2, 구리염:환원제=1:0.5Copper salt: colloidal stabilizer = 1: 2, copper salt: reducing agent = 1: 0.5

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

라우릴디메틸아미노아세트산베타인--------------5g/L  Lauryldimethylaminoacetic acid betaine -------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

글루콘산---------------------------------0.4몰/L  Gluconic acid --------------------------------- 0.4 mol / L

[환원제 용액]      [Reducing agent solution]

디메틸아민보란----------------------------0.1몰/L  Dimethylamine borane 0.1 mol / L

pH4.0으로 한 35℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to the copper solution at 35 DEG C adjusted to pH 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 20nm였다.The average diameter of the copper colloid particles produced was about 20 nm.

(13) 실시예 13(수용성 폴리머를 첨가한 경우)(13) Example 13 (when a water-soluble polymer is added)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급암모늄염---------------5g/L  Quaternary ammonium salt of diarylamine polymer --------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산-----------------------------------0.8몰/L  Citric acid ----------------------------------- 0.8 mol / L

폴리에틸렌이민----------------------------1.5g/L  Polyethyleneimine ---------------------------- 1.5g / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨--------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 17nm였다.The average diameter of the copper colloid particles produced was about 17 nm.

(14) 실시예 14(수용성 폴리머를 첨가한 경우)(14) Example 14 (when a water-soluble polymer is added)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급암모늄염---------------5g/L  Quaternary ammonium salt of diarylamine polymer --------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산-----------------------------------0.8몰/L  Citric acid ----------------------------------- 0.8 mol / L

폴리비닐피롤리돈(분자량 300,000)--------------1.0g/L  Polyvinylpyrrolidone (molecular weight 300,000) -------------- 1.0 g / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨--------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 15nm였다.The average diameter of the copper colloid particles produced was about 15 nm.

(15) 실시예 15(가용성 구리염 변경, 수용성 폴리머를 첨가한 경우)(15) Example 15 (soluble copper salt change, addition of water-soluble polymer)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급암모늄염---------------5g/L  Quaternary ammonium salt of diarylamine polymer --------------- 5 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

아세트산구리일수화물(Cu2 +로서)---------------0.2몰/LCopper acetate monohydrate (as Cu 2 + ) --------------- 0.2 mol / L

구연산-----------------------------------0.8몰/L  Citric acid ----------------------------------- 0.8 mol / L

폴리아크릴아미드---------------------------0.5g/L  Polyacrylamide --------------------------- 0.5 g / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨--------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 22nm였다.The average diameter of the copper colloid particles produced was about 22 nm.

(16) 실시예 16(실시예 1의 pH를 올린 예)(16) Example 16 (Example of raising the pH of Example 1)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액(단, pH 조건은 제외)이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption-promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, a copper colloid catalyst solution (except for the pH condition) and the method of producing the electroless copper- The processing conditions of the process were the same as those in Example 1.

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:3, 구리염:환원제=1:0.5Copper salt: Colloidal stabilizer = 1: 3, Copper salt: Reducing agent = 1: 0.5

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급암모늄염---------------5g/L  Quaternary ammonium salt of diarylamine polymer --------------- 5 g / L

폴리옥시알킬렌 분기데실에테르----------------1g/L  Polyoxyalkylene branched decyl ether ---------------- 1 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

에틸렌디아민테트라아세트산-------------------0.6몰/L  Ethylene diamine tetraacetic acid - 0.6 mol / L

폴리비닐피롤리돈(분자량 300,000)--------------1.0g/L  Polyvinylpyrrolidone (molecular weight 300,000) -------------- 1.0 g / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨--------------------------0.1몰/L  Sodium borohydride 0.1 mol / L

pH9.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at pH 9.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 18nm였다.The average diameter of the copper colloid particles produced was about 18 nm.

(17) 실시예 17(실시예 1의 pH를 올린 예)(17) Example 17 (Example of raising the pH of Example 1)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액(단, pH 조건은 제외)이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption-promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, a copper colloid catalyst solution (except for the pH condition) and the method of producing the electroless copper- The processing conditions of the process were the same as those in Example 1.

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염--------------5g/L  Quaternary ammonium salt of diarylamine polymer -------------- 5g / L

폴리옥시알킬렌 분기데실에테르----------------1g/L  Polyoxyalkylene branched decyl ether ---------------- 1 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

니트릴로트리아세트산-----------------------0.8몰/L  Nitrilotriacetic acid ----------------------- 0.8 mol / L

폴리아크릴아미드--------------------------1.0g/L  Polyacrylamide - 1.0 g / L

[환원제 용액]      [Reducing agent solution]

디메틸아민보란----------------------------0.2몰/L  Dimethylamine borane 0.2 mol / L

pH10.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 10.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 15nm였다.The average diameter of the copper colloid particles produced was about 15 nm.

(18) 실시예 18(실시예 1의 pH를 올린 예)(18) Example 18 (Example of raising the pH of Example 1)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액(단, pH 조건은 제외)이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption-promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, a copper colloid catalyst solution (except for the pH condition) and the method of producing the electroless copper- The processing conditions of the process were the same as those in Example 1.

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:3, 구리염:환원제=1:0.5Copper salt: Colloidal stabilizer = 1: 3, Copper salt: Reducing agent = 1: 0.5

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염--------------5g/L  Quaternary ammonium salt of diarylamine polymer -------------- 5g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

디에틸렌트리아민펜타아세트산-----------------0.6몰/L  Diethylene triamine pentaacetic acid - 0.6 mol / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨---------------------------0.1몰/L  Sodium borohydride 0.1 mol / L

pH10.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 10.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 20nm였다.The average diameter of the copper colloid particles produced was about 20 nm.

(19) 비교예 1(촉매액에 안정제가 없는 경우)(19) Comparative Example 1 (when the stabilizer is not present in the catalyst liquid)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액의 각 성분 몰 비율은 다음과 같다.The mole ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:0, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 0, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염--------------5g/L  Quaternary ammonium salt of diarylamine polymer -------------- 5g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨---------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

구리 콜로이드 입자는 생성되었으나, 응집, 침전하였다.Copper colloidal particles were formed but aggregated and precipitated.

(20) 비교예 2(구리와 안정제의 비율이 최소한도 미만일 경우)(20) Comparative Example 2 (when the ratio of copper to stabilizer is less than minimum)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액 각 성분의 몰 비율은 다음과 같다.The molar ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:0.01, 구리염:환원제=1:1Copper salt: colloid stabilizer = 1: 0.01, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염--------------5g/L  Quaternary ammonium salt of diarylamine polymer -------------- 5g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산-----------------------------------0.002몰/L  Citric acid ----------------------------------- 0.002 mol / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨---------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

구리 콜로이드 입자는 생성되었으나, 응집, 침전하였다.Copper colloidal particles were formed but aggregated and precipitated.

(21) 비교예 3(구리와 안정제의 비율이 최대한도를 초과할 경우)(21) Comparative Example 3 (when the ratio of copper to stabilizer exceeds the maximum limit)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액 각 성분의 몰 비율은 다음과 같다.The molar ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:36, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 36, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염--------------5g/L  Quaternary ammonium salt of diarylamine polymer -------------- 5g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

젖산------------------------------------7.2몰/L  Lactic acid ------------------------------------ 7.2 mol / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨---------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

구리 콜로이드 입자는 생성되지 않았다.No copper colloid particles were produced.

(22) 비교예 4(실시예1의 촉매액에 본원 규정치를 초과하여 계면활성제를 함유한 예)(22) Comparative Example 4 (Example in which the surfactant was contained in the catalyst liquid of Example 1 in excess of the value specified in the present invention)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액 각 성분의 몰 비율은 다음과 같다.The molar ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염--------------5g/L  Quaternary ammonium salt of diarylamine polymer -------------- 5g / L

폴리옥시알킬렌 분기데실에테르----------------1g/L  Polyoxyalkylene branched decyl ether ---------------- 1 g / L

(b) 구리 콜로이드 촉매액의 제조 (b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산-----------------------------------0.8몰/L  Citric acid ----------------------------------- 0.8 mol / L

폴리옥시에틸렌-옥틸페닐에테르(EO15몰)----------1.0g/L  Polyoxyethylene-octyl phenyl ether (EO 15 moles) - 1.0 g / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨---------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 15nm였다.The average diameter of the copper colloid particles produced was about 15 nm.

(23) 비교예 5(실시예1의 촉매액에 계면활성제를 다량 함유한 예)(23) Comparative Example 5 (Example in which the catalyst liquid of Example 1 contains a large amount of surfactant)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액 각 성분의 몰 비율은 다음과 같다.The molar ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염--------------5g/L  Quaternary ammonium salt of diarylamine polymer -------------- 5g / L

폴리옥시알킬렌 분기데실에테르----------------1g/L  Polyoxyalkylene branched decyl ether ---------------- 1 g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산-----------------------------------0.8몰/L  Citric acid ----------------------------------- 0.8 mol / L

폴리옥시에틸렌-옥틸페닐에테르(EO15몰)----------8.0g/L  Polyoxyethylene-octylphenyl ether (EO 15 moles) - 8.0 g / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨---------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

구리 콜로이드 입자는 생성되었으나, 응집, 침전하였다.Copper colloidal particles were formed but aggregated and precipitated.

(24) 비교예 6(실시예1의 공정에서 흡착 촉진공정이 없는 블랭크 예)(24) Comparative Example 6 (Blank example without the adsorption promoting step in the process of Example 1)

상기 실시예 1을 기초로 하고, 흡착 촉진공정을 생략한 예로서, 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.As an example of omitting the adsorption promoting step on the basis of Example 1, except that the copper colloid catalyst solution was prepared with the following composition, the production method of the electroless copper plating solution and the treatment conditions of each step were the same as those of Example 1 .

상기 촉매액 각 성분의 몰 비율은 다음과 같다.The molar ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 1

(a) 구리 콜로이드 촉매액의 제조(a) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산-----------------------------------0.8몰/L  Citric acid ----------------------------------- 0.8 mol / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨---------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

생성된 구리 콜로이드 입자의 평균 입경은 약 17nm였다.The average diameter of the copper colloid particles produced was about 17 nm.

(25) 비교예 7(촉매액에 젤라틴을 첨가한 예) (25) Comparative Example 7 (Example in which gelatin is added to the catalyst liquid)

상기 실시예 1을 기초로, 흡착촉진제 함유액 및 구리 콜로이드 촉매액을 다음의 조성으로 제조한 것 이외에는, 구리 콜로이드 촉매액이나 무전해 구리도금액의 제조방법 및 각 공정의 처리조건은 실시예 1과 동일하게 하였다.Based on the above Example 1, except that the adsorption promoting agent-containing liquid and the copper colloid catalyst solution were prepared in the following composition, the production method of the copper colloid catalyst solution or the electroless copper plating solution and the treatment conditions of each step were the same as in Example 1 .

상기 촉매액 각 성분의 몰 비율은 다음과 같다.The molar ratio of each component of the catalyst solution is as follows.

구리염:콜로이드 안정제=1:4, 구리염:환원제=1:1Copper salt: colloidal stabilizer = 1: 4, copper salt: reducing agent = 1: 1

(a) 흡착촉진제 함유액의 제조(a) Preparation of adsorption accelerator-containing liquid

[흡착촉진제의 함유액]      [Content of Adsorption Accelerator]

디아릴아민폴리머의 4급 암모늄염--------------5g/L  Quaternary ammonium salt of diarylamine polymer -------------- 5g / L

(b) 구리 콜로이드 촉매액의 제조(b) Preparation of Copper Colloidal Catalyst Solution

[구리 용액]      [Copper solution]

황산구리(Cu2 +로서)-------------------------0.2몰/LCopper sulfate (as Cu 2 + ) ------------------------- 0.2 mol / L

구연산-----------------------------------0.8몰/L  Citric acid ----------------------------------- 0.8 mol / L

젤라틴-----------------------------------1.0g/L  Gelatin ----------------------------------- 1.0 g / L

[환원제 용액]      [Reducing agent solution]

수소화붕소나트륨---------------------------0.2몰/L  Sodium borohydride - 0.2 mol / L

pH4.0으로 한 25℃의 구리 용액에 환원제 용액을 적하하여 45분 교반하였다.The reducing agent solution was added dropwise to a copper solution at 25 DEG C at a pH of 4.0 and stirred for 45 minutes.

구리 콜로이드 입자는 생성되었으나, 응집, 침전되었다.Copper colloidal particles were formed but coagulated and precipitated.

<촉매액의 경시안정성 시험예>&Lt; Example of stability stability test of catalyst liquid &

여기서, 상기 실시예 1~18 및 비교예1~7에서 제조된 각 구리 콜로이드 촉매액에 대하여, 하기 기준으로 콜로이드 안정성의 우열을 평가하였다.Herein, the copper colloid catalyst solutions prepared in Examples 1 to 18 and Comparative Examples 1 to 7 were evaluated for colloidal stability by the following criteria.

○: 건욕 후 1개월간 침전, 혹은 분해가 일어나지 않았다.○: No sedimentation or decomposition occurred for one month after the bathing.

×: 건욕 후 바로 침전, 혹은 분해되었다.X: Precipitation or disintegration immediately after bathing.

<무전해 구리도금으로 석출된 구리 피막의 외관평가시험 예>&Lt; Evaluation test example of appearance evaluation of copper film deposited by electroless copper plating >

이어서, 상기 실시예 1~18 및 비교예1~7의 무전해 구리도금 방법으로 얻어진 구리의 무전해 피막에 대하여, 하기 기준으로 피막 외관의 우열을 육안평가 하였다.Next, with respect to the electroless copper plating film obtained by the electroless copper plating methods of Examples 1 to 18 and Comparative Examples 1 to 7, the superiority of the outer appearance of the coating film was visually evaluated on the basis of the following criteria.

◎：구리도금 피막이 균일하며 얼룩이 없다.◎: Copper plating film is uniform, and there is no unevenness.

○：구리도금 피막에 얼룩이 보였다.○: The copper plating film was stained.

△：구리도금 피막에 일부 미석출(도금 결함)이 보였다.B: Partial precipitation (plating defect) was observed in the copper-plated film.

×：구리피막이 석출되지 않았다.X: Copper film was not deposited.

여기서, 석출 피막의 “얼룩”은, 피막의 치밀성이나 평활성 등에 주위와 다른 부분이 있는 것으로 인정된다. 피막의 “얼룩”은 피막의 균일성과는 별개의 관점이다.Here, it is recognized that the &quot; smudge &quot; of the deposited film has a different portion from that of the surrounding, such as the denseness and smoothness of the film. The "smear" of the film is a view that is independent of the uniformity of the film.

<구리 콜로이드 촉매액의 경시안정성과 피막 외관에 대한 시험결과>&Lt; Test results on the stability of the copper colloid catalyst solution with respect to time and the outer appearance of the coating film &

피막외관Coating appearance 경시안정성Stability over time 피막외관Coating appearance 경시안정성Stability over time 실시예1Example 1 ◎◎ ○○ 비교예1Comparative Example 1 ×× ×× 실시예2Example 2 ◎◎ ○○ 비교예2Comparative Example 2 ×× ×× 실시예3Example 3 ○○ ○○ 비교예3Comparative Example 3 ×× ×× 실시예4Example 4 ◎◎ ○○ 비교예4Comparative Example 4 △△ ○○ 실시예5Example 5 ◎◎ ○○ 비교예5Comparative Example 5 ×× ○○ 실시예6Example 6 ◎◎ ○○ 비교예6Comparative Example 6 △△ ○○ 실시예7Example 7 ○○ ○○ 비교예7Comparative Example 7 △△ ×× 실시예8Example 8 ◎◎ ○○ 실시예9Example 9 ◎◎ ○○ 실시예10Example 10 ◎◎ ○○ 실시예11Example 11 ◎◎ ○○ 실시예12Example 12 ○○ ○○ 실시예13Example 13 ◎◎ ○○ 실시예14Example 14 ◎◎ ○○ 실시예15Example 15 ◎◎ ○○ 실시예16Example 16 ◎◎ ○○ 실시예17Example 17 ◎◎ ○○ 실시예18Example 18 ◎◎ ○○

<촉매액의 경시안정성과 도금피막 외관의 종합평가>&Lt; Evaluation of aging stability of catalyst solution and appearance of plating film appearance >

구리 콜로이드 촉매액 콜로이드 안정제를 제외하는 비교예 1은 촉매액의 경시안정성이 떨어지며, 따라서 촉매액과 접촉 후 비도전성 기판에 무전해 도금을 실시해도 구리 피막의 석출은 없었다 .In Comparative Example 1 except for the copper colloid catalyst solution colloid stabilizer, the stability of the catalyst solution with time was inferior. Therefore, even when electroless plating was performed on the non-conductive substrate after contact with the catalyst solution, there was no precipitation of the copper film.

또한 콜로이드 안정제와 구리염 비율에서, 콜로이드 안정제의 상대적인 양이 너무 적으면 비교예 2에 나타내는 바와 같이, 역시 촉매액의 경시안정성이 떨어지고, 따라서 무전해 도금에서 구리 피막의 석출이 없었다. 이는 콜로이드 안정제의 상대적인 양이 너무 많은 경우도 마찬가지로, 비교예 3에 나타내는 바와 같이, 촉매액의 경시안정성이 떨어지고, 무전해 도금에서 구리 피막의 석출은 없었다.When the relative amount of the colloidal stabilizer was too small in the ratio of the colloidal stabilizer and the copper salt, as shown in Comparative Example 2, the stability of the catalyst solution with the elapse of time was lowered, and thus the copper film was not precipitated by electroless plating. Even when the relative amount of the colloidal stabilizer was too large, as shown in Comparative Example 3, the stability of the catalyst solution with time deteriorated, and there was no precipitation of the copper film by electroless plating.

비도전성 기판을 흡착촉진 처리 없이 촉매 부여하고, 무전해 구리 도금을 실시한 비교예 6에서는 촉매액의 경시안정성은 각 실시예와 동일했지만, 석출 된 구리 피막에서는 일부에 미석출 부분이 생기는 「도금 결여」가 인정된 점에서, 촉매 부여 전에 흡착촉진 예비 처리가 없음에 기인하여 촉매활성이 부족하고, 기판으로의 구리 콜로이드 입자의 흡착이 실시예에 비해 뒤떨어짐을 알 수 있다.In Comparative Example 6 in which a non-conductive substrate was provided with a catalyst without an adsorption promoting treatment and the electroless copper plating was performed, the stability of the catalyst solution with respect to time was the same as in each Example. However, in the precipitated copper film, , It is understood that the catalytic activity is insufficient due to the absence of the adsorption promoting pretreatment before the application of the catalyst and the adsorption of the copper colloid particles on the substrate is inferior to that in the embodiment.

한편, 흡착촉진 예비처리를 한 후 촉매부여 처리를 하고, 이어서 무전해 구리 도금을 실시한 실시예 1~18에서는, 모두 촉매액의 경시안정성은 양호하며, 무전해 도금으로 석출된 구리 피막은 대체로 얼룩이 없이 균일성이 우수했다.On the other hand, in Examples 1 to 18 in which electroless copper plating was carried out after the adsorption promoting pretreatment and after the catalyst imparting treatment, the stability of the catalyst solution with respect to time was good, and the copper film precipitated by electroless plating was largely uneven Uniformity was excellent.

당해 실시예 1~18을 상기 비교예 1과 대비하면, 얼룩이 없고 우수한 균일성의 구리 피막을 얻기 위하여, 촉매액에는 구리염과 환원제만이 아닌, 콜로이드 안정제의 함유가 필수임을 알 수 있다. 또한, 실시예 1~18를 비교예 2~3과 대비하면, 얼룩이 없고 우수한 균일성의 구리 피막을 얻기 위해서는, 콜로이드 안정제를 함유하는 것만으로는 부족하며, 콜로이드 안정제와 구리염의 함유비율의 적정화가 중요하다는 것을 판단할 수 있다.Comparing Examples 1 to 18 with Comparative Example 1, it is understood that the colloidal stabilizer is required to be contained in the catalyst solution, not only the copper salt and the reducing agent, in order to obtain a copper film having no unevenness and excellent uniformity. Comparing Examples 1 to 18 with Comparative Examples 2 to 3, it is not sufficient to contain a colloidal stabilizer in order to obtain a copper film having no unevenness and excellent uniformity, and it is important to optimize the content ratio of the colloidal stabilizer and the copper salt Can be judged.

촉매액에 계면 활성제를 본 발명 1의 억제 규정량을 초과하여 함유한 비교예 4에서는, 무전해 도금에서 석출된 구리 피막의 일부에 미출이 발생하는「도금 결여」가 인정되었다. 그리고 촉매액에 비교예 4보다 많이 계면활성제를 함유시킨 비교예 5에서는, 무전해 도금에서 구리 피막은 석출되지 않았다. 이에 반해 계면활성제를 본 발명 1의 규정량 이하의 극히 소량으로 억제한 실시예 7에서는, 무전해 도금에서 도금 결여 등이 발생하는 일 없이, 구리 피막은 원활하게 석출되었다(단, 피막에 얼룩이 인정되었다). 또한 촉매액에 계면활성제를 함유하지 않는 실시예 1~4, 실시예 8~12 및 실시예 18에서는 당연히 얼룩이 없고 우수한 균일성의 구리 피막이 석출되었다. 즉, 촉매액에 본 발명의 규정치를 초과하여 계면활성제를 첨가하면, 구리 콜로이드 촉매액의 촉매활성이 저하되어 무전해 도금에서 얻어지는 구리 피막에는 도금 결여가 발생하며, 또한 계면활성제의 함유량을 많이 하면 액체의 촉매활성을 잃어 구리 피막이 석출되지 않은 점에서, 계면활성제의 함량을 극히 소량으로 억제하는 경우에만 구리 피막이 원활하게 석출되나, 촉매액으로의 계면활성제의 함량이 높을수록 촉매액의 활성은 저하되기 때문에, 구리 콜로이드 촉매액의 촉매활성을 유지하기 위해서는, 기본적으로 계면활성제를 첨가하지 않는 것이 바람직하다고 판단 할 수 있다.In Comparative Example 4 in which the surfactant contained the surfactant in an amount exceeding the inhibiting specified amount of the present invention 1, a "plating lack" in which part of the copper film deposited by the electroless plating occurred was recognized. In Comparative Example 5 in which the surfactant was contained in the catalyst solution more than Comparative Example 4, no copper film was precipitated by electroless plating. On the other hand, in Example 7 in which the surfactant was suppressed to a very small amount below the specified amount of the present invention 1, the copper film was smoothly precipitated without occurrence of plating failure or the like in the electroless plating (however, ). In Examples 1 to 4, Examples 8 to 12, and Example 18 in which the surfactant was not contained in the catalyst solution, copper coatings with no unevenness and excellent uniformity were naturally precipitated. That is, when the surfactant is added to the catalyst liquid in excess of the specified value of the present invention, the catalytic activity of the copper colloid catalyst solution is lowered, and plating failure occurs in the copper film obtained by the electroless plating. When the content of the surfactant is increased The copper film is smoothly precipitated only when the content of the surfactant is suppressed to a very small amount because the copper film is not precipitated due to the loss of the catalytic activity of the liquid. However, the higher the content of the surfactant in the catalyst liquid, , It can be judged that it is preferable to basically not add a surfactant in order to maintain the catalytic activity of the copper colloid catalyst liquid.

또한 천연 유래의 수용성 폴리머의 대표적인 예인 젤라틴을 촉매액에 함유시킨 비교예 7에서는, 촉매액의 경시안정성이 떨어지고, 이로써 무전해 도금 시에는 얻어지는 구리 피막에서 일부에 미석출의 「도금 결여」가 인정되었다. 한편, 촉매액에 합성계의 수용성 폴리머를 함유한 실시예 5~6 및 실시예 13~17에서는 얼룩이 없고 우수한 균일성의 구리피막이 석출된 점에서, 뛰어난 실용 수준의 구리피막을 얻기 위해서는, 수용성 폴리머 중에서도 합성계 폴리머를 선택할 필요가 있다는 것이 증명되었다.Further, in Comparative Example 7 in which gelatin, which is a representative example of a water-soluble polymer derived from natural origin, is contained in the catalyst liquid, stability with time of the catalyst liquid is lowered. As a result, in the electroless plating, a "plating lack" . On the other hand, in Examples 5 to 6 and Examples 13 to 17 in which a water-soluble polymer of a synthetic system was contained in the catalyst solution, copper coatings having no unevenness and excellent uniformity were precipitated. In order to obtain copper coatings of excellent practical level, It has been demonstrated that there is a need to choose polymers.

이어서, 실시예 1~18에 대하여 상세히 검토한다.Next, Examples 1 to 18 will be examined in detail.

실시예 1을 기준으로 하여 다른 실시예와의 상대적인 평가를 설명한다. 우선, 실시예 1은, 양이온계 계면활성제인 디알릴아민폴리머의 4급 암모늄염을 포함하는 흡착촉진제로 비도전성 기판을 예비처리하고, 황산구리를 구리염으로 하며, 수소화붕소나트륨을 환원제로 하고, 구연산을 콜로이드 안정제로 하는 촉매액에서 촉매 부여한 후, 무전해 구리 도금을 실시한 예인데, 촉매액의 경시안정성은 양호하며, 건욕 후 1 개월이 경과해도 침전이 생기거나 분해되는 일은 없으며, 또 무전해 도금에서 얻어진 구리 피막은 균일성이 우수하고, 석출 불균일도 보이지 않았다.The relative evaluation with respect to the other embodiments will be described with reference to the first embodiment. First, in Example 1, a non-conductive substrate was preliminarily treated with an adsorption promoter containing a quaternary ammonium salt of a diallylamine polymer as a cationic surfactant, copper sulfate was used as a copper salt, sodium borohydride was used as a reducing agent, And the electroless copper plating is performed. The stability of the catalyst solution with respect to time is good, and precipitation does not occur or decomposition does not occur even after one month from the operation of the bath, and the electroless plating The copper film obtained in the above was excellent in uniformity and showed no precipitation unevenness.

실시예 2는 실시예 1에 대하여 콜로이드 안정제의 구리염에 대한 함유 비율을 낮춘 예, 실시예 4는 실시예 1에 대하여 환원제의 함량을 낮춘 예, 실시예 5는 환원제의 함량을 늘린 예, 실시예 8은 콜로이드 안정제를 실시예 1의 구연산에서 글리콜산으로 변경한 예인데, 촉매액의 경시안정성 및 도금 피막의 외관에 대해서는, 각각 실시예 1과 같은 평가였다.Example 2 is an example in which the content of the colloidal stabilizer in the copper salt is lowered in Example 1, Example 4 is an example in which the content of the reducing agent is lowered in Example 1, Example 5 is an example in which the content of the reducing agent is increased Example 8 was an example in which the colloidal stabilizer was changed from citric acid to glycolic acid in Example 1, and the stability of the catalyst solution with respect to time and the appearance of the plated film were evaluated in the same manner as in Example 1, respectively.

실시예 9는 실시예 1에 대하여, 환원제를 실시예 1의 수소화붕소나트륨에서 디메틸아민보란으로 변경하고, 촉매액의 온도를 올린 예인데, 촉매액의 경시안정성 및 도금피막의 외관은 실시예 1과 동일한 평가였다. 실시예 10은 메탄술폰산을 구리염으로 한 예, 실시예 11은 염화구리를 구리염으로 한 예인데, 촉매액의 경시안정성 및 도금피막의 외관은 실시예 1과 동일한 평가였다.Example 9 is an example in which the reducing agent is changed from sodium borohydride in Example 1 to dimethylamine borane and the temperature of the catalyst liquid is raised. Example 9 shows the stability of the catalyst solution over time and the appearance of the plated film in Example 1 . Example 10 is an example in which methanesulfonic acid is used as a copper salt, and Example 11 is an example in which copper chloride is used as a copper salt. The stability of the catalyst solution over time and the appearance of the plating film were evaluated in the same manner as in Example 1.

전술한 바와 같이, 촉매액에 계면활성제를 함유하지 않는 실시예 1~4, 실시예 8~12 및 실시예 18에서, 도금 피막은 균일성이 우수하고, 얼룩도 인정되지 않았다. 또 계면활성제가 본 발명 1의 규정량 이하의 극히 소량 존재하는 실시예 7에서는, 무전해 도금에서 도금 결여 등이 발생하는 일 없이, 구리피막은 원활하게 석출되었으나, 피막에 석출 불균일이 인정되었다.As described above, in Examples 1 to 4, Examples 8 to 12 and Example 18 in which the surfactant was not contained in the catalyst solution, the plating film was excellent in uniformity and no stain was observed. In Example 7 in which the surfactant was present in an extremely small amount of less than the specified amount of the present invention 1, the copper film was smoothly deposited without plating loss or the like in the electroless plating, but deposition irregularity was recognized in the film.

촉매액에 수용성 폴리머로서 PVP(평균 분자량 40000)을 함유한 실시예5, 마찬가지로 PEG를 함유한 실시예 6, PEI를 함유한 실시예 13, PVP(평균 분자량 300000)을 함유한 실시예 9와 14, PAM을 함유한 실시예 15에서는, 촉매액의 경시안정성 및 도금피막의 외관에 대하여 각각 실시예 1과 동일한 평가였다.Example 5 containing PEG as the water-soluble polymer, PVP (average molecular weight of 40000), Example 6 containing PEG, Example 13 containing PEI, Examples 9 and 14 containing PVP (average molecular weight of 300000) In Example 15 containing PAM, the stability of the catalyst solution with respect to time and the appearance of the plated film were evaluated in the same manner as in Example 1, respectively.

촉매액을 pH4.0으로 설정한 실시예 1에 대하여, pH3의 실시예 10, pH5의 실시예 11, pH9의 실시예 16, pH10의 실시예 17~18에서는 촉매액의 경시안정성과 도금피막의 외관에 대하여 각각 실시예 1과 동일한 평가였다.In Example 1 where the catalyst solution was set to pH 4.0, the stability of the catalyst solution with respect to time and stability of the plating solution in Example 10 of pH 3, Example 11 of pH 5, Example 16 of pH 9 and Examples 17 to 18 of pH 10 The appearance was the same as in Example 1, respectively.

Claims (6)

무전해 구리도금을 실시할 비도전성 기판에 접촉시켜 촉매 부여를 하기 위한 수계 구리 콜로이드 촉매액에 있어서,
(A) 가용성 구리염과,
(B) 환원제와,
(C) 옥시카르복시산류, 아미노카르복시산류로 이루어지는 군에서 선택된 콜로이드 안정제의 적어도 1 종을 함유하며, 상기 성분 (A)와 (C)의 함유 몰비율을 A:C = １：0.03 ~ 1:35로 함과 더불어,
계면활성제를 함유하지 않고,
폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리비닐피롤리돈, 폴리비닐알콜, 폴리아크릴아마이드, 폴리에틸렌이민 중에서 선택된 합성계 수용성 폴리머를 함유하지 않고,
젤라틴을 포함하지 않고,
염소 이온을 포함하지 않고,
pH가 2~5 또는 9~10인 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액.An aqueous copper colloid catalyst solution for bringing a catalyst into contact with a non-conductive substrate to be subjected to electroless copper plating,
(A) a soluble copper salt,
(B) a reducing agent,
(C) oxycarboxylic acids and aminocarboxylic acids, wherein the molar ratio of the components (A) to (C) is in the range of A: C = 1: 0.03 to 1:35 In addition,
Without containing a surfactant,
A water-soluble polymer selected from polyethylene glycol, polypropylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylamide, and polyethylene imine,
Without gelatin,
Without chlorine ions,
wherein the pH is 2 to 5 or 9 to 10. The aqueous copper-colloidal catalyst solution for electroless copper plating according to claim 1, 제1항에 있어서,
환원제(B)가 수소화붕소화합물, 아민보란류, 차아인산류, 알데히드류, 아스코르빈산류, 하이드라진류, 다가페놀류, 다가나프톨류, 페놀술폰산류, 나프톨술폰산류, 술핀산(sulfinic acid)류로 이루어지는 군에서 선택된 적어도 1 종인 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액.The method according to claim 1,
Wherein the reducing agent (B) is at least one compound selected from the group consisting of a borohydride compound, an amine borane, a hypophosphorous acid, an aldehyde, an ascorbic acid, a hydrazine, a polyhydric phenol, a divalent naphthol, a phenolsulfonic acid, a naphthosulfonic acid and a sulfinic acid Wherein the copper-colloidal solution is at least one member selected from the group consisting of copper-colloid-based catalysts for electroless copper plating. 제1항에 있어서,
옥시카르복시산류(C)가, 구연산, 주석산, 사과산, 글루콘산, 글루코헵탄(Glucoheptonic acid), 글리콜산, 젖산, 트리옥시부티르산, 이소구연산, 타르트론산, 글리세린산, 하이드록시부티르산, 로이신산, 시트라말산(citramalic acid)및 이들의 염으로 이루어진 군에서 선택된 적어도 1 종인 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액.The method according to claim 1,
Wherein the oxycarboxylic acids (C) are at least one selected from the group consisting of citric acid, tartaric acid, malic acid, gluconic acid, glycolic acid, lactic acid, trioxybutyric acid, isocitric acid, tartronic acid, glyceric acid, hydroxybutyric acid, Wherein the copper-colloidal solution is at least one member selected from the group consisting of citramalic acid and salts thereof. 제1항에 있어서,
아미노카르복시산류(C)가 하이드록시에틸 에틸렌디아민트리아세트산, 디에틸렌트리아민펜타아세트산, 트리에틸렌테트라민헥사아세트산, 에틸렌디아민테트라아세트산, 에틸렌디아민테트라프로피온산, 니트릴로트리아세트산, 이미노디아세트산, 하이드록시에틸 이미노디아세트산, 이미노디프로피온산, 1,3-프로판 디아민테트라아세트산, 1,3-디아미노-2-하이드록시프로판 테트라아세트산, 글리콜에테르 디아민테트라아세트산, 메타페닐렌 디아민테트라아세트산, 1,2-디아미노시클로헥산-N,N,N',N'-테트라아세트산, 디아미노프로피온산, 글루타민산, 디카르복시메틸글루타민산, 오르니틴, 시스테인, N,N-비스(2-하이드록시에틸)글리신, (S,S)-에틸렌디아민숙신산 및 이들의 염으로 이루어진 군에서 선택된 적어도 1 종인 것을 특징으로 하는 무전해 구리도금용 수계 구리 콜로이드 촉매액.The method according to claim 1,
Wherein the aminocarboxylic acids (C) are selected from the group consisting of hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyl Iminodiacetic acid, iminodipropionic acid, 1,3-propanediamine tetraacetic acid, 1,3-diamino-2-hydroxypropane tetraacetic acid, glycol ether diamine tetraacetic acid, metaphenylenediamine tetraacetic acid, 1,2- N, N-bis (2-hydroxyethyl) glycine, (S, N-diethylaminomethyl) glutamic acid, glutamic acid, dicarboxymethylglutamic acid, ornithine, cysteine, S) -ethylenediamine succinic acid and salts thereof. The electroless copper plating Aqueous copper colloid catalyst solution. (a) 노니온계 계면활성제, 카티온계 계면활성제, 아니온계 계면활성제, 양성 계면활성제로 이루어진 군에서 선택된 흡착촉진제의 적어도 1 종의 함유액에 비도전성 기판을 침지하는 흡착촉진공정(전처리 공정)과,
(b) 청구항 제1항의 수계 구리 콜로이드 촉매액에 비도전성 기판을 침지하여, 기판 표면상에 구리 콜로이드 입자를 흡착시키는 촉매부여공정, 및
(c) 흡착 처리된 상기 기판 상에 무전해 구리도금액을 사용하여 구리피막을 형성하는 무전해 도금공정으로 이루어지는 것을 특징으로 하는 무전해 구리도금 방법.(a) an adsorption promoting step (pretreatment step) for immersing a non-conductive substrate in a liquid containing at least one kind of an adsorption promoter selected from the group consisting of a nonionic surfactant, a cationic surfactant, an anionic surfactant and an amphoteric surfactant; ,
(b) a catalyst imparting step of immersing the non-conductive substrate in the aqueous copper colloid catalyst solution of claim 1 to adsorb copper colloid particles on the surface of the substrate, and
(c) an electroless plating step of forming a copper film on the substrate subjected to the adsorption treatment using an electroless copper plating solution. 제5항에 있어서,
공정(a)의 흡착촉진제가, 카티온계 계면활성제 및/또는 양성(兩性) 계면활성제인 것을 특징으로 하는 무전해 구리도금 방법.6. The method of claim 5,
The electroless copper plating method characterized in that the adsorption promoter of the step (a) is a cationic surfactant and / or a amphoteric surfactant.
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