KR960001851B1 - Thermoplastic resin composition for plating - Google Patents

Thermoplastic resin composition for plating Download PDF

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KR960001851B1
KR960001851B1 KR1019920012050A KR920012050A KR960001851B1 KR 960001851 B1 KR960001851 B1 KR 960001851B1 KR 1019920012050 A KR1019920012050 A KR 1019920012050A KR 920012050 A KR920012050 A KR 920012050A KR 960001851 B1 KR960001851 B1 KR 960001851B1
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weight
plating
thermoplastic resin
resin composition
monomer
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KR940002306A (en
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김정호
한종순
최장현
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한남화학주식회사
이덕림
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

(A) 40-60 wt.% of a graft copolymer to be prepd. by grafting 30-80 wt.% of conjugated dien based rubber with 40-60 wt.% of aromatic vinyl monomer and 20-30 wt.% of unsatd. nitrile; (b) 40-60 wt.% of a SAN copolymer to prepd. by suspension polymerising the monomer mixture comprising 30-70 wt.% of aromatic vinyl monomer and 30-70 wt.% of vinyl cyanide monomer with multifunctional organic peroxide as an initiator in pure water contg. suspension stabilizer. The obtd. thermoplastic resin compsn. has a good etching property, a stickness and a chemical resistance.

Description

도금용 열가소성수지 조성물Thermoplastic composition for plating

본 발명은 도금용 열가소성수지 조성물에 관한 것으로서, 더욱 상세하게는 공액디엔계 고무, 방향족 비닐 단량체 및 불포화니트릴을 그라프트한 그라프트 공중합체(A)와 방향족 비닐단량체 및 시안화 비닐단량체로 된 산(SAN) 공중합체(B)로 된 에칭성, 밀착강도 및 내약품이 우수한 도금용 열가소성수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition for plating, and more particularly, to a graft copolymer (A) grafted with a conjugated diene rubber, an aromatic vinyl monomer, and an unsaturated nitrile, an aromatic vinyl monomer, and an acid made of a vinyl cyanide monomer ( SAN) It is related with the thermoplastic resin composition for plating which is excellent in the etching property, adhesive strength, and chemical-resistance of a copolymer (B).

일반적으로 플라스틱 제품에 도금하여 사용되는 플라스틱 도금제품은 도금용 열가소성수지를 성형한후 에칭공정을 비롯한 도금공정 열가소성수지 조성물에 관한 것이다.Generally, a plastic plated product used by plating on a plastic product relates to a plating process thermoplastic resin composition including an etching process after molding a thermoplastic resin for plating.

일반적으로 플라스틱 제품에 도금하여 사용되는 플라스틱 도금제품은 도금용 열가소성수지를 성형한후 에칭공정을 비롯한 도금공정등의 일련의 제조과정을 통해서 제조된다.In general, plastic plating products used by plating on plastic products are manufactured through a series of manufacturing processes, such as plating process after molding thermoplastic resin for plating.

통상 이러한 제조과정을 통해서 제조되는 플라스틱 도금제품은 에칭공정에서 사용되는 에칭액에 대한 열 가소성수지의 내약품성이 만족스럽지 못해 밀착강도가 저하되고 이로인해 부분적인 미도금 형상이 발생되거나 표면의 금속층과 내부의 수지층간의 선팽창 계수의 차에서 발생되는 환경의 변화로 인해 박리현상이 빈번히 발생되는 문제점이 있었다. 종래의 플라스틱도금 제품으로 폭넓게 이용되어 왔던 ABS 수지 역시 이러한 도금용 열가소성 수지가 가지고 있는 문제점 즉, 성형조건에 따발생된 잔류응력이 고무의 배향을 일으킴으로서 미에칭에 의한 미도금의 발생, 금속층과 수지층간의 선팽창계수의 차에 따른 박리현상 발생등이 문제점으로 지적되어 왔다. 최근, 자동차를 위시한 공업용 제품의 경량화와 원가절감 등의 목적으로 플라스틱 도금제품에 대한 수요가 늘고 있으며 복잡한 성형물과 가혹한 조건에서 사용가능한 수지에 대한 요구가 심화되어 보다 높은 밀착강도와 내약품성 및 성형성이 우수한 플라스틱의 개발이 요구되고 있다 한편, 국내특허공고 제83-2459호에서는 그라프트 공중합체, 산(SAN) 공중합체, 유기균소화합물 및 활제로 구성된 열가소성수지 조성물에 관해 기술되어 있는바, 이 기술은 유기규소화합물을 첨가하여 열순환성을 향상시킨 것이기는 하지만 내약품성이 떨어지는 결점이 있었다.Usually, the plastic plating products manufactured through this manufacturing process are not satisfactory in the chemical resistance of the thermoplastic resin to the etching liquid used in the etching process, and thus the adhesion strength is lowered, resulting in partial unplated shape or the surface metal layer and the interior. Due to the change in the environment caused by the difference in the coefficient of linear expansion between the resin layers of the resin was a problem that frequently occurs peeling phenomenon. ABS resin, which has been widely used as a conventional plastic plating product, also has a problem with such a thermoplastic resin for plating, that is, residual stress caused by molding conditions causes rubber to be oriented so that unplating by unetching, metal layer and The problem of peeling phenomenon caused by the difference of linear expansion coefficient between resin layers has been pointed out as a problem. Recently, the demand for plastic-plated products is increasing for the purpose of reducing weight and cost of industrial products including automobiles, and the demand for resins that can be used in complicated moldings and harsh conditions is intensified, resulting in higher adhesion strength, chemical resistance and moldability. On the other hand, there is a demand for development of such excellent plastics. On the other hand, Korean Patent Publication No. 83-2459 describes a thermoplastic resin composition composed of a graft copolymer, an acid (SAN) copolymer, an organobacterial compound, and a lubricant. Although the technique improves thermocycling by adding an organosilicon compound, it has a disadvantage of poor chemical resistance.

또한, 이러한 문제점을 개선키 위하여 충격 보강제로 사용되는 고무의 종류나 크기등을 변화시켜 잔류응력을 최소화 하기 위한 방법과 각종 첨가제의 혼합등을 통한 밀착강도를 향상시키는 방법이 알려져 있으나 그 효과도 충분한 것은 아니었다.In addition, in order to improve such a problem, a method for minimizing residual stress by changing the type or size of rubber used as an impact reinforcing agent and a method for improving adhesion strength through mixing various additives are known, but the effect is sufficient. It was not.

따라서, 본 발명의 발명자들은 위와같은 종래의 문제점을 극복하고 에칭성과 밀착강도 및 내약품성이 우수한 도금용 열가소성수지를 제조하기 위하여 매트릭스 SAN 수지의 내약품성을 향상시켜 에칭시 매트릭스 SAN의 손상없이 고무의 용출이 충분토록 하므로써 에칭성을 향상시키고, 금속층과 수지층간의 밀착력을 강화시켜 선팽창계수의 차에 따라 발생되는 환경 변화에 대한 박리현상을 극소화시키기 위하여 분자량의 분포가 적어 기계적인 물성 및 내약품성이 우수한 현탁중합에 의하여 제조된 공중합체를 열가소성수지의 매트릭스상으로 도입하는 방법을 사용하므로써 물성이 우수한 도금용 열가소성 수지의 조성물을 제조할 수 있게 되어 본 발명을 완성하게 되었다.Therefore, the inventors of the present invention overcome the conventional problems as described above and improve the chemical resistance of the matrix SAN resin in order to manufacture the thermoplastic resin for plating excellent in etching resistance, adhesive strength and chemical resistance, so that the rubber of the matrix SAN is not damaged during etching. In order to improve the etching property by sufficient dissolution and to enhance the adhesion between the metal layer and the resin layer, the molecular weight distribution is small to minimize the peeling phenomenon due to the environmental change caused by the difference of the linear expansion coefficient. By using a method of introducing a copolymer prepared by excellent suspension polymerization into a matrix of thermoplastic resin, it is possible to prepare a composition of a thermoplastic resin for plating having excellent physical properties, thereby completing the present invention.

본 발명은 플라스틱 도금용 재료로 사용되는 에칭성과 내약품성 및 밀착 강도가 우수하게 개선된 새로운 조성의 도금용 열가소성수지 조성물은 제공하는데 그 목적이 있다.SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition for plating having a new composition with excellent etching, chemical resistance and adhesion strength used as a plastic plating material.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명은 도금용 열가소성수지 조성물에 있어서, 공액디엔계 공무 30∼70중량%에 방향족 비닐 단량체 20∼60중량%와 불포화 니트릴 10∼30중량%를 그라프트한 그라프트 공중합체(A) 40∼60중량%와, 방향족 비닐 단량체 30∼70중량% 및 시안화 비닐 단량체 30∼70중량%의 조성의 단량체 혼합물을 다관능성 유기과산화물을 개시제로서 사용하고 현탁안정제를 포함하는 순수중에서 현탁중합하여 제조된 산(SAN) 공중합체 (B) 40∼60중량%로 이루어진 도금용 열가소성수지 조성물을 그 특징으로 한다.In the thermoplastic resin composition for plating, graft copolymers (A) 40 to 20 to 60% by weight of aromatic vinyl monomer and 10 to 30% by weight of unsaturated nitrile are grafted to 30 to 70% by weight of conjugated diene-based azeotrope. An acid prepared by using a monomer mixture having a composition of 60% by weight and 30 to 70% by weight of an aromatic vinyl monomer and 30 to 70% by weight of a vinyl cyanide monomer using a polyfunctional organic peroxide as an initiator and suspension polymerization in pure water containing a suspension stabilizer. (SAN) Copolymer (B) It is characterized by the thermoplastic resin composition for plating which consists of 40 to 60 weight%.

위와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.Referring to the present invention in more detail as follows.

본 발명은 공액디엔계 고무에 방향족 비닐 단량체와 불포화 니트릴을 그라프트한 공중합체(A)와, 방향족 비닐 단량체와 시안화 비닐 단량체로된 공중합체(B)로 된 고금용 열가소성수지 조성물에 관한 것으로서, 본 발명의 그라프트 공중합체(A)는 입자경 범위 2,000∼3,500Å인 공액 디엔계 고무 30∼70중량%에 방향 족의 비닐단량체 20∼60중량% 및 불포화 니트릴 10∼30중량%를 그라프트 중합한 것으로서 중합방법은 유화중합법이 바람직스러우나 중합법에 큰 제한은 없다. 공액디엔계 고무의 입자경 범위는 도금특성에 큰 영향이 있으므로 매우 중요하며 입자경이 2,000Å 미만일 경우에는 극히 작은 범위를 제외하고는 밀착강도에 큰 영향은 없으나 최종 수지의 충격강도가 저하되므로 바람직하지 않고 입자경이 3,500Å을 초과하면 에칭 하여 고무가 용출된 부분의 크기가 너무 크므로 밀착강도가 떨어지는 결점이 있다.The present invention relates to a high molecular weight thermoplastic resin composition comprising a copolymer (A) obtained by grafting an aromatic vinyl monomer and an unsaturated nitrile to a conjugated diene rubber, and a copolymer (B) comprising an aromatic vinyl monomer and a vinyl cyanide monomer. The graft copolymer (A) of the present invention graft-polymerizes 20 to 60 wt% of aromatic vinyl monomer and 10 to 30 wt% of unsaturated nitrile to 30 to 70 wt% of conjugated diene rubber having a particle size range of 2,000 to 3,500 mm 3. As for the polymerization method, the emulsion polymerization method is preferable, but the polymerization method is not particularly limited. The particle size range of conjugated diene rubber is very important because it has a great effect on the plating properties.If the particle size is less than 2,000Å, it has no significant effect on the adhesion strength except for the extremely small range, but the impact strength of the final resin is not preferable. If the particle size exceeds 3,500Å, the size of the part where the rubber is eluted by etching is too large, which results in a poor adhesion strength.

여기서 방향족 비닐단량체의 함량이 20중량% 미만이면 최종수지의 유동성이 저하되어 성형가공시 응력을 받기 쉬운 문제가 있고 60중량%를 초과하면 수지의 성형성은 우수하나 내약품성이 저하되는 문제가 있으며, 불포화 니트릴이 10중량% 미만이면 내약품성이 저하되는 문제가 있고 30중량%를 초과하면 성형성이 저하되는 문제가 있다.If the content of the aromatic vinyl monomer is less than 20% by weight, there is a problem that the flowability of the final resin is lowered, so that it is susceptible to stress during molding, and when it exceeds 60% by weight, the moldability of the resin is excellent but the chemical resistance is lowered. If the unsaturated nitrile is less than 10% by weight, there is a problem that the chemical resistance is lowered, and if it exceeds 30% by weight, there is a problem that the moldability is lowered.

또한, 산(SAN) 공중합체(B)는 방향족 비닐단량체 30∼70중량% 및 시안화 비닐단량체 30∼70중량%의 조성의 단량체 혼합물을 다 관능성 유기과산화물을 개시제로서 현탁 안정제를 포함하는 순수중에서 중합온도 80∼130℃에서 현탁중합하여 제조하는데, 여기서 단량체 혼합물의 조성중 신안화 비닐단량체의 조성이 30∼70중량% 범위외에서는 내약품성이 저하되거나 성형성이 떨어져 잔류응력의 발생이 쉬우므로 에칭성이 좋지않아 미도금의 발생이 쉽게 일어날 우려가 있으며, 방향족 비닐단량체의 함량이 30중량% 미만이면 상대적으로 시안화비닐 단량체의 양이 많아져 최종수지의 분자량이 증가되어 성형성이 떨어지는 문제가 있고 70중량%를 초과하면 미반응 단량체의 양이 많아져 성형품의 표면에 은색흔적(Silver streak)등이 발생되는 문제가 생길 우려가 있다. 또 현탁 중합온도가 80℃ 미만이면 중합시간이 느려져 공중합체의 분자량이 하강될 우려가 있고 130℃를 초과하면 중합시간이 빨라져 공중합체의 분자량이 상승될 우려가 있다.The acid (SAN) copolymer (B) is a monomer mixture of 30 to 70% by weight of an aromatic vinyl monomer and 30 to 70% by weight of a vinyl cyanide monomer in a pure water containing a polyfunctional organic peroxide as an initiator and a suspension stabilizer. It is prepared by suspension polymerization at a polymerization temperature of 80 to 130 ° C, wherein the composition of the monomer mixture is in the range of 30 to 70 wt. There is a possibility that the unplating occurs easily due to poor properties, if the content of the aromatic vinyl monomer is less than 30% by weight, the amount of the vinyl cyanide monomer is relatively increased, the molecular weight of the final resin is increased and the moldability is inferior If it exceeds 70% by weight, the amount of unreacted monomer increases, which may cause a problem such as silver streak on the surface of the molded product. . If the suspension polymerization temperature is less than 80 ° C., the polymerization time may be slowed down and the molecular weight of the copolymer may be lowered.

여기서 다관능성 유기과산화물의 종류로서는 t-부틸퍼옥시 아세테이트, 1-부틸퍼옥시 이소프로필카보네이트, di-t-부틸퍼옥사이드 하이드로 테레프탈레이트, 1,1-di-t-부틸퍼옥시-3,3,5-트리메틸 시클로 헥산, di-t-부틸퍼옥시 헥사 하이드로 이소프탈레이트 등을 사용하는데, 상기 유기과산화물 이외의 개시제를 사용할 경우에는 중합 시간이 길거나 중합 전화율이 떨어져 부적당하다.Here, as the type of polyfunctional organic peroxide, t-butylperoxy acetate, 1-butylperoxy isopropyl carbonate, di-t-butylperoxide hydro terephthalate, 1,1-di-t-butylperoxy-3,3 , 5-trimethyl cyclohexane, di-t-butylperoxy hexahydro isophthalate, and the like are used. When an initiator other than the organic peroxide is used, the polymerization time is long or the polymerization conversion ratio is inadequate.

또한 현탁중합에 이용되는 분산제로서는 폴리비닐 알콜, 메칠 세롤셀로우즈 등의 수용성 고분자, 인산칼슘, 피로린산 칼슘, 탄산 마그네슘 등의 무기 분사제등이 이용되는데, 무기분산제의 경우에는 도데실벤젠 설폰산나트륨 등의 계면활성제를 소량 사용하면 분산성이 더욱 우수하며, 분산제의 사용량은 순수에 대하여 0.05∼0.1중량%로 사용한다.As the dispersant used in the suspension polymerization, water-soluble polymers such as polyvinyl alcohol and methyl ceroloserose, inorganic propellants such as calcium phosphate, calcium pyrophosphate and magnesium carbonate are used. In the case of the inorganic dispersant, dodecylbenzene sulfide is used. When a small amount of surfactant such as sodium fonate is used, the dispersibility is further excellent, and the amount of dispersant used is 0.05 to 0.1% by weight based on pure water.

본 발명의 그라프트 공중합체(A) 및 산(SAN) 공중합체(B)를 구성하는 각 성분에 대해서는 공액디엔계 고무로서는 폴리부타디엔 공중합체를 사용하고 방향족 비닐은 스티렌, 시안화비닐은 아크릴로 니트릴 또는 메타크릴로니트릴 등이 바람직하며 그라프트 공중합체(A)의 사용량은 40∼60중량%로서 40중량% 미만이면 상대적으로 산(SAN) 공중합체(B)의 양이 많아져 밀착강도가 떨어지고 내충격성 등의 기계적 물성이 저하 되며 사용량이 60중량%를 넘으면 유동성이 떨어지므로 성형시 잔류 응력의 발생이 많아 미도금 등의 불량 발생이 많아지므로 실용화가 어렵다.For each component constituting the graft copolymer (A) and the acid (SAN) copolymer (B) of the present invention, a polybutadiene copolymer is used as the conjugated diene rubber, and aromatic vinyl is styrene and vinyl cyanide is acrylonitrile. Alternatively, methacrylonitrile is preferred, and the graft copolymer (A) is used in an amount of 40 to 60% by weight and less than 40% by weight, so that the amount of the acid (SAN) copolymer (B) increases, resulting in poor adhesion strength. Mechanical properties such as impact resistance are lowered, and when the amount of use exceeds 60% by weight, the fluidity is lowered, so that residual stress is generated during molding, and defects such as unplating are more likely to be practical.

본 발명외 도금용 열가소성수지 조성물은 유화중합에 의해 제조된 그라프트 공중합체와 현탁 중합에 의해 제조된 산(SAN) 공중합체로 구성되어 있는데, 분자량 분포가 작고 내약품성이 우수한 현탁 산(SAN) 공중합체를 사용하면 내약품성이 향상되므로 에칭성이 개량되고 밀착강도가 향상되어 자동차를 위시한 공업용 제품, 특히 플라스틱 도금제품에 매우 유용하게 사용될 수 있다.In addition to the present invention, the thermoplastic resin composition for plating is composed of a graft copolymer prepared by emulsion polymerization and an acid (SAN) copolymer prepared by suspension polymerization, and has a small molecular weight distribution and excellent suspension resistance (SAN). When the copolymer is used, the chemical resistance is improved, so that the etching resistance is improved and the adhesion strength is improved, and thus it can be very useful for industrial products including automobiles, especially plastic plating products.

이하, 본 발명을 실시예에 의거 상세히 설명하겠는 바. 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples. The present invention is not limited by the examples.

[실시예 1]Example 1

[그라프트 공중합체(A)의 제조][Production of Graft Copolymer (A)]

교반기를 부착한 중합조에 평균 입자경이 2,500Å인 공액디엔계 고무 40중량%에 아크릴로 니트릴 20중량%, 스티렌 40중량%의 단량체 흔합물과 순수, 유화제 및 유화분산제를 첨가한후 교반시키면서 70℃로 승온하여 중합율이 98%될 때까지 중합한후 재차 80℃로 승온하여 3시간동안 중합시켜 그라프트 공줌합체(A)를 제조하였다.To a polymerization tank equipped with a stirrer, 20% by weight of acrylonitrile and 40% by weight of a monomer mixture of 40% by weight of acrylonitrile and 40% by weight of a conjugated diene rubber having an average particle size of 2,500 kPa were added thereto, followed by stirring, followed by stirring. After the polymerization was performed until the polymerization rate was 98%, the temperature was again increased to 80 ° C., and polymerization was performed for 3 hours to prepare a graft co-conjugate (A).

이때 중합개시제는 수용성 개시제인 K2S2O8를 0.5중량% 사용한다.At this time, the polymerization initiator uses 0.5% by weight of K 2 S 2 O 8 which is a water-soluble initiator.

[실시예 2]Example 2

[공중합체 (B)의 제조][Production of Copolymer (B)]

교반기를 부착한 중합조에 순수 100중량%, 스티렌 60중량%, 아크릴로 니트릴 40중량%와 개시제 t-부틸퍼옥시 아세테이트 0.7중량%와 분산제로서 폴리비닐알콜 0.09중량% 첨가한 후, 교반하면서 90℃에서 6시간 중합하고 다시 125℃로 승온후 3시간 중합시켜 산(SAN) 공중합체(B)를 제조하였다.100% by weight of pure water, 60% by weight of styrene, 40% by weight of acrylonitrile, 0.7% by weight of initiator t-butylperoxy acetate and 0.09% by weight of polyvinyl alcohol as a dispersant were added to the polymerization tank with a stirrer, followed by stirring at 90 ° C. The polymerization was carried out at 6 hours, and the temperature was further increased to 125 ° C., followed by polymerization for 3 hours to prepare an acid (SAN) copolymer (B).

[비교예 1,2][Comparative Examples 1,2]

공액디엔계 고무의 평균 입자경을 각각 1,000Å 및 5,000Å인 것을 사용한 것을 제외하고는 실시예 1과 동일하게 중합시켜 그라프트 공중합체(A)를 제조하였다.The graft copolymer (A) was prepared in the same manner as in Example 1 except that the average particle diameter of the conjugated diene rubber was 1,000 kPa and 5,000 kPa, respectively.

[비교예 3,4][Comparative Example 3, 4]

현탁 중합시 단량체 혼합물중 아크릴로니트릴의 양을 각각 20중량%와 80중량%로 한 것을 제외하고는 실시예 2와 동일하게 중합하여 산(SAN) 공중합체(B)를 제조하였다.An acid (SAN) copolymer (B) was prepared in the same manner as in Example 2 except that the amount of acrylonitrile in the monomer mixture during suspension polymerization was 20% by weight and 80% by weight, respectively.

[비교예 5][Comparative Example 5]

교반기를 부착한 중합조에 순수 150 중량%, 유화제 1,2중량부, 스티렌 70중량%, 아크릴로니트릴 30중량%로 된 단량체 혼합물을 중합물을 중합온도 70℃에서 게시제인 K2S2O8를 0.5중량%를 첨가하여 4시간동안 유화중합한 후 염석, 탈수 및 건조하여 공중합체를 제조하였다.In a polymerization tank equipped with a stirrer, a monomer mixture consisting of 150% by weight of pure water, 1,2 parts by weight of an emulsifier, 70% by weight of styrene, and 30% by weight of acrylonitrile was added to the polymerization product at a polymerization temperature of 70 ° C., K 2 S 2 O 8 . The copolymer was prepared by emulsion polymerization for 4 hours by adding 0.5% by weight, followed by salting out, dehydration and drying.

[실시예 3]Example 3

상기의 실시예 1∼2와 비교예 1∼4에 의하여 제조된 공중합체(A), (B)를 다음 표1에 나타낸 배합비로 혼합하여 수지조성물을 1∼14를 얻었다.The copolymers (A) and (B) produced by the above Examples 1 to 2 and Comparative Examples 1 to 4 were mixed at the compounding ratios shown in Table 1 below to obtain resin compositions 1 to 14.

[표 1]TABLE 1

(단위 : 중량%)(Unit: weight%)

[시험예][Test Example]

통상의 도금법에 의하여 도금된 제품은 밀착강도의 시험으로서 내냉열 순환시험으로 평가하며 내냉열 순환시험의 조건은 90℃에서 1시간, 상온에서 1시간, -30℃에서 1시간의 순환시험을 3회 연속실시하는 것으로 하는데 도금제품의 깨짐발생과 도금층의 박리현상등의 외관상의 문제점이 없는 것을 합격품으로 한다.Products plated by ordinary plating methods are tested for adhesion strength and evaluated by a cold-resistant heat cycle test. The conditions of the cold-heat cycle test are 1 hour at 90 ° C, 1 hour at room temperature, and 1 hour at -30 ° C. It is to be carried out continuously, and it is considered that there is no problem in appearance such as cracking of plating product and peeling phenomenon of plating layer.

상기 실시예 3의 표1에 나타낸 수지조성물 1∼13을 3온스의 사출성형기를 사용하여 사출성형하고 조성물 당 10개의 성형품을 제작한후 내냉열 순환시험에 의거하여 시험한 결과를 다음 표2에 나타내었다.The resin compositions 1 to 13 shown in Table 1 of Example 3 were injection molded using a 3 ounce injection molding machine, 10 molded articles were prepared per composition, and tested according to the cold / heat cycle test. Indicated.

[표 2]TABLE 2

단위 : 합격수(10회의 시험당)Unit: Number of Passes (per test 10)

Claims (7)

도금용 열가소성수지 조성물에 있어서, 공액디엔계 고무 30∼80중량%에 방향족 비닐 단량체 40∼60중량%와 불포화 니트릴 20∼30중량%이 그라프트된 그라프트 공중합체(A) 40∼60중량%와, 방향족 비닐 단량체 30∼70중량% 및 시안화 비닐 단량체 30∼70중량%의 조성의 단량체 혼합물을 다관능성 유기과산화물을 개시제로서 사용하고 현탁안정제를 포함하는 순수중에서 현탁중합하여 제조된 산(SAN) 공중합체(B) 40∼60중량%로 이루어진 것을 특징으로 하는 도금용 열가소성수지 조성물.In the thermoplastic resin composition for plating, 40 to 60% by weight of the graft copolymer (A) in which 30 to 80% by weight of the conjugated diene rubber is grafted to 40 to 60% by weight of the aromatic vinyl monomer and 20 to 30% by weight of the unsaturated nitrile. And an acid (SAN) prepared by using a monomer mixture having a composition of 30 to 70% by weight of an aromatic vinyl monomer and 30 to 70% by weight of a vinyl cyanide monomer, using a polyfunctional organic peroxide as an initiator and suspending polymerization in a pure water containing a suspension stabilizer. A thermoplastic resin composition for plating, comprising a copolymer (B) 40 to 60% by weight. 제1항에 있어서, 상기 공액디엔계 고무는 그 입자경의 크기가 2,000-3,500Å인 것을 특징으로 하는 도금용 열가소성수지 조성물The thermoplastic resin composition for plating according to claim 1, wherein the conjugated diene rubber has a particle size of 2,000-3,500 kPa. 제1항 또는 제2항에 있어서, 상기 공액디엔계 고무는 폴리부타디엔 고무인 것을 특징으로 하는 도금용 열가소성수지 조성물.3. The plating thermoplastic resin composition according to claim 1 or 2, wherein the conjugated diene rubber is a polybutadiene rubber. 제1항에 있어서, 상기 현탁중합은 80∼130℃의 온도에서 이루어진 것을 특징으로 하는 도금용 열가소성수지 조성물The thermoplastic resin composition for plating according to claim 1, wherein the suspension polymerization is performed at a temperature of 80 to 130 ° C. 제1항에 있어서, 상기 방향족 비닐은 스티렌인 것을 특징으로 하는 도금용 열가소성수지 조성물The thermoplastic resin composition for plating according to claim 1, wherein the aromatic vinyl is styrene. 제1항에 있어서, 상기 시안화비닐은 아크릴로니트릴 또는 메타크릴로니트릴인 것을 특징으로 하는 도금용 열가소성수지 조성물.The plating resin composition of claim 1, wherein the vinyl cyanide is acrylonitrile or methacrylonitrile. 제1항에 있어서, 상기의 개시제로 사용되는 다관능성 유기과산화물은 t-부틸퍼옥시 아세테이트, t-부틸퍼옥시 이소프로필 카보네이트, di-t-부틸퍼옥사이드 하이드로 테레프탈레이트, 1,1-di-t-부틸퍼옥시-3,3,5-트리메틸 시클로헥산 또는 di-t-부틸퍼옥시 헥사 하이드로 이소프탈레이트인 것을 특징으로 하는 도금용 열가소성수지 조성물The method of claim 1, wherein the multifunctional organic peroxide used as the initiator is t-butylperoxy acetate, t-butylperoxy isopropyl carbonate, di-t-butylperoxide hydro terephthalate, 1,1-di- t-butylperoxy-3,3,5-trimethyl cyclohexane or di-t-butylperoxy hexa hydro isophthalate, characterized in that the thermoplastic resin composition for plating
KR1019920012050A 1992-07-07 1992-07-07 Thermoplastic resin composition for plating KR960001851B1 (en)

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