KR101861626B1 - PC-ABS Resin parts Non-degradable Metal plating method - Google Patents

PC-ABS Resin parts Non-degradable Metal plating method Download PDF

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KR101861626B1
KR101861626B1 KR1020160074322A KR20160074322A KR101861626B1 KR 101861626 B1 KR101861626 B1 KR 101861626B1 KR 1020160074322 A KR1020160074322 A KR 1020160074322A KR 20160074322 A KR20160074322 A KR 20160074322A KR 101861626 B1 KR101861626 B1 KR 101861626B1
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plating
acid
ternary alloy
abs resin
agent
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KR20170141834A (en
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정경범
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유현테크닉스(주)
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Abstract

본 발명은 PC-ABS 수지 부품의 금속도금 공정에 있어서 종래의 3가 크롬의 하지 도금으로 일반화 되어있는 니켈도금의 대체 및 Cu-Sn-Zn 삼원합금 도금에 사용되고 있는 시안화합물을 배제한 도금방법에 관한 것으로, 먼저 수지 표면의 전처리 단계→동 전기도금 단계→Cu-Sn-Zn 삼원합금 전기도금 단계→3가크롬 도금단계를 포함하는 도금방법에 있어서, 3가크롬 도금단계 이전의 하지도금에 있어서 니켈도금 공정을 Cu-Sn-Zn 삼원합금 도금으로 대체하고 삼원합금 도금공정에서 사용하는 시안화합물의 사용을 배제한 인체 및 환경친화적인 수지 제품의 금속 도금방법에 관한 것이다. The present invention relates to a plating method excluding a cyanide compound which is used for the substitution of nickel plating and the Cu-Sn-Zn ternary alloy plating which are generalized by the conventional trivalent chromium base plating in the metal plating process of the PC-ABS resin component In the plating method including the pretreatment step of the resin surface, the electroplating step, the Cu-Sn-Zn ternary alloy electroplating step, and the trivalent chromium plating step, nickel The present invention relates to a metal plating method for a human body and an environmentally friendly resin product in which the plating process is replaced with a Cu-Sn-Zn ternary alloy plating and the use of a cyanide compound used in a ternary alloy plating process is excluded.

Description

PC-ABS 수지 부품의 비전해성 금속도금방법{PC-ABS Resin parts Non-degradable Metal plating method}Non-electrolytic metal plating method for PC-ABS resin parts {PC-ABS Resin parts Non-degradable metal plating method}

본 발명은 자동차용 혹은 장식용 PC-ABS 수지 부품의 금속도금방법에 관한 것이다. 특히 상세하게는 PC-ABS 수지 부품의 3가 크롬의 하지 도금공정에 있어서 니켈 및 시안화합물을 함유하지 않은 환경친화성 도금방법에 관한 것이다.The present invention relates to a metal plating method for automobile or decorative PC-ABS resin parts. And more particularly to an environmentally friendly plating method which does not contain nickel and a cyanide compound in a trivalent chromium undercoating process of a PC-ABS resin component.

자동차 부품 또는 장식용 제품이나 가전제품 등에 실용화 되고 있는 플라스틱 수지인 PC-ABSAcrylonitrile Butadien Styrene, (C8H8)x(C4H8)y(C3H3N)2 수지 혹은 에폭시 수지와 같은 열가소성 또는 열경화성 수지)의 3가크롬 도금은 부도체인 도금 소재를 고농도의 크롬산염이나 황산으로 에칭처리한 후 이 위에 다시 촉매를 부여하여 이 촉매를 핵으로 무전해 도금 혹은 전기도금에 의한 동-니켈-크롬 도금을 수행하는 것이 일반적이다.(특허문헌 1; 일본공개특허공보 특개2013-142188 및 ㅂ비특허문헌; SF SUR/FIN 2003 Proceedings 참조)(C 8 H 8 ) x (C 4 H 8 ) y (C 3 H 3 N) 2 resin or epoxy resin, which is a plastic resin that has been put into practical use in automobile parts or decorative products or household appliances, such as PC-ABSAcrylonitrile Butadiene Styrene Or trivalent chromium plating of a thermosetting resin) is etched with chromium salt or sulfuric acid at a high concentration and then a catalyst is applied to the plated material, which is an inductor, as an insulator, and the copper- It is common to perform chromium plating (see Patent Document 1: JP-A-2013-142188 and Patent Document: SF SUR / FIN 2003 Proceedings)

그러나 최근에 이르러 니켈이 상대적으로 고가이고 인체에 엘러지 반응을 일으키는 등의 문제점이 대두되어 무 니켈 도금공정이나 고농도의 6가크롬산을 배제하는 도금공정이 개발되고 있다. However, recently, there has been a problem that nickel is relatively expensive and causes an elder reaction to the human body, so that a nickel-free plating process or a plating process for eliminating a hexavalent chromic acid at a high concentration is being developed.

상기한 개발 과정에서 개시되고 있는 것 중의 하나로, 특허문헌 2(대한민국특허청 등록특허 10-1332301 (2013. 11. 18))에서는 3가 크롬도금에서의 하지도금인 니켈도금을 대체 할 수 있는 니켈 무 함유 Cu-Sn-Zn삼원합금 및 3가크롬 도금방법에 대하여 개시하고 있다. As one of the processes disclosed in the above-mentioned development process, Patent Document 2 (Korean Patent Application No. 10-1332301 (Mar. 11, 2013)) discloses a nickel-plated nickel- Containing Cu-Sn-Zn ternary alloy and a trivalent chromium plating method.

전술한 삼원합금 도금방법은 경제성이나, 내식성, 내마모성, 경도, 전기전도성 등이 니켈도금과 비교하여 필적할 만한 우수한 물성을 가지고 있으나, 크롬도금에 앞서 동 스트라이크 및 동전기도금과 Cu-Sn-Zn 삼원합금 도금에 있어서 시안화동 및 시안화소다 등의 유독성 화합물을 필수적으로 사용하고 있으며, 특허문헌 3(US patent 4,814,049 (1989. 3. 21)) 의 Cu-Sn-Zn 삼원합금 도금방법에 있어서도 역시 시안화합물을 사용하고 있어 환경문제를 야기할 소지가 충분하다. The ternary alloy plating method described above has excellent physical properties comparable to those of nickel plating in view of economy, corrosion resistance, abrasion resistance, hardness, electrical conductivity, etc. However, prior to chromium plating, copper strike and coin- In the ternary alloy plating, toxic compounds such as copper cyanide and sodium cyanide are essentially used, and also in the Cu-Sn-Zn ternary alloy plating method of Patent Document 3 (US Patent 4,814,049, March 21, 1989) The use of compounds is sufficient to cause environmental problems.

또한 시안화합물을 사용하는 수지 도금의 경우 광택 황산동 도금 층위에 시안을 함유하는 Cu-Sn-Zn 삼원합금 도금액이 스며들어 부품의 표면과 황산동 도금 피막 사이에 밀착불량이 발생할 우려가 있다.Furthermore, in the case of resin plating using a cyanide compound, a Cu-Sn-Zn ternary alloy plating solution containing cyan is permeated on the glossy copper sulfate plating layer, and the adhesion between the surface of the component and the copper sulfate plating film is poor There is a possibility of occurrence.

3가크롬 도금에 있어서는 [특허문헌 4∼7; 대한민국특허청 등록특허 10-1266252, 대한민국특허청 등록특허 10-1198353, 대한민국특허청 등록특허 10-0572496, US patent 4,107,004]등에서 개시한 바와 같이 수많은 연구개발이 이루어지고 있으나 저렴한 3가 크롬화합물의 조성물에 있어서, 삼원합금 층과의 밀착성, 3가 크롬 원 이외의 첨가제로 착화제, 전도성 보조제, 감극제, 무기 색상 발현제, 광택제, 전착제 등에 대한 고려가 필요하다. In the case of trivalent chromium plating [Patent Documents 4 to 7; A number of researches and developments have been made as disclosed in Korean Patent Registration No. 10-1266252, Korean Patent Application No. 10-1198353, Korean Patent Application No. 10-0572496, and US Patent No. 4,107,004. However, in a composition of a cheap trivalent chromium compound, It is necessary to consider the adhesion with the ternary alloy layer, the complexing agent, the conductive auxiliary agent, the antistatic agent, the inorganic color developing agent, the polishing agent, the electrodeposition agent and the like as additives other than the trivalent chromium source.

따라서 PC-ABS 수지 부품의 금속도금에 있어서 수지 층과 도금 층과의 밀착성, 내식성, 내마모성, 경도, 전기전도성 등의 물성이 우수한 보다 경제적이고 친환경적인 도금 조성물 및 도금방법의 개발이 요구되고 있다. Therefore, development of a more economical and environmentally friendly plating composition and plating method which is excellent in physical properties such as adhesion, corrosion resistance, abrasion resistance, hardness and electrical conductivity between the resin layer and the plating layer in the metal plating of the PC-ABS resin component is required.

일본공개특허공보 특개2013-142188 (2013. 7. 22)Japanese Unexamined Patent Application Publication No. 2013-142188 (March 23, 2013) 대한민국특허청 등록특허 10-1332301 (2013. 11. 18)Korea Patent Office Registration No. 10-1332301 (Mar. 11, 201) 미국 특허 US patent 4,814,049 (1989. 3. 21)US Patent 4,814,049 (Mar. 21, 1989) 대한민국특허청 등록특허 10-1266252 (2013. 5. 15.)Korea Patent Office Registration No. 10-1266252 (Feb. 대한민국특허청 등록특허 10-1198353Korea Patent Office Registration No. 10-1198353 대한민국특허청 등록특허 10-0572496 (2006. 4. 13.)Korea Patent Office Registration No. 10-0572496 (March 13, 2006) US patent 4,107,004 (1978. 4. 15.)U.S. Patent 4,107,004 (issued Apr. 15, 1978)

AESF SUR/FIN 2003 ProceedingsAESF SUR / FIN 2003 Proceedings

따라서 본 발명에서는 PC-ABS 수지 부품의 금속도금방법을 제공하되, 해당 금속도금 과정에서 필수적으로 수반되는 시안화합물을 배제하여 인체 유해성 및 환경공해 문제를 해결 할 수 있는 가장 경제적이고 친환경적인 도금방법을 제공하는데 그 목적이 있다.Therefore, the present invention provides a metal plating method for a PC-ABS resin part, and it is the most economical and environmentally friendly plating method which can solve the human hazard and environmental pollution problem by excluding the cyanide which is essentially involved in the metal plating process The purpose is to provide.

또한 본 발명은 무 전기니켈(니켈 free) 및 무 시안화합물(Non-Cynide)도금 방법을 사용하여 제반 물성이 우수한 PC-ABS 수지 부품의 표면 금속도금 공정을 확립하고, 도금 과정에서의 안정성을 확보함은 물론 도금 과정에 따른 작업 효율성과 신뢰성을 얻도록 하는 데 다른 목적이 있다. The present invention also provides a surface metal plating process for a PC-ABS resin component having excellent physical properties by using electroless nickel (non-nickel) and non-cynide plating methods and securing stability in the plating process There is also a different purpose in obtaining work efficiency and reliability in the plating process.

이와 같은 과제를 달성하기 위해 본 발명은 PC-ABS 수지 부품의 비전해성 금속도금방법에 있어서,In order to achieve the above object, the present invention provides a non-electrolytic metal plating method for a PC-ABS resin component,

PC-ABS 수지 부품의 전처리 단계(S10): PC-ABS resin component preprocessing step (S10):

상기 전처리 단계(S10)에 의해 전처리된 부품 상에 동을 도금하기 위한 동 전기도금 단계(S20): An electro-electroplating step (S20) for plating copper on the component pretreated by the preprocessing step (S10)

상기 동 전기도금 단계(S20)를 거친 대상물의 동 전기도금층 위에 Cu-Sn-Zn 삼원합금으로 도금 처리하는, Cu-Sn-Zn 삼원합금 도금 단계(S30): A Cu-Sn-Zn ternary alloy plating step (S30) in which the copper electroplating layer of the object subjected to the electro-electroplating step (S20) is plated with a Cu-Sn-Zn ternary alloy,

상기 Cu-Sn-Zn 삼원합금 도금 단계(S30)를 거친 대상물의 삼원합금 도금층 위에 최종적으로 3가크롬 도금단계(S40)를 거치는 것을 포함하는, PC-ABS 수지 부품의 비전해성 금속도금방법을 특징으로 한다. Characterized by comprising a non-electrolytic metal plating method of a PC-ABS resin part, comprising the step of finally subjecting a ternary alloy plating layer of an object subjected to the Cu-Sn-Zn ternary alloy plating step (S30) to a trivalent chromium plating step (S40) .

또한 본 발명은 해당 도금 과정에서의 도금조건 등에 관한 변수를 제공하는 것을 특징으로 한다.Further, the present invention is characterized by providing a parameter related to plating conditions and the like in the plating process.

이때 상기한 전처리 공정은 탈지→에칭→촉매부여→무전해니켈→ 수세 공정을 포함하며 탈지공정은 NaOH, KOH, 등의 약 20% 강알칼리 용액에 침적, 에칭공정은 무기산인 인산, 황산, 질산, 크롬산군으로부터 선택된 1종 또는 그 이상의 산(농도 10g/ℓ),과 과망간산염(100g/ℓ)을 함유하는 에칭액에 약10분간 상온에서 침적, 촉매부여 공정은 PdCl2(0.2g/ℓ,)/SnCl2(10g/ℓ) 혼합 콜로이드 촉매용액에 1∼10분간 침적하여 활성화 시킨 다음 무전해 니켈 도금 후 세척 단계를 포함하는 것을 특징으로 한다. 상기한 무전해니켈 공정은 Ni-P혹은 Ni-B 무전해도금 방법으로 니켈 원으로 황산니켈(NiSO46H2O), 염화니켈(NiCl2), 니켈아세테이트Ni(CH3CO2)H2O, 환원제로는 차아인산나트륨(NaH2PO2H2O) 또는 디메틸아민보레인(CH3)2NHBH3), 소디운보로하이드라이드(NaBH4), 착화제로는 카복실산계인 아세트산, 글리콜산, 숙신산, 사과산, 구연산 등을 사용하고 안정화제로는 Bi, Sb, Tl, Zn, Te의 무기염이나 치오우리아SC(NH2)2, 머켑탄(CH4S) 등을 사용한다. 무전해 니켈도금은 공지의 도금방법을 적용하는 것을 특징으로 한다. At this time, the pretreatment process includes degreasing -> etching -> catalyst application -> electroless nickel -> water washing process, and the degreasing process is immersed in a solution of about 20% strong alkali such as NaOH, KOH, etc., and the etching process is performed with phosphoric acid, sulfuric acid, (10 g / l) and perchloric acid (100 g / l) selected from chromic acid group for about 10 minutes at room temperature. The catalyst addition process was carried out by adding PdCl 2 (0.2 g / / SnCl 2 (10 g / ℓ) mixed colloid catalyst solution for 1 to 10 minutes, and then electroless nickel plating And a cleaning step. The above electroless nickel process is an electroless Ni-P or Ni-B electroless plating process in which nickel sulfate (NiSO 4 6H 2 O), nickel chloride (NiCl 2 ), nickel acetate Ni (CH 3 CO 2 ) H 2 O, a reducing agent such as sodium hypophosphite (NaH 2 PO 2 H 2 O) or dimethylamine borane (CH 3 ) 2 NHBH 3 ), sodium borohydride (NaBH 4 ), a complexing agent such as acetic acid, , Succinic acid, malic acid, citric acid and the like are used. As the stabilizer, inorganic salts such as Bi, Sb, Tl, Zn and Te, Chiosia SC (NH 2 ) 2 and mercaptans (CH 4 S) are used. The electroless nickel plating is characterized in that a known plating method is applied.

다음 동 도금 단계는 공지의 황산동 용액을 이용하는 도금방식 즉 CuSO4 200∼220g/ℓ, H2SO4 40∼80g/ℓ, Cl이온 40∼80mg/ℓ, 도금액 온도 20∼30℃, 전류밀도 1∼5A/dm2에서 약 5∼10분간 도금하는 공정을 채택하는 것을 특징으로 한다. The subsequent copper plating step is a plating method using a known copper sulfate solution, that is, 200-200 g / l CuSO 4, 40-80 g / l H 2 SO 4, 40-80 mg / l Cl ion, 20-30 ° C plating temperature, To 5 A / dm < 2 > for about 5 to 10 minutes.

Cu-Sn-Zn 삼원합금 도금은 기존의 시안화 화합물시안화동(CuCN), 시안화소다(NaCN 등을 첨가하는 도금방식을 탈피한 방법으로 금속 원으로 동, 및 아연 황산염(CuSO45H2O, ZnSO47H2O)과 주석산나트륨(Na2SnO33H2O) 전구체와 착화제로 피로인산염(sodium or potassium pyrophosphate, Na4P2O7, K4P2O7) 구연산칼륨(potassium citrate, K3C6H5O7), 아세트산(acetic acid, CH3COOH), 에틸렌디아민ethylenediamine, C2H4(NH2)2 등을 사용하는 도금방법을 제공한다.Cu-Sn-Zn ternary alloy plating is a method of dissolving the existing cyanide compound cyanide (CuCN), sodium cyanide (NaCN, etc.) plating method and copper as a metal source and zinc sulfate (CuSO 4 5H 2 O, ZnSO 4 7H 2 O) and sodium tartrate (Na 2 SnO 3 3H 2 O) precursors and complexing agents such as sodium or potassium pyrophosphate (Na 4 P 2 O 7 , K 4 P 2 O 7 ), potassium citrate 3 C 6 H 5 O 7 ), acetic acid (CH 3 COOH), ethylenediamine ethylenediamine, C 2 H 4 (NH 2 ) 2 , and the like.

3가크롬 도금에 있어서는 3가 크롬 원으로 황산크롬Cr2(SO4)3, 염화크롬(CrCl3), 질산크롬Cr(NO3)3, 초산크롬Cr2(OAc)42H2O을 사용하고 전도성 보조제와 감극제 역할의 도전성염으로 염화암모늄(NH4Cl), 황산칼륨(K2SO4), 황산암모늄(NH4)2SO4, 염화나트륨(NaCl), 염화칼륨(KCl), 불화칼륨(KF), 불화나트륨(NaF), pH 조절제 및 완충제는 (KOH, NaOH, HSO4, HBO3), 이외에 다른 첨가제로 안정제, 착화제, 광택제, 습윤제, 등으로 인산수소나트륨, 인산수소칼륨, 피로인산나트륨 혹은 칼륨염과, 모노카복실산(monocarboxylic acid),인 개미산(formic acid, HCOOH)과 옥살산(oxalic acid, C2H2O4) 등을 사용 할 수 있으며, 도금조건으로 도금액의 pH, 온도, 전류밀도, 도금시간 등의 변수 등을 포함하는 도금방법을 사용하는 것을 특징으로 한다In the trivalent chromium plating, Cr 2 (SO 4 ) 3 , chromium chloride (CrCl 3 ), chromium nitrate Cr (NO 3 ) 3 and chromium acetate Cr 2 (OAc) 4 2H 2 O are used as a trivalent chromium source (NH 4 Cl), potassium sulfate (K 2 SO 4 ), ammonium sulfate (NH 4 ) 2 SO 4 , sodium chloride (NaCl), potassium chloride (KCl) and potassium fluoride (KF), sodium fluoride (NaF), pH adjusting agent and buffer (KOH, NaOH, HSO 4 , HBO 3 ), other additives such as stabilizers, complexing agents, brighteners, wetting agents, Sodium carbonate or potassium pyrophosphate, monocarboxylic acid, formic acid (HCOOH) and oxalic acid (C 2 H 2 O 4 ) can be used. A temperature, a current density, a plating time, etc.

이와 같은 본 발명에 의하면 기존의 수지 부품의 3가 크롬도금에 있어서 하지 니켈도금을 대체하여 시안화 무첨가 Cu-Zn-Sn 삼원합금 도금방식을 채택하고 마지막으로 3가크롬 도금방법을 채택하는 공정을 제공함으로써 환경 및 인체에 유해한 화합물의 사용을 배제하고 친환경적인 공정 개발과 더불어 내식성, 내마모성, 외관성 등 제반 물성이 우수한 수지부품을 생산 할 수 있는 효과를 얻을 수 있다.According to the present invention, the trivalent chromium plating of a conventional resin part replaces the base nickel plating, adopts the cyanide-free Cu-Zn-Sn ternary alloy plating method, and finally the process of adopting the trivalent chromium plating method The use of compounds harmful to the environment and the human body is excluded and an effect of producing an eco-friendly process and a resin component having excellent physical properties such as corrosion resistance, abrasion resistance and appearance can be obtained.

도 1은 본 발명의 공정 흐름도를 도시한 도면1 is a view showing a process flow chart of the present invention

본 명세서에 개시되어 있는 본 발명의 개념에 따른 실시 예들에 대해서 특정한 구조적 또는 기능적 설명들은 단지 본 발명의 개념에 따른 실시 예들을 설명하기 위한 목적으로 예시된 것으로서, 본 발명의 개념에 따른 실시 예들은 다양한 변경들을 가할 수 있고 여러 가지 형태들을 가질 수 있으므로 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물, 또는 대체물을 포함하며, 명세서 및 청구범위에 사용되는 용어나 단어는 통상적이거나 사전적인 의미로 한정 해석되지 않음은 물론, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 점에 입각하여, 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야 한다. 따라서, 본 발명의 명세서에 기재된 실시예와 도면에 도시된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아닌바, 본 발명의 출원 시점에 있어서 이를 대체할 수 있는 다양한 균등물과 변형예들이 가능하거나 존재할 수 있음을 이해하여야 할 것이다.It is to be understood that the specific structural or functional descriptions of embodiments of the present invention disclosed herein are only for the purpose of illustrating embodiments of the inventive concept, It is intended to include all changes, equivalents, or alternatives falling within the spirit and scope of the present invention, as various changes can be made and have various forms, and terms and words used in the specification and claims are to be understood to be either conventional The inventor of the present invention is not limited to the meaning of the present invention and the inventor can define the concept of the term appropriately in order to explain his invention in the best way. . Therefore, the embodiments described in the specification of the present invention and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. It should be understood that various equivalents and modifications are possible or possible.

또한, 본 발명의 명세서에서 다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥상 가지는 의미와 일치하는 의미를 갖는 것으로 해석되어야 하며, 본 명세서에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다. Also, unless otherwise defined in the description of the present invention, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs I have. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the meaning of the context in the relevant art and, unless explicitly defined herein, are to be interpreted as ideal or overly formal Do not.

이하, 본 발명의 바람직한 실시예 및 첨부도면을 참조하여 상세히 설명한다.DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention and the accompanying drawings.

본 발명을 설명함에 있어, 관련된 공지의 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다. In the following description of the present invention, a detailed description of known configurations and functions will be omitted when it is determined that the gist of the present invention may be obscured.

본 발명에 따른 도금액 조성물, 작업조건 등 도금방법을 각 단계별로 설명하면 다음과 같다. The plating solution composition, working conditions and plating method according to the present invention will be described step by step.

도 1은 본 발명의 PC-ABS 수지 부품 금속 표면처리 공정도를 나타낸 것으로 도 1에서 보듯이 본 발명은 PC-ABS 수지 부품의 전처리 단계(S10)와, 전처리된 부품 상에 동을 도금하기 위한 동 전기도금 단계(S20)와, 상기 동 전기도금 단계(S20)를 거친 대상물의 동 전기도금층 위에 Cu-Sn-Zn 삼원합금으로 도금 처리하는, Cu-Sn-Zn 삼원합금 도금 단계(S30)와, 상기 Cu-Sn-Zn 삼원합금 도금 단계(S30)를 거친 대상물의 삼원합금 도금층 위에 최종적으로 3가 크롬 도금단계(S40)를 거치게 된다.1 is a view showing a process of a metal surface treatment of a PC-ABS resin part of the present invention. As shown in FIG. 1, the present invention relates to a PC-ABS resin part preprocessing step (S10) A Cu-Sn-Zn ternary alloy plating step S30 for plating the copper electroplating layer of an object subjected to the electroplating step S20 and the copper electroplating step S20 with a Cu-Sn-Zn ternary alloy, The trivalent chromium plating step (S40) is finally performed on the ternary alloy plating layer of the object through the Cu-Sn-Zn ternary alloy plating step (S30).

PC-ABS 수지 부품의 전처리 단계; S10Pretreatment of PC-ABS resin parts; S10

본 발명에서의 PC-ABS 수지 부품의 전처리 단계(S10)는, 도금 대상물인 PC-ABS 수지 부품을 탈지하기 위한 탈지공정(S10-1)과, 상기 탈지공정을 거친 대상물을 에칭하는 에칭공정(S10-2)과, 상기 에칭공정(S10-2)을 거친 대상물을 침적하여 활성화 시키기 위한 촉매부여공정(S10-3)과, 상기 촉매부여공정(S10-3)을 거친 대상물을 무전해 니켈 도금하게 되는 무전해니켈도금공정(S10-4)과, 상기 무전해니켈도금공정(S10-4)을 거친 대상물을 수세 처리하게 되는 수세공정(S10-5)을 포함하게 된다. The preprocessing step (S10) of the PC-ABS resin component in the present invention comprises a degreasing step (S10-1) for degreasing the PC-ABS resin component as the object to be plated, an etching step for etching the object through the degreasing step (S10-3) for immersing and activating an object through the etching step (S10-2), and a step for applying an electroless nickel plating (S10-3) An electroless nickel plating step (S10-4) for performing electroless nickel plating step (S10-4), and a water washing step (S10-5) for subjecting an object subjected to the electroless nickel plating step (S10-4) to water treatment.

상기 탈지공정(S10-1)은, 상기한 전 처리공정에 있어서의 탈지는 NaOH, KOH, 등의 약 20% 강알칼리 용액에 약 1∼5분간 침적하여 탈지하는 것을 의미하고, 상기 에칭공정(S10-2)은, 무기산인 인산(H3PO4), 황산(H2SO4), 질산(HNO3), 크롬산(CrO3)군으로부터 선택된 1종 또는 그 이상의 산(농도 10g/ℓ),과 과망간산염(100g/ℓ)을 함유하는 에칭액에 약 10분간 상온에서 침적 처리하는 공정을 의미한다.In the degreasing step (S10-1), degreasing in the above-mentioned pretreatment step means degreasing by immersing in a 20% strong alkaline solution such as NaOH, KOH, etc. for about 1 to 5 minutes, and the etching step S10 -2), one or more acids (concentration 10 g / l) selected from phosphoric acid (H 3 PO 4 ), sulfuric acid (H 2 SO 4 ), nitric acid (HNO 3 ) and chromic acid (CrO 3 ) And permanganate (100 g / l) at a room temperature for about 10 minutes.

또한 상기 촉매부여공정(S10-3)은, PdCl2(0.2g/ℓ,)/SnCl2(10g/ℓ) 혼합 콜로이드 촉매용액에 20∼50℃의 온도에서 1∼10분간 침지시켜 처리하게 되며, 상기 무전해니켈도금공정(S10-4)에서 선택되는 니켈 원은 황산니켈(NiSO46H2O), 염화니켈(NiCl2), 니켈아세테이트Ni(CH3CO2)H2O 중 어느 하나를 이루고, 환원제로 차아인산나트륨(NaH2PO2H2O) 또는 디메틸아민보레인(CH3)2NHBH3), 소디운보로하이드라이드(NaBH4) 중 어느 하나로 이루어지며, 착화제로 카복실산계인 아세트산, 글리콜산, 숙신산, 사과산, 구연산 중 어느 하나로 이루어지고, 안정화제로는 Bi, Sb, Tl, Zn, Te의 무기염이나 치오우리아{SC(NH2)2},머켑탄(CH4S) 중 어느 하나를 선택하여 무전해니켈도금공정(S10-4)을 진행하게 된다.Further, the catalyst application step (S10-3) is performed by immersing the catalyst in a solution of PdCl 2 (0.2 g / L) / SnCl 2 (10 g / L) mixed colloid catalyst at a temperature of 20 to 50 ° C. for 1 to 10 minutes (NiSO 4 6H 2 O), nickel chloride (NiCl 2 ), and nickel acetate Ni (CH 3 CO 2 ) H 2 O, the nickel source selected in the electroless nickel plating process (S10-4) (NaH 2 PO 2 H 2 O) or dimethylamine borane (CH 3 ) 2 NHBH 3 ) as a reducing agent, and sodium borohydride (NaBH 4 ) as a reducing agent, and a carboxylic acid-based acetic acid, comprises any one of glycolic acid, succinic acid, malic acid, citric acid, one, stabilizing agent, Bi, Sb, Tl, Zn, an inorganic salt of Te or Bang Uriah {SC (NH 2) 2} , Murray keptan (CH 4 S) And the electroless nickel plating process (S10-4) proceeds.

동 전기도금 Electroplating 단계 ; S20step ; S20

본 단계는, 상기한 촉매가 부여된 PC-ABS 수지 표면에 공지의 황산동 도금공정 즉 황산동 도금용액으로 CuSO4 200∼220g/ℓ, H2SO4 40∼80g/ℓ, Cl이온 40∼80mg/ℓ, 도금액 온도 20∼30℃, 전류밀도 1∼5A/dm2에서 약 5∼10분간 도금한 후 세척하는 과정을 거쳐 동 전기도금을 완성하게 된다. In this step, 200 to 200 g / l of CuSO 4, 40 to 80 g / l of H 2 SO 4, 40 to 80 mg / l of Cl ion, ℓ, the plating solution temperature is 20 to 30 ° C, the current density is 1 to 5 A / dm 2 for about 5 to 10 minutes, and then the electrodeposition is completed.

Cu-Cu- SnSn -Zn 삼원합금 도금 -Zn ternary alloy plating 단계 ; S30step ; S30

본 단계는 상기 동 전기도금 단계(S20)를 거친 피대상물인 수지 부품에 Cu-Sn-Zn 삼원합금 도금을 시행하는 단계를 의미한다. This step refers to a step of performing Cu-Sn-Zn ternary alloy plating on the resin component to be subjected to the electro-electroplating step (S20).

삼원합금 전구체로는 Cu 및 Zn은 +2 상태의 피로인산염, 탄산염, 수소탄산염, 아황산염, 황산염, 인산염, 아질산염, 질산염 등을 사용 할 수 있으며 본 발명에서는 황산동(CuSO45H2O) 및 황산아연(ZnSO47H2O)을 사용하였다. As the ternary alloy precursor, Cu and Zn may be pyrophosphate, carbonate, hydrogen carbonate, sulfite, sulfate, phosphate, nitrite and nitrate in the +2 state. In the present invention, copper sulfate (CuSO 4 5H 2 O) and zinc sulfate (ZnSO 4 7H 2 O) was used.

주석은 +4가 상태의 주석산나트륨(Na2SnO33H2O), 주석산칼륨(K2SnO33H2O)을 사용하고 도금액의 pH는 약산성 및 강알칼리성으로 6∼13범위이고, 바람직하게는 pH 7∼12 범위가 적합하다. The tin used is sodium tartrate (Na 2 SnO 3 3H 2 O) and potassium tartrate (K 2 SnO 3 3H 2 O) in the +4 state, the pH of the plating solution is in the range of 6 to 13 in weak acidity and strong alkaline, A range of pH 7-12 is suitable.

다른 첨가제로 안정제, 착화제, 광택제, 습윤제, 감극제 등으로 인산수소나트륨(Na2H2P2O7), 인산수소칼륨(K2H2P2O7), 피로인산나트륨(Na4P2O7nH2O) 혹은 칼륨염과, 모노카복실산(monocarboxylic acid), 디카복실산(dicarboxylic acid), 트리카복실산(tricarboxylic acid), 베타인(betaines, 트리알킬아미노산, C5H11NO2), 및 에틸렌디아민ethylenediamine, C2H4(NH2)2 등을 사용 할 수 있으며 이 가운데 모노카복실산으로 아세트산(acetic acid, CH3COOH), 글리콜릭산(glycolic acid, HOCH2COOH), 글리신(glycine, NH2CH2COOH), 아닐린(aniline, C6H5NH2). 젖산lactic acid, CH3CH(OH)COOH, 개미산(HCOOH) 등이고, 디카복실산으로는 숙신산(succinic acid, CH2)2(COOH)2, 사과산(malic acid, C8H6O5), 타타르산tataric acid, (CHOH)2(COOH)2, 옥살산oxalic acid, (COOH)2 등이고, 트리카복실산으로는 구연산(citric acid, C6H8O7), 아코니니틱산(aconitic acid(C6H6O8), 트리메스틱산(trimestic acid, C9H5O6), 프로판 1,2,3 트리카복실산propane-1,2,3-tricarboxylic acid, C3H5(COOH)3 등이며 또는 이들의 알칼리염을 사용하는 것이 바람직하다. With other additives stabilizer, a complexing agent, a brightener, a humectant, a sense of sodium hydrogen phosphate in geukje such as (Na 2 H 2 P 2 O 7), hydrogen phosphate and potassium (K 2 H 2 P 2 O 7), sodium pyrophosphate (Na 4 P 2 O 7 nH 2 O) or a potassium salt with a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a betaines, a trialkyl amino acid, C 5 H 11 NO 2 , , Ethylenediamine ethylenediamine and C 2 H 4 (NH 2 ) 2. Of these, acetic acid (CH 3 COOH), glycolic acid (HOCH 2 COOH), glycine , NH 2 CH 2 COOH), aniline (C 6 H 5 NH 2 ). Lactate lactic acid, CH 3 CH (OH) COOH, formic acid (HCOOH) or the like, dicarboxylic acids include succinic acid (succinic acid, CH 2) 2 (COOH) 2, malic acid (malic acid, C 8 H 6 O 5), tartaric acid tataric acid, (CHOH) 2 ( COOH) 2, oxalic acid oxalic acid, (COOH) 2 or the like, tricarboxylic acid include citric acid (citric acid, C 6 H 8 O 7), Acre nini lactic acid (aconitic acid (C 6 H 6 O 8 ), trimestic acid (C 9 H 5 O 6 ), propane 1,2,3-tricarboxylic acid propane-1,2,3-tricarboxylic acid, and C 3 H 5 (COOH) 3 Or an alkali salt thereof is preferably used.

Cu-Zn-Sn 삼원합금 도금액 조성물의 동(Cu) 농도는 10∼40g/ℓ(CuSO45H2O), 아연(Zn)농도는 0.5∼3.0g/ℓ(ZnSO47H2O), 주석(Sn)농도는 10∼60g/ℓNa2(Sn(OH)6이나 합금의 색상이나 용도에 따라 각 합금 원소의 첨가량은 적절한 조절이 가능하다. The copper (Cu) concentration of the Cu-Zn-Sn ternary alloy plating solution composition is 10 to 40 g / l (CuSO 4 5H 2 O), the zinc concentration is 0.5 to 3.0 g / l (ZnSO 4 7H 2 O) (Sn) concentration is 10 to 60 g / l Na 2 (Sn (OH) 6 ), and the amount of each alloy element can be appropriately adjusted depending on the color or application of the alloy.

안정제로 피로인산수소나트륨 100∼300g/ℓ, 착화제 구연산 15∼20g/ℓ, 아세트산 15∼25g/ℓ, 에틸렌디아민 40∼60ml/ℓ, pH 조절제로 NaOH 15∼25g/ℓ, 를 첨가한다. 도금 색상이나 밀착성 및 미려한 외관을 위해 미량의 Ni 및 Ag을 약 10∼100ppm 첨가하여도 무방하다. 도금 두께는 0.5∼5㎛가 바람직하고 도금액의 온도는 30∼60℃, 전류밀도는 0.1∼2.0A/dm2가 바람직하다. 15 to 25 g / l of acetic acid, 40 to 60 ml / l of ethylenediamine, and 15 to 25 g / l of NaOH as a pH regulator are added as stabilizers. A small amount of Ni and Ag may be added in an amount of about 10 to 100 ppm for the plating color, the adhesion, and the beautiful appearance. The plating thickness is preferably 0.5~5㎛ the temperature of the plating solution is 30~60 ℃, the current density is preferably in the 0.1~2.0A / dm 2.

양극재료는 불용성 흑연 혹은 백금도금 티타늄, 이리듐양극이나, 용해성 양극으로 Sn-Cu, Zn-Cu, Zn-Sn-Cu 합금 양극을 사용하여도 무방하다. The positive electrode material may be an insoluble graphite or platinum-plated titanium or iridium anode, or a Sn-Cu, Zn-Cu or Zn-Sn-Cu alloy anode as a soluble anode.

3가크롬Trivalent chromium 도금단계; S40 A plating step; S40

본 단계인 3가크롬 도금단계(S40)는 상기한 Cu-Sn-Zn 3원합금 도금 층위에 3가 크롬도금을 시행하는 단계를 의미한다. The trivalent chromium plating step (S40) in this step means a step of performing trivalent chromium plating on the Cu-Sn-Zn ternary alloy plating layer.

3가크롬 원으로는 황산크롬Cr2(SO4)3, 염화크롬(CrCl3), 질산크롬HNO3)3, 초산크롬Cr2(OAc)42H2O 등을 사용하고, 기타 첨가제로는 착화제, 전도성염(전도성 보조제, 또는 감극제), 광택제, 전착제, pH 안정제, 계면활성제, 및 무기물 색상 발현제 등을 사용한다. As the trivalent chromium source, chromium sulfate (Cr 2 (SO 4 ) 3 , chromium chloride (CrCl 3 ), chromium nitrate HNO 3 ) 3 and chromium acetate Cr 2 (OAc) 4 2H 2 O were used. An electroconductive salt (a conductive auxiliary agent or a surfactant), a brightener, an electrodeposition agent, a pH stabilizer, a surfactant, and an inorganic color developing agent.

착화제로는 옥살산(C2H2O4), 개미산(HCOOH)을 사용하고 전도성 보조제로는 염화암모늄(NH4Cl), 염화칼륨(KCl), 염화칼슘(CaCl2), 산화제는 황산칼륨(K2SO4), 황산알루미늄Al2(SO4)3, 아황산암모늄(NH4)2S2O8을 감극제로 NH4Br, NaBr, NaF, KF를 습윤제로 소디움라우릴설페이트sodium lauryl sulfate, CH3(CH2)11SO4Na, pH 조절제 및 안정제로 KOH, NaOH, NH4OH, H2BO3, 무기물 색상발현제로 Fe, Co 이온 등을 사용 할 수 있다. (NH 4 Cl), potassium chloride (KCl) and calcium chloride (CaCl 2 ) are used as the conductive auxiliary agents, potassium sulfate (K 2 ) is used as the oxidizing agent, and oxalic acid (C 2 H 2 O 4 ) SO 4), aluminum sulphate Al 2 (SO 4) 3, sulfurous acid, ammonium (NH 4) 2 of S 2 O 8 in a sense geukje NH 4 Br, NaBr, NaF, sodium lauryl sulfate the KF with the wetting agent sodium lauryl sulfate, CH 3 (CH 2 ) 11 SO 4 Na, KOH, NaOH, NH 4 OH, H 2 BO 3 as a pH adjusting agent and stabilizer, and Fe and Co ions as an inorganic color developing agent.

상기한 도금 조성물은 크롬원인 황산크롬Cr2(SO4)36H2O은 100∼300g/ℓ, 착화제인 옥살산(C2H2O42H2O)는 50∼70g/ℓ, 개미산(HCOOH)은 30∼50g/ℓ으로 3가크롬 1몰에 대하여 착화제는 0.1∼2.0몰 첨가하는 것이 적당하다. 전도성 보조제인 황산암모늄NH4)2SO4은 40∼100g/ℓ, 산화제인 아황산암모늄((NH4)2S2O8)은 5∼15g/ℓ, pH 완충제인 붕산(HBO3)는 30∼80g/ℓ, 감극제인 브롬화암모늄(NH4Br), 불화칼륨(KF)은 5∼40g/ℓ, 이외에 계면활성제로 소디움라우릴설페이트CH3(CH2)11SO4Na은 0.05∼0.1g/ℓ, 무기물 색상 발현제는 2∼15g/ℓ, 첨가한다. The above-mentioned plating composition contains 100 to 300 g / l of chromium sulfate, Cr 2 (SO 4 ) 3 6H 2 O, which is chromium sulfate, 50 to 70 g / l of oxalic acid (C 2 H 2 O 4 2H 2 O) ) Is 30 to 50 g / l, and the complexing agent is suitably added in an amount of 0.1 to 2.0 mol per mol of trivalent chromium. The conductive auxiliary ammonium sulfate NH 4) 2 SO 4 is 40~100g / ℓ, the oxidizing agent is ammonium sulfite ((NH 4) 2 S 2 O 8) is 5~15g / ℓ, pH buffering agent is boric acid (HBO 3) 30 (NH 4 Br) and potassium fluoride (KF) of 5 to 40 g / l as surfactants, and sodium lauryl sulfate CH 3 (CH 2 ) 11 SO 4 Na as a surface active agent in an amount of 0.05 to 0.1 g / l, and inorganic coloring agent is added in an amount of 2 to 15 g / l.

도금공정 조건으로는 도금액의 온도 30∼60℃, 도금액의 pH 1.5∼5.0로 조정하고, 전류밀도 5∼20A/dm2, 양극은 불용성 흑연 혹은 스테인레스 316L, 이리듐판을 사용하고, 도금시간은 1∼10분으로 조절한다. As the plating process conditions, the temperature of the plating solution was adjusted to 30 to 60 캜 and the pH of the plating solution was adjusted to 1.5 to 5.0, the current density was 5 to 20 A / dm 2 , insoluble graphite or 316 L of stainless steel and iridium plate were used as the positive electrode, To 10 minutes.

이하는 상기한 단계들을 이용하여 도금 처리하게 되는 본 발명의 실시예를 예시한다. The following illustrates an embodiment of the present invention that is subject to plating using the above steps.

본 실시예에서는 자동차 혹은 장식 부품용 PC-ABS 수지 제품을 대상으로 한다. 각 단계별 처리공정을 예시하면 다음과 같다. In this embodiment, PC-ABS resin products for automobiles or decorative parts are targeted. The processing steps of each step are exemplified as follows.

PC-ABS 수지 부품의 전처리 단계(S10)In the preprocessing step (S10) of the PC-ABS resin component,

(탈지공정; S10-1)(Degreasing step S10-1)

본 단계에서 도금 대상물을 탈지하기 위한 탈지공정을 진행하기 위하여, 가성소다(NaOH) 20% 용액에 1분간 침적하는 조건에 의해 탈지공정을 진행하였다.In this step, in order to carry out the degreasing process for degreasing the object to be plated, the degreasing process was performed under the condition of immersing in a 20% solution of caustic soda (NaOH) for 1 minute.

(에칭공정; S10-2)(Etching step: S10-2)

본 단계에서 에칭공정을 진행하기 위해, 크롬산(Cro3) 420g/L, 황산(H2SO4) 220g/L, 인산(H3PO4) 10g/ℓ, 과망간산염(100g/ℓ) 으로 이루어지는 혼합용액에 65℃에서 10분간 침적하여 에칭공정을 진행하였다. In order to carry out the etching process in this step, a solution of 420 g / L of chromic acid (Cro 3 ), 220 g / L of sulfuric acid (H 2 SO 4 ), 10 g / L of phosphoric acid (H 3 PO 4 ), and permanganate (100 g / And then immersed in the mixed solution at 65 DEG C for 10 minutes to carry out the etching process.

(촉매부여공정; S10-3)(Catalyst addition step S10-3)

본 단계에서의 촉매부여를 위해, 본 공정에서는 PdCl2 0.2g/ℓ+ SnCl4 10g/ℓ 혼합 콜로이드 용액에 5분간 침적하여 촉매를 부여하는 공정을 진행하였다.In this step, the catalyst was immersed in a colloidal solution of 0.2 g / l of PdCl 2 and 10 g / l of SnCl 4 for 5 minutes in order to impart the catalyst in this step.

(무전해니켈도금공정; S10-4)(Electroless nickel plating process: S10-4)

본 단계에서의 무전해니켈도금을 위해, NiSO46H2O 25g/ℓ, 차아인산나트륨(NaH2PO2H2O) 15g/ℓ, 구연산(C6H7O8) 20g/ℓ, 사과산CH2OH(COOH)2 20g/ℓ, 치오우리아 5ppm, 온도 85∼90℃, pH 4.5의 조건을 충족하는 도금액을 이용하여 본 공정인 무전해니켈도금공정을 진행하였다. For electroless nickel plating in this step, 15 g / L of NiSO 4 6H 2 O, 15 g / L of sodium hypophosphite (NaH 2 PO 2 H 2 O), 20 g / L of citric acid (C 6 H 7 O 8 ) Electroless nickel plating process was carried out using a plating solution satisfying the conditions of CH 2 OH (COOH) 2 20 g / L, TiO2 5 ppm, temperature 85-90 ° C and pH 4.5.

(수세공정; S10-5)(Washing process S10-5)

상기 무전해니켈도금공정을 거친 대상물을 냉수로 충분히 수세 처리하였다. The object subjected to the electroless nickel plating process was sufficiently washed with cold water.

동 전기도금단계(S20)In the electroplating step S20,

본 단계는 상기한 탈지공정(S10-1), 에칭공정(S10-2), 촉매부여공정(S10-3), 무전해니켈도금공정( S10-4), 수세공정(S10-5)을 거쳐 진행되는 상기 PC-ABS 수지 부품의 전처리 단계(S10)에 의해 얻게 되는 PC-ABC 수지 부품을 동 전기도금하기 위한 단계이다.This step is performed through the degreasing step (S10-1), the etching step (S10-2), the catalyst applying step (S10-3), the electroless nickel plating step (S10-4), and the water washing step (S10-5) Is a step for electro-electroplating the PC-ABC resin component obtained by the preprocessing step (S10) of the PC-ABS resin component in progress.

이를 위해, 황산동(CuSO4) 200g/ℓ, 황산(H2SO4) 60g/ℓ, Cl 50 ml/ℓ으로 이루어지는 도금액을 30℃의 온도에서 전류밀도 3A/dm2 의 조건을 충족하며 5분간 도금 처리한 후, 수세처리하게 된다.To this end, a copper sulfate (CuSO 4) 200g / ℓ, sulfuric acid (H 2 SO 4) 60g / ℓ, Cl a plating solution consisting of 50 ml / ℓ satisfy the conditions of a current density of 3A / dm 2 at a temperature of 30 ℃ and 5 minutes Plated, and then treated with water.

Cu-Cu- SnSn -Zn 삼원합금 도금 단계(S30)-Zn ternary alloy plating step (S30)

본 단계는 상기한 동 전기도금단계(S20)를 거친, PC-ABC 수지 부품을 Cu-Sn-Zn 삼원합금 도금하기 위한 단계이다.This step is a step for plating the Cu-Sn-Zn ternary alloy with the PC-ABC resin part through the above-described electro-electroplating step (S20).

이를 위해, 황산동(CuSO45H2O) 20g/ℓ, 황산아연(ZnSO47H2O 2.0g/ℓ), 주석산나트륨Na2(Sn(OH)6 40g/ℓ, 피로수소인산나트륨(Na2H2P2O7) 200g/ℓ, 구연산칼륨K3C6H5O7 15g/ℓ, 아세트산CH3COOH 15g/ℓ, KOH(pH 8.0), 에틸렌디아민C2H4(NH2)2 50㎖/ℓ로 이루어지는 도금액을 25℃의 온도로 유지하며, 전류밀도 2.0A/dm2의 조건을 충족시킨 상태에서, PC-ABC 수지 부품을 Cu-Sn-Zn 삼원합금 도금 처리하였다.To this end, a copper sulfate (CuSO 4 5H 2 O) 20g / ℓ, a zinc sulfate (ZnSO 4 7H 2 O 2.0g / ℓ), sodium stannate Na 2 (Sn (OH) 6 40g / ℓ, fatigue hydrogen sodium phosphate (Na 2 H 2 P 2 O 7 ), 15 g / L potassium citrate K 3 C 6 H 5 O 7, 15 g / L acetic acid CH 3 COOH, KOH (pH 8.0), ethylenediamine C 2 H 4 (NH 2 ) 2 The PC-ABC resin component was subjected to a Cu-Sn-Zn ternary alloy plating treatment while maintaining the plating solution at 50 캜 / L at a temperature of 25 캜 and at a current density of 2.0 A / dm 2 .

3가 크롬 도금단계(S40)In the trivalent chromium plating step (S40)

본 단계는 상기 Cu-Sn-Zn 삼원합금 도금 단계(S30)를 거친 PC-ABC 수지 부품을 3가 크롬 도금하기 위한 단계이다.This step is a step for plating the PC-ABC resin part having undergone the Cu-Sn-Zn ternary alloy plating step (S30) with trivalent chromium.

이를 위해, 황산크롬Cr2(SO4)3 150g/ℓ, 개미산(HCOOH) 5g/ℓ, 붕산(HBO3) 80g/ℓ, 황산알루미늄Al2(SO4)3 30g/ℓ, 불화칼륨(KF) 30g/ℓ, 황산알루미늄NH4)2SO4 100g/ℓ, 소디움라우릴설페이트CH3(CH2)11SO4Na 0.1g/ℓ, pH 3.0의 조건을 만족하는 도금액을 온도 40℃를 유지하는 상태에서, 전류밀도 10A/dm2, 의 조건을 충족시키며 3가 크롬 도금하였다. To this end, 150 g / l of chromium sulfate Cr 2 (SO 4 ) 3 , 5 g / l of formic acid (HCOOH), boric acid (HBO 3 ) 80g / ℓ, aluminum sulphate Al 2 (SO 4) 3 30g / ℓ, potassium fluoride (KF) 30g / ℓ, aluminum sulfate NH 4) 2 SO 4 100g / ℓ, sodium lauryl sulfate CH 3 (CH 2) 11 SO 4 Na 0.1 g / l, and pH 3.0 were subjected to trivalent chromium plating while satisfying the conditions of a current density of 10 A / dm 2 while maintaining the temperature at 40 占 폚.

전처리, 동 도금 및 Cu-Sn-Zn 3원합금 도금은 (실시예 1)과 동일하다. Pretreatment, copper plating, and Cu-Sn-Zn ternary alloy plating were the same as in Example 1.

그러나 실시예 1과는 달리 본 실시예 2에서는 3가 크롬도금에 있어서 착화제, 전도성염, 감극제, pH완충제, 계면활성제 등의 도금액 조성물과 도금조건 등을 변화시켜가면서 도금하였을 경우, 도금피막의 경도 및 내식성 등의 물성을 조사한 결과를 표 1에 나타내었다. However, unlike Embodiment 1, in Embodiment 2, when plating is performed while varying the plating solution composition such as a complexing agent, a conductive salt, a conductive salt, a surfactant, a pH buffer, a surfactant, and plating conditions in a trivalent chromium plating, Hardness and corrosion resistance of the steel sheet are shown in Table 1. < tb > < TABLE >

<표 1. 3가 크롬 도금액 조성물, 도금조건 및 물성><Table 1> Trivalent Chromium Plating Solution Composition, Plating Conditions and Physical Properties> 도금액 조성Plating solution composition 실시예Example 1 One 실시예Example 2 2 실시예Example 3 3 비교예Comparative Example 1 One 황산크롬(g/ℓ)Chromium sulfate (g / l) 150150 180180 200200 150150 개미산(g/ℓ)Formic acid (g / l) 5050 -- 옥살산(g/ℓ)Oxalic acid (g / l) -- 5050 3030 -- 붕산(g/ℓ)Boric acid (g / l) 8080 8080 8080 100100 아황산알루미늄(g/ℓ)Aluminum sulfite (g / l) -- 5050 8080 -- 황산암모늄(g/ℓ)Ammonium sulfate (g / l) 3030 2020 1010 브롬화암모늄(g/ℓ)Ammonium bromide (g / l) -- 3030 1010 2020 불화칼륨(g/ℓ)Potassium fluoride (g / l) 3030 2020 -- 계면활성제(mg/ℓ)Surfactant (mg / l) 0.10.1 0.10.1 0.10.1 -- 도금 조건Plating condition pHpH 3.03.0 2.52.5 2.02.0 3.33.3 전류밀도(A/dm2)Current density (A / dm 2 ) 1010 1212 1515 1010 도금액 온도(℃)Plating solution temperature (캜) 4040 4040 4040 4040 도금시간(분)Plating time (min) 55 55 55 55 피막 특성Film property 도금층 두께(㎛)Plating layer thickness (탆) 2.02.0 2.12.1 2.42.4 2.32.3 경도(Hv)Hardness (Hv) 890890 1,0001,000 900900 800800 내식성(염수분무시험)Corrosion resistance (Salt spray test) ◎※◎ ※ ◎◎ ◎◎ ◎◎ 마모특성(마모량 mg)Wear characteristics (wear amount mg) 1.31.3 1.21.2 1.51.5 2020

※3.5% NaCl용액 72시간 분무테스트에서 부식현상 발생하지 않음.※ No corrosive phenomenon occurred in spray test of 3.5% NaCl solution for 72 hours.

상기한 표에 의하면 실시예 에서는 거의 유사한 결과를 나타내고 있으나 비교예에서는 내마모성이 급격히 저하하는 결과를 나타낸다. According to the above table, the results of the examples show almost similar results, but the abrasion resistance of the comparative examples show a sharp decrease.

즉 착화제를 사용하지 않을 경우 삼원합금 도금 층과 3가 크롬도금 층 사이의 밀착성이 감소하는 현상이 발생한다. 본 실시예에 의하면 도금 층의 표면경도, 내식성 및 마모 특성이 모두 양호한 결과를 나타내고 있음을 알 수 있다. That is, when the complexing agent is not used, the adhesion between the ternary alloy plating layer and the trivalent chromium plating layer is reduced. According to this embodiment, it can be seen that the surface hardness, corrosion resistance and wear characteristics of the plated layer are both good.

상기한 피막특성을 측정하는 방법에 있어서 도금층 두께는 도금된 부품을 절단하여 단면을 연마하여 금속현미경으로 관찰하여 측정하였고, 도금 층의 표면경도는 비카스 경도계(Laryee Technology사 제품, HVS-10)로 측정하고 내마모성은 스가 마모시험기(須賀사 제품 NVS-ISO-3)로 측정하였다.        The surface hardness of the plated layer was measured with a Vickers hardness meter (HVS-10, manufactured by Laryee Technology Co., Ltd.), and the surface hardness of the plated layer was measured with a metal microscope. And abrasion resistance was measured with a Sugar abrasion tester (NVS-ISO-3 manufactured by Suga Co., Ltd.).

이상과 같이 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 상기 실시예에 한정되지 않음은 물론이며, 본 발명이 속하는 분야에서 통상의 기술적 지식을 가진 자에 의해 상기 기재된 내용으로부터 다양한 수정 및 변형이 가능할 수 있음은 물론이다.While the present invention has been described with reference to the particular embodiments and drawings, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and changes may be made.

따라서 본 발명에서의 기술적 사상은 아래에 기재되는 청구범위에 의해 파악되어야 하되 이의 균등 또는 등가적 변형 모두 본 발명의 기술적 사상의 범주에 속함은 자명하다 할 것이다.Accordingly, it is to be understood that the technical idea of the present invention is to be understood by the following claims, and all of its equivalents or equivalents fall within the technical scope of the present invention.

S10; PC-ABS 수지 부품의 전처리 단계
S10-1; 탈지공정
S10-2; 에칭공정
S10-3; 촉매부여공정
S10-4; 무전해니켈도금공정
S10-5; 수세공정
S20; 동 전기도금 단계
S30; Cu-Sn-Zn 삼원합금 도금 단계
S40; 3가 크롬 도금단계S10; Pre-treatment of PC-ABS resin parts
S10-1; Degreasing process
S10-2; Etching process
S10-3; Catalyst application process
S10-4; Electroless nickel plating process
S10-5; Washing process
S20; Electroplating step
S30; Cu-Sn-Zn ternary alloy plating step
S40; Trivalent chromium plating step

Claims (25)

삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete PC-ABS 수지 부품의 전처리 단계(S10): 상기 전처리 단계(S10)에 의해 전처리된 부품 상에 동을 도금하기 위한 동 전기도금 단계(S20): 상기 동 전기도금 단계(S20)를 거친 대상물의 동 전기도금층 위에 Cu-Sn-Zn 삼원합금으로 도금 처리하는, Cu-Sn-Zn 삼원합금 도금 단계(S30): 상기 Cu-Sn-Zn 삼원합금 도금 단계(S30)를 거친 대상물의 삼원합금 도금층 위에 최종적으로 3가크롬 도금단계(S40)를 거치는, PC-ABS 수지 부품의 비전해성 금속도금방법에 있어서,
상기 Cu-Sn-Zn 삼원합금 도금 단계(S30)에서, 도금액 중의 동(Cu) 농도는 10∼40g/ℓ(CuSO45H2O), 아연(Zn) 농도는 0.5∼3.0g/ℓ(ZnSO47H2O), 주석(Sn) 농도는 10∼60g/ℓNa2(Sn(OH)6, 피로인산수소나트륨(Na2H2P2O7) 농도는 100∼300g/ℓ, 구연산(C6H8O7) 농도는 15∼20g/ℓ, 아세트산(CH3COOH) 농도는 15∼25g/ℓ, 에틸렌디아민 농도는 40∼60ml/ℓ, NaOH 또는 KOH의 농도는 15∼25g/ℓ로 이루어지는 도금액을 이용하는 것을 포함하는, PC-ABS 수지 부품의 비전해성 금속도금방법.
(S10) of the PC-ABS resin component: an electro-electroplating step (S20) for plating the copper on the component pretreated by the preprocessing step (S10); a step Cu-Sn-Zn ternary alloy plating step (S30) in which the copper electroplating layer is plated with a Cu-Sn-Zn ternary alloy: On the ternary alloy plating layer of the object subjected to the Cu-Sn-Zn ternary alloy plating step (S30) In a non-electrolytic metal plating method of a PC-ABS resin component, which is finally subjected to a trivalent chromium plating step (S40)
In the Cu-Sn-Zn ternary alloy plating step (S30), the copper concentration in the plating solution is 10 to 40 g / l (CuSO 4 5H 2 O) and the zinc concentration is 0.5 to 3.0 g / 4 7H 2 O), tin (Sn) concentration 10~60g / ℓNa 2 (Sn (OH ) 6, hydrogen sodium pyrophosphate (Na 2 H 2 P 2 O 7) concentration 100~300g / ℓ, citric acid (C 6 H 8 O 7) concentration 15~20g / ℓ, acetic acid (CH 3 COOH) concentrations 15~25g / ℓ, the concentration of ethylenediamine is the concentration of 40~60ml / ℓ, NaOH or KOH is in 15~25g / ℓ A method for plating a non-electrolytic metal of a PC-ABS resin component, which comprises using a plating solution.
제 11 항에 있어서,
상기 도금액의 온도30∼60℃, 전류밀도 0.1∼2.0A/dm2 , 의 조건에서 1∼10분간 도금하는 것을 특징으로 하는, PC-ABS 수지 부품의 비전해성 금속도금방법.
12. The method of claim 11,
Characterized in that the plating 1-10 minutes at a temperature of 30~60 ℃, current density 0.1~2.0A / dm 2, the conditions of the plating solution, the water-decomposable non-metallic plating method of PC-ABS resin component.
삭제delete 삭제delete 삭제delete PC-ABS 수지 부품의 전처리 단계(S10): 상기 전처리 단계(S10)에 의해 전처리된 부품 상에 동을 도금하기 위한 동 전기도금 단계(S20): 상기 동 전기도금 단계(S20)를 거친 대상물의 동 전기도금층 위에 Cu-Sn-Zn 삼원합금으로 도금 처리하는, Cu-Sn-Zn 삼원합금 도금 단계(S30): 상기 Cu-Sn-Zn 삼원합금 도금 단계(S30)를 거친 대상물의 삼원합금 도금층 위에 최종적으로 3가크롬 도금단계(S40)를 포함하고, 상기 Cu-Sn-Zn 삼원합금 도금 단계(S30)에 적용되는 도금액에 안정제, 착화제, 광택제, 습윤제, 감극제 중 적어도 하나 이상 선택 조합 첨가하여서 되는 도금액을 이용하여 Cu-Sn-Zn 삼원합금 도금하는, PC-ABS 수지 부품의 비전해성 금속도금방법에 있어서,
상기 안정제, 착화제, 광택제, 습윤제, 감극제는 인산수소나트륨(Na2H2P2O7), 인산수소칼륨(K2H2P2O7), 피로인산나트륨(Na4P2O7nH2O), 칼륨염과, 모노카복실산(monocarboxylic acid), 디카복실산(dicarboxylic acid), 트리카복실산(tricarboxylic acid), 베타인(betaines, 트리알킬아미노산, C5H11NO2), 및 에틸렌디아민ethylenediamine, C2H4(NH2)2 으로 이루어지는 도금액을 이용하여 Cu-Sn-Zn 삼원합금 도금하는 것을 포함하는, PC-ABS 수지 부품의 비전해성 금속도금방법.
(S10) of the PC-ABS resin component: an electro-electroplating step (S20) for plating the copper on the component pretreated by the preprocessing step (S10); a step Cu-Sn-Zn ternary alloy plating step (S30) in which the copper electroplating layer is plated with a Cu-Sn-Zn ternary alloy: On the ternary alloy plating layer of the object subjected to the Cu-Sn-Zn ternary alloy plating step (S30) (S40), and at least one selected from the group consisting of a stabilizer, a complexing agent, a polishing agent, a wetting agent, and a surfactant is added to the plating solution applied to the Cu-Sn-Zn ternary alloy plating step (S30) A non-electrolytic metal plating method for a PC-ABS resin component, which is used for plating a Cu-Sn-Zn ternary alloy using a plating solution,
The stabilizer, a complexing agent, a brightener, a humectant, a sense geukje are sodium hydrogen phosphate (Na 2 H 2 P 2 O 7), hydrogen phosphate and potassium (K 2 H 2 P 2 O 7), sodium pyrophosphate (Na 4 P 2 O 7 nH 2 O), a potassium salt, a monocarboxylic acid, a dicarboxylic acid, a tricarboxylic acid, a betaines, a trialkylamino acid, C 5 H 11 NO 2 , A non-electrolytic metal plating method for PC-ABS resin parts, comprising plating a Cu-Sn-Zn ternary alloy using a plating solution comprising diamine ethylenediamine and C 2 H 4 (NH 2 ) 2 .
제 16 항에 있어서,
상기 모노카복실산으로 아세트산(acetic acid, CH3COOH), 글리콜릭산(glycolic acid, HOCH2COOH), 글리신(glycine, NH2CH2COOH), 아닐린(aniline, C6H5NH2). 젖산lactic acid, CH3CH(OH)COOH, 개미산(HCOOH) 중 어느 하나로 이루어지는 도금액을 이용하여 Cu-Sn-Zn 삼원합금 도금하는 것을 포함하는, PC-ABS 수지 부품의 비전해성 금속도금방법.
17. The method of claim 16,
Acetic acid (CH 3 COOH), glycolic acid (HOCH 2 COOH), glycine (NH 2 CH 2 COOH), aniline (C 6 H 5 NH 2 ), and the like are used as the monocarboxylic acid. Lactate lactic acid, CH 3 CH (OH ) COOH, formic acid (HCOOH) of any one of the non-water-decomposable metal plating method, PC-ABS resin components, comprising plated Cu-Sn-Zn ternary alloy using a plating solution composed.
제 16 항에 있어서,
상기 디카복실산으로는 숙신산(succinic acid, CH2)2(COOH)2, 사과산(malic acid, C8H6O5), 타타르산tataric acid, (CHOH)2(COOH)2, 옥살산oxalic acid, (COOH)2 중 어느 하나로 이루어지는 도금액을 이용하여 Cu-Sn-Zn 삼원합금 도금하는 것을 포함하는, PC-ABS 수지 부품의 비전해성 금속도금방법.
17. The method of claim 16,
Examples of the dicarboxylic acid include succinic acid (CH 2 ) 2 (COOH) 2 , malic acid, C 8 H 6 O 5 , tataric acid, (CHOH) 2 (COOH) 2 , oxalic acid, (COOH) 2 in a plating solution containing Cu-Sn-Zn ternary alloy.
제 16 항에 있어서,
상기 트리카복실산으로는 구연산(citric acid, C6H8O7), 아코니니틱산(aconitic acid(C6H6O8), 트리메스틱산(trimestic acid, C9H5O6), 프로판 1,2,3 트리카복실산propane-1,2,3-tricarboxylic acid, C3H5(COOH)3 중 어느 하나 또는 이들의 알칼리염으로 이루어지는 도금액을 이용하여 Cu-Sn-Zn 삼원합금 도금하는 것을 포함하는, PC-ABS 수지 부품의 비전해성 금속도금방법.
17. The method of claim 16,
Examples of the tricarboxylic acid include citric acid (C 6 H 8 O 7 ), aconitic acid (C 6 H 6 O 8 ), trimestic acid (C 9 H 5 O 6 ) Cu-Sn-Zn ternary alloy plating using a plating solution comprising any one of 1,2,3-tricarboxylic acid propane-1,2,3-tricarboxylic acid and C 3 H 5 (COOH) 3 or an alkali salt thereof A method of non-electrolytic metal plating of PC-ABS resin parts, comprising:
제 16 항에 있어서,
상기 안정제로 피로인산수소나트륨 100∼300g/ℓ, 착화제 구연산 15∼20g/ℓ, 아세트산 15∼25g/ℓ, 에틸렌디아민 40∼60ml/ℓ, pH 조절제로 NaOH 15∼25g/ℓ, 가 첨가되는 도금액을 이용하여 Cu-Sn-Zn 삼원합금 도금하는 것을 포함하는, PC-ABS 수지 부품의 비전해성 금속도금방법.
17. The method of claim 16,
The stabilizer is added with 100 to 300 g / l of sodium pyrophosphate, 15 to 20 g / l of a complexing agent citric acid, 15 to 25 g / l of acetic acid, 40 to 60 ml / l of ethylenediamine and 15 to 25 g / l of NaOH as a pH regulator A non-electrolytic metal plating method for PC-ABS resin parts, comprising plating a Cu-Sn-Zn ternary alloy using a plating solution.
삭제delete 삭제delete PC-ABS 수지 부품의 전처리 단계(S10): 상기 전처리 단계(S10)에 의해 전처리된 부품 상에 동을 도금하기 위한 동 전기도금 단계(S20): 상기 동 전기도금 단계(S20)를 거친 대상물의 동 전기도금층 위에 Cu-Sn-Zn 삼원합금으로 도금 처리하는, Cu-Sn-Zn 삼원합금 도금 단계(S30): 상기 Cu-Sn-Zn 삼원합금 도금 단계(S30)를 거친 대상물의 삼원합금 도금층 위에 최종적으로 3가크롬 도금단계(S40)를 거치는 것을 포함하되, 상기 3가크롬 도금단계(S40)에서 3가크롬 원으로는 황산크롬Cr2(SO4)3, 염화크롬(CrCl3), 질산크롬HNO3)3, 초산크롬Cr2(OAc)42H2O 에서 선택되는 어느 하나 이상의 군을 사용하여서 되는 도금액을 이용하되, 상기 도금액에 기타 첨가제로 착화제, 전도성 보조제, 산화제, 감극제, 습윤제, pH조절제 및 안정제, 무기물 색상발현제가 더 첨가되는 도금액을 이용하여 도금 처리하는 PC-ABS 수지 부품의 비전해성 금속도금방법에 있어서,
상기 착화제로는 옥살산(C2H2O4), 개미산(HCOOH) 중 어느 하나를, 상기 전도성 보조제로는 염화암모늄(NH4Cl), 염화칼륨(KCl), 염화칼슘(CaCl2) 중 어느 하나를, 상기 산화제로는 황산칼륨(K2SO4), 황산알루미늄Al2(SO4)3, 아황산암모늄(NH4)2S2O8 중 어느 하나를, 상기 감극제는 NH4Br, NaBr, NaF, KF 중 어느 하나를, 상기 습윤제는 소디움라우릴설페이트sodium lauryl sulfate, CH3(CH2)11SO4Na 를, 상기 pH 조절제 및 안정제로 KOH, NaOH, NH4OH, H2BO3, 중 어느 하나를, 상기 무기물 색상발현제로 Fe, Co 이온 중 어느 하나를 사용하여 첨가되는 도금액을 이용하여, 도금 처리하는 것을 포함하는, PC-ABS 수지 부품의 비전해성 금속도금방법.
(S10) of the PC-ABS resin component: an electro-electroplating step (S20) for plating the copper on the component pretreated by the preprocessing step (S10); a step Cu-Sn-Zn ternary alloy plating step (S30) in which the copper electroplating layer is plated with a Cu-Sn-Zn ternary alloy: On the ternary alloy plating layer of the object subjected to the Cu-Sn-Zn ternary alloy plating step (S30) comprising the final 3 passes through the chrome-plating step (S40), the trivalent chromium plating step (S40) trivalent chromium source in the Cr 2 chromium sulfate (SO 4) 3, chloride, chromium (CrCl 3), nitric acid in chromium HNO 3) 3, acetic acid chromium Cr 2 (OAc) 4 2H but using a plating liquid which hayeoseo using any one or more of the group selected from 2 O, complexed with other additives in the plating solution of claim, the conductive auxiliary agent, an oxidizing agent, a sense geukje, A wetting agent, a pH adjusting agent and a stabilizer, and a plating solution in which an inorganic coloring agent is further added In the water-decomposable non-metallic plating method of PC-ABS resin component than the plating process,
As the complexing agent, any one of oxalic acid (C 2 H 2 O 4 ) and formic acid (HCOOH) may be used as the complexing agent and ammonium chloride (NH 4 Cl), potassium chloride (KCl) and calcium chloride (CaCl 2 ) (K 2 SO 4 ), aluminum sulfate Al 2 (SO 4 ) 3 and ammonium sulfite (NH 4 ) 2 S 2 O 8 as the oxidizing agent, NH 4 Br, NaBr, NaF, KF, sodium lauryl sulfate and CH 3 (CH 2 ) 11 SO 4 Na were added to the wetting agent, and the pH adjuster and the stabilizer were KOH, NaOH, NH 4 OH, H 2 BO 3 , Wherein the plating is performed using a plating solution to which any one of Fe and Co ions is added as the inorganic color developing agent.
삭제delete PC-ABS 수지 부품의 전처리 단계(S10): 상기 전처리 단계(S10)에 의해 전처리된 부품 상에 동을 도금하기 위한 동 전기도금 단계(S20): 상기 동 전기도금 단계(S20)를 거친 대상물의 동 전기도금층 위에 Cu-Sn-Zn 삼원합금으로 도금 처리하는, Cu-Sn-Zn 삼원합금 도금 단계(S30): 상기 Cu-Sn-Zn 삼원합금 도금 단계(S30)를 거친 대상물의 삼원합금 도금층 위에 최종적으로 3가크롬 도금단계(S40)를 거치는 것을 포함하되, 상기 3가크롬 도금단계(S40)에 적용되는 도금액에서의 황산크롬Cr2(SO4)36H2O은 100∼300g/ℓ, 착화제인 옥살산(C2H2O42H2O)는 50∼70g/ℓ, 개미산(HCOOH) 30∼50g/ℓ의 농도를 유지하며, 3가크롬 1몰에 대하여 착화제는 0.1∼2.0몰로, 황 조정, 황산암모늄NH4)2SO4 40∼100g/ℓ, 아황산암모늄((NH4)2S2O8) 5∼15g/ℓ, 붕산(HBO3) 30∼80g/ℓ, 브롬화암모늄(NH4Br), 또는 불화칼륨(KF) 5∼40g/ℓ, 소디움라우릴설페이트CH3(CH2)11SO4Na 0.05∼0.1g/ℓ, 무기물 색상 발현제 2∼15g/ℓ을 첨가한 도금액을 사용하여 도금하는 것을 포함하는 PC-ABS 수지 부품의 비전해성 금속도금방법에 있어서,
상기 도금액의 온도 30∼60℃, pH 1.5∼5.0, 전류밀도 5∼20A/dm2, 양극은 불용성 흑연 또는 이리듐판을 채택하고, 도금시간은 1∼10분 범위내로 도금하는 것을 특징으로 하는 PC-ABS 수지 부품의 비전해성 금속도금방법.




(S10) of the PC-ABS resin component: an electro-electroplating step (S20) for plating the copper on the component pretreated by the preprocessing step (S10); a step Cu-Sn-Zn ternary alloy plating step (S30) in which the copper electroplating layer is plated with a Cu-Sn-Zn ternary alloy: On the ternary alloy plating layer of the object subjected to the Cu-Sn-Zn ternary alloy plating step (S30) Wherein the chromium sulfate (Cr 2 (SO 4 ) 3 6H 2 O) in the plating solution applied to the trivalent chromium plating step (S40) comprises 100 to 300 g / l, The concentration of oxalic acid (C 2 H 2 O 4 2H 2 O) as a complexing agent is 50 to 70 g / L and the concentration of formic acid (HCOOH) is 30 to 50 g / L, the complexing agent is 0.1 to 2.0 mol per 1 mol of trivalent chromium , sulfur adjustment, ammonium sulfate NH 4) 2 SO 4 40~100g / ℓ, ammonium sulfite ((NH 4) 2 S 2 O 8) 5~15g / ℓ, boric acid (HBO 3) 30~80g / ℓ, ammonium bromide (NH 4 Br), or Plating with a plating solution containing 5 to 40 g / l of potassium fluoride (KF), 0.05 to 0.1 g / l of sodium lauryl sulfate CH 3 (CH 2 ) 11 SO 4 Na and 2 to 15 g / l of inorganic color development Wherein the non-electrolytic metal plating method of the PC-ABS resin component comprises:
Characterized in that the temperature of the plating solution is 30 to 60 캜, the pH is 1.5 to 5.0, the current density is 5 to 20 A / dm 2 , the insoluble graphite or the iridium plate is used as the anode, and the plating is carried out within the range of 1 to 10 minutes - Non-electrolytic metal plating method of ABS resin parts.




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