KR20030034405A - Thermoplastic Resin Composition Having Good Surface Gloss, High Impact Strength and High Flowability - Google Patents

Thermoplastic Resin Composition Having Good Surface Gloss, High Impact Strength and High Flowability Download PDF

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KR20030034405A
KR20030034405A KR1020010065331A KR20010065331A KR20030034405A KR 20030034405 A KR20030034405 A KR 20030034405A KR 1020010065331 A KR1020010065331 A KR 1020010065331A KR 20010065331 A KR20010065331 A KR 20010065331A KR 20030034405 A KR20030034405 A KR 20030034405A
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weight
parts
resin
abs resin
san
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KR100433572B1 (en
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나희석
하두한
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제일모직주식회사
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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
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: Provided is a thermoplastic resin composition which comprises g-ABS(acrylonitrile-butadiene-styrene) resin and SAN(styrene-acrylonitrile copolymer) resin, and ethylene bis-stearoamide, and has excellent appearance quality such as surface gloss, impact resistance, and fluidity. CONSTITUTION: The composition comprises (A) 15-40 parts by weight of g-ABS resin consisting of (a1) the first g-ABS resin produced by using small particle size of rubber polymer having average particle diameter of 0.05-0.20 micrometers through emulsion graft polymerization, and (a2) the second g-ABS resin produced by using small particle size of rubber polymer having average particle diameter of 0.25-0.40 micrometers through emulsion graft polymerization, with the ratio((a1)and (a2)) of 20:80 to 80:20 wt%; (B) 60-85 parts by weight of SAN resin consisting of (b1) 10-70 parts by weight of first SAN resin having acrylonitrile content of 20-35% and weight average molecular weight of 110,000-140,000, and (b2) 90-30 parts by weight of second SAN resin having acrylonitrile content of 20-35% and weight average molecular weight of 80,000-100,000; and (C) 1-6 parts by weight of ethylene bis-stearoamide with respect to 100 parts by weight of the sum of components(A) and (B).

Description

표면광택, 내충격성 및 유동성이 우수한 열가소성 수지 조성물{Thermoplastic Resin Composition Having Good Surface Gloss, High Impact Strength and High Flowability}Thermoplastic Resin Composition Having Good Surface Gloss, High Impact Strength and High Flowability}

발명의 분야Field of invention

본 발명은 표면광택, 내충격성 및 유동성이 우수한 열가소성 수지 조성물에 관한 것이다. 보다 구체적으로, 본 발명은 입경이 서로 다른 2종의 고무질 중합체를 유화 그라프트 중합방법에 의해 별도로 중합한 아크릴로니트릴-부타디엔-스티렌 공중합체(이하 'g-ABS 수지'라 함)의 혼합물 및 매트릭스로 작용하는 특정의 아크릴로니트릴 함량을 갖고 분자량이 서로 다른 2종의 스티렌-아크릴로니트릴 공중합체(이하 'SAN 수지'라 함)의 혼합물로 이루어지고, 첨가제로 에틸렌비스스테아로아마이드를 포함하며, 선택적으로 특정한 힌더드 페놀계 산화방지제, 포스파이트계 산화방지제, 금속 스테아레이트계 활제, 실리콘계 충격보강제, 할스계 광안정제, 아민계 대전방지제 등을 조합하여 제조되는 표면광택, 내충격성 및 유동성이 우수한 열가소성 수지 조성물 관한 것이다.The present invention relates to a thermoplastic resin composition excellent in surface gloss, impact resistance and fluidity. More specifically, the present invention provides a mixture of acrylonitrile-butadiene-styrene copolymers (hereinafter referred to as 'g-ABS resins') obtained by separately polymerizing two rubbery polymers having different particle diameters by an emulsion graft polymerization method. It consists of a mixture of two styrene-acrylonitrile copolymers (hereinafter referred to as 'SAN resins') of different molecular weights, having a specific acrylonitrile content that acts as a matrix, and includes ethylene bis stearamide as an additive. Surface gloss, impact resistance and fluidity, optionally prepared by combining a specific hindered phenolic antioxidant, phosphite antioxidant, metal stearate lubricant, silicone impact modifier, Hals light stabilizer, amine antistatic agent, and the like. This excellent thermoplastic resin composition relates.

발명의 배경Background of the Invention

아크릴로니트릴-부타디엔-스티렌 공중합체 수지(이하 'ABS 수지'라 함)는 부타디엔계 고무질 중합체의 존재 하에서 방향족 비닐화합물인 스티렌 단량체와 불포화니트릴계 화합물인 아크릴로니트릴 단량체를 유화 그라프트 중합하여 제조된다. 이 때, 사용되는 고무질 중합체와 g-ABS 수지, 그리고 매트릭스 중합체의 조성을 조절하면 원하는 수지를 얻을 수 있다. 이렇게 제조된 ABS 수지는 내충격성, 내화학성, 내약품성, 내열성, 기계적 강도 등이 우수하고 성형가공이 용이하여 전기전자 제품의 부품 및 내외장재, 자동차 부품, 일반잡화 등에 광범위하게 사용되고 있다.Acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as 'ABS resin') is prepared by emulsion graft polymerization of an styrene monomer, an aromatic vinyl compound, and an acrylonitrile monomer, an unsaturated nitrile compound, in the presence of a butadiene rubbery polymer. do. At this time, the desired resin can be obtained by adjusting the composition of the rubbery polymer, g-ABS resin and matrix polymer used. The ABS resin thus prepared is widely used in electric and electronic parts, interior and exterior materials, automotive parts, general miscellaneous goods because of excellent impact resistance, chemical resistance, chemical resistance, heat resistance, and mechanical strength, and easy molding processing.

그러나, 최근 들어 수려한 외관과 광택을 가진 전기전자 제품에 대한 소비자의 요구가 증대되고 성형품은 점점 더 대형화, 소형화, 박막화, 경량화 되어감에 따라 이를 만족시키기 위해서 고유동성을 나타내면서도 내충격성은 일정 수준 이상을 보유한 ABS 수지의 필요성이 더욱 커지고 있다.However, in recent years, consumer demand for electrical and electronic products with beautiful appearance and gloss has increased, and molded articles have high flowability and shock resistance to meet this requirement as they become larger, smaller, thinner, and lighter. The need for ABS resins having increased is even greater.

종래에는 ABS 수지의 표면광택을 향상시키기 위해서 ABS 수지 중 SAN 수지의 함량을 늘려주거나, ABS 수지의 제조에 필요한 고무질 중합체의 입자 크기를 줄이는 방법을 사용하였으나 제품의 내충격성이 저하되어 성형품의 조립시에 크랙(crack)이 발생할 가능성이 있다. 또한 ABS 수지의 내충격성 및 유동성을 향상시키기 위해서 ABS 수지 중 SAN 수지의 분자량을 저하시키고 고무 함량을 줄여주는방법을 사용하였으나, 그러한 종래 방법으로는 유동성 및 내충격성을 동시에 만족시키기는 어렵다.Conventionally, in order to improve the surface gloss of the ABS resin, the method of increasing the content of the SAN resin in the ABS resin or reducing the particle size of the rubbery polymer required for the manufacture of the ABS resin was used. There is a possibility of cracking. In addition, in order to improve the impact resistance and fluidity of the ABS resin, a method of lowering the molecular weight of the SAN resin and reducing the rubber content of the ABS resin was used, but such a conventional method is difficult to satisfy the fluidity and impact resistance at the same time.

따라서 본 발명자들은 이상과 같은 문제점을 해결하고자 소입경 고무질 중합체를 사용하여 중합된 g-ABS 수지와 중입경 고무질 중합체를 사용하여 중합된 g-ABS 수지를 별도로 제조하여 이를 혼합 사용함으로써 우수한 표면광택과 내충격성을 나타내면서 우수한 물성 발란스를 갖도록 하였으며, 특정의 아크릴로니트릴 함량을 갖고 중량 평균 분자량이 서로 다른 2종의 SAN 수지 혼합물을 혼합하여 사용하고, 여기에 에틸렌비스스테아로아마이드를 첨가제로 사용함으로써 우수한 유동성과 내충격성을 보유한 열가소성 수지 조성물을 개발하기에 이른 것이다.Accordingly, the present inventors separately prepared a polymerized g-ABS resin using a small particle rubbery polymer and a polymerized g-ABS resin using a medium particle rubbery polymer to solve the above problems. It has excellent physical balance while showing impact resistance, and it is used by mixing two kinds of SAN resin mixtures having specific acrylonitrile content and different weight average molecular weight, and by using ethylene bis stearamide as an additive. To develop a thermoplastic resin composition having fluidity and impact resistance.

본 발명의 목적은 표면광택을 비롯한 외관 품질이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a thermoplastic resin composition having excellent appearance quality including surface gloss.

본 발명의 다른 목적은 내충격성이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance.

본 발명의 또 다른 목적은 유동성이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.Still another object of the present invention is to provide a thermoplastic resin composition having excellent fluidity.

발명의 상기 목적 및 기타의 목적들은 하기 설명되는 본 발명에 의해 모두 달성될 수 있다.The above and other objects of the invention can be achieved by the present invention described below.

본 발명에 따른 열가소성 수지 조성물은 (A) (a1) 평균 입자 크기가 0.05∼0.20 ㎛인 소입경 고무질 중합체를 사용하여 유화 그라프트 중합법으로 제조된 제1 g-ABS 수지 및 (a2) 평균 입자 크기가 0.25∼0.40 ㎛인 중입경 고무질 중합체를 사용하여 유화 그라프트 중합법으로 제조된 제2 g-ABS 수지가 20 : 80 에서 80 : 20 중량%의 비율로 구성된 g-ABS 수지 15∼40 중량부; (B) (b1) 아크릴로니트릴 함량이 20∼35 중량%이고 중량 평균 분자량이 110,000∼140,000인 제1 SAN 수지 10∼70 중량부 및 (b2) 아크릴로니트릴 함량이 20∼35 중량%이고 중량 평균 분자량이 80,000∼100,000인 제2 SAN 수지 90∼30 중량부로 구성된 SAN 수지 60∼85 중량부; 및 (C) 구성성분 (A) 및 (B)의 전체 100 중량부에 대해서 에틸렌비스스테아로아마이드 1∼7 중량부로 이루어지는 것을 특징으로 하는 수지 조성물로서, 우수한 표면광택, 내충격성 및 유동성을 갖는다. 이하 본 발명의 내용을 상세하게 설명하면 다음과 같다.The thermoplastic resin composition according to the present invention comprises (A) (a 1 ) a first g-ABS resin prepared by an emulsion graft polymerization method using a small particle rubbery polymer having an average particle size of 0.05 to 0.20 μm and (a 2 ) G-ABS resins 15 to 20 composed of a ratio of 20:80 to 80: 20% by weight of a second g-ABS resin prepared by emulsion graft polymerization using a medium-size rubbery polymer having an average particle size of 0.25 to 0.40 µm. 40 parts by weight; (B) (b 1) is 20-35% by weight of acrylonitrile content and having a weight average molecular weight of 110000-140000 of claim 1 SAN resin and 10 to 70 parts by weight of (b 2) is an acrylonitrile content of 20-35% by weight 60 to 85 parts by weight of a SAN resin composed of 90 to 30 parts by weight of a second SAN resin having a weight average molecular weight of 80,000 to 100,000; And (C) 1 to 7 parts by weight of ethylenebisstearoamide relative to 100 parts by weight of the total of the components (A) and (B), and has excellent surface gloss, impact resistance and fluidity. Hereinafter, the content of the present invention will be described in detail.

본 발명의 상기 구성 성분 중 g-ABS 수지 (A)는 (a1) 평균 입자 크기가 0.05∼0.20 ㎛인 소입경 고무질 중합체를 사용하여 유화 그라프트 중합법으로 제조된 제1 g-ABS 수지 및 (a2) 평균 입자 크기가 0.25∼0.40 ㎛인 중입경 고무질 중합체를 사용하여 유화 그라프트 중합법으로 제조된 제2 g-ABS 수지가 20 : 80 에서 80 : 20 중량%의 비율로 구성된 g-ABS 수지를 ABS 수지 전체 100 중량부에 대해서15∼40 중량부의 비율로 혼합 사용한다.G-ABS resin (A) in the above constituents of the present invention is (a 1 ) the first g-ABS resin prepared by the emulsion graft polymerization method using a small particle rubbery polymer having an average particle size of 0.05 to 0.20 ㎛ and (a 2 ) g-ABS resin prepared by the emulsion graft polymerization method using a medium-size rubbery polymer having an average particle size of 0.25 to 0.40 μm is composed of g- at a ratio of 20:80 to 80: 20% by weight. ABS resin is mixed and used in the ratio of 15-40 weight part with respect to 100 weight part of total ABS resin.

상기와 같이 고무질 중합체의 입경이 서로 다른 제1 g-ABS 수지 및 제2 g-ABS 수지를 혼합하여 사용하는 이유는 고무질 중합체의 입경이 0.20 ㎛ 이하인 g-ABS 수지를 단독으로 사용하는 경우에 표면광택은 개선되지만 내충격성이 현저하게 저하되는 단점이 있으며, 고무질 중합체의 입경이 0.30 ㎛ 이상인 g-ABS 수지를 단독으로 사용하는 경우에는 내충격성은 개선되지만 표면광택도가 현저하게 저하되는 단점이 있기 때문이다.The reason why the first g-ABS resin and the second g-ABS resin having different particle diameters of the rubbery polymer are mixed as described above is that when the g-ABS resin having a particle diameter of the rubbery polymer of 0.20 μm or less is used alone. Gloss is improved but impact resistance is remarkably lowered. When g-ABS resin having a particle size of 0.30 μm or more of rubbery polymer is used alone, impact resistance is improved but surface glossiness is remarkably lowered. to be.

이러한 단점을 보완하고, 각각의 g-ABS 수지가 갖는 특성을 동시에 수득하기 위해서는 평균입경이 0.05 내지 0.20 ㎛ 정도의 작은 입자로 이루어진 고무질 중합체를 사용한 g-ABS 수지와 0.25 내지 0.40 ㎛ 정도의 비교적 큰 입자로 이루어진 고무질 중합체를 사용한 g-ABS 수지를 혼합하여 사용하는 것이 바람직하다.In order to compensate for these disadvantages and simultaneously obtain the characteristics of each g-ABS resin, a g-ABS resin using a rubbery polymer composed of small particles having an average particle diameter of about 0.05 to 0.20 μm and a relatively large amount of 0.25 to 0.40 μm It is preferable to mix and use g-ABS resin using the rubbery polymer which consists of particle | grains.

따라서, 본 발명에서는 입자 크기가 다른 2 종의 고무질 중합체를 각각 유화 그라프트 중합하여 2 종의 g-ABS 수지를 별도로 제조하고, 이들을 컴파운딩 공정 중에 혼합 사용함으로써, 소입경 고무질 중합체가 갖는 외관품질의 우수성과 중입경 고무질 중합체가 갖는 내충격성 등의 물성 발란스와 더불어 중합공정을 안정화시켜 코아귤럼(coagulaum) 및 미가소화(unplasticized) 입자를 최소화한 것이다.Therefore, in the present invention, two kinds of g-ABS resins are separately prepared by emulsion graft polymerization of two kinds of rubber polymers having different particle sizes, and these are mixed and used in the compounding process, thereby providing the appearance quality of the small particle rubber polymers. It is to minimize the coagulaum and unplasticized particles by stabilizing the polymerization process together with the balance of physical properties such as superiority and impact resistance of the medium-size rubbery polymer.

본 발명에 사용 가능한 소입경 고무질 중합체의 평균입경은 0.05∼0.20 ㎛의 범위가 바람직하며, 특히 0.08∼0.18 ㎛ 정도가 더 바람직하다. 또한, 중입경 고무질 중합체의 평균입경은 0.25∼0.40 ㎛의 범위가 바람직하며, 0.28∼0.38 ㎛ 정도가 더 바람직하다.The average particle diameter of the small particle size rubbery polymer usable in the present invention is preferably in the range of 0.05 to 0.20 µm, more preferably about 0.08 to 0.18 µm. Moreover, the range of 0.25-0.40 micrometer is preferable, and, as for the average particle diameter of a medium particle size rubbery polymer, about 0.28-0.38 micrometer is more preferable.

상기 입자크기가 다른 고무질 중합체를 각각 유화 그라프트 중합하고 소입경 g-ABS 수지 : 중입경 g-ABS 수지를 20 : 80 내지 80 : 20 중량%의 비율로 혼합하여 사용한다. 상기 비율을 벗어나면, 각각의 입자 크기를 가지고 있는 고무질 중합체의 특성을 조화시키지 못하고, 소입경 고무질 중합체에 의해 깨지기 쉬운 특성을 갖게 되거나 중입경 고무질 중합체에 의해 표면광택이 저하되는 문제점이 있다.The rubbery polymers having different particle sizes are emulsified by graft polymerization, respectively, and a small particle size g-ABS resin is mixed with a medium particle size g-ABS resin in a ratio of 20:80 to 80: 20% by weight. If the ratio is out of the range, the characteristics of the rubbery polymers having the respective particle sizes may not be harmonized, and the surface gloss may be degraded by the small-size rubbery polymer or may be broken by the small-size rubbery polymer.

상기 각각의 g-ABS 수지의 그라프트율은 40∼90%로 하는 것이 바람직하다. 그라프트율이 이보다 낮으면, 응고, 건조시 입경 분포가 균일한 백색분말을 획득하기 어려울 뿐만 아니라, 압출 또는 사출시 성형품 표면에 미가소화 입자로서 피쉬아이(fisheye), 핀홀(pinhole) 또는 모래표면(sandsurface)과 같은 현상이 나타나 표면광택도가 저하된다. 또한, 그라프트율이 90%를 초과하면 오히려 충격강도, 유동성 및 표면광택 등의 물성저하가 생기게 된다.It is preferable that the graft ratio of each said g-ABS resin shall be 40 to 90%. If the graft rate is lower than this, it is difficult to obtain a white powder having a uniform particle size distribution during solidification and drying, as well as fisheye, pinhole or sandsurface as unplasticized particles on the surface of the molded part during extrusion or injection. ), The surface gloss is reduced. In addition, when the graft ratio exceeds 90%, physical properties such as impact strength, fluidity, and surface gloss decrease.

본 발명에 있어서 상기 g-ABS 수지(A)는 15∼40 중량부로 사용되는 것이 바람직하다. g-ABS 수지 사용함량이 15 중량부 이하에서는 본 발명에서 요구하는 내충격성이 우수한 ABS 수지를 수득하기 어렵고, 40 중량부 이상에서는 유동성을 저하시켜 본 발명을 완성할 수 없다.In the present invention, the g-ABS resin (A) is preferably used in 15 to 40 parts by weight. When the g-ABS resin content is 15 parts by weight or less, it is difficult to obtain an ABS resin having excellent impact resistance required by the present invention. When the content of the g-ABS resin is 40 parts by weight or more, the fluidity is lowered to complete the present invention.

본 발명의 상기 구성 성분 중 SAN 수지(B)는 (b1) 아크릴로니트릴 함량이 20∼35%이고 중량 평균 분자량이 110,000∼140,000인 제1 SAN 수지와 (b2) 아크릴로니트릴 함량이 20∼35%이고 중량 평균 분자량이 80,000∼100,000인 제2 SAN 수지로 이루어지며 전체 SAN 수지(B) 중 상기 제1 SAN 수지(b1)는 10∼70 중량부로 사용되고 상기 제2 SAN 수지(b2)는 90∼30 중량부로 사용된다.Among the components of the present invention, the SAN resin (B) has a (b 1 ) acrylonitrile content of 20 to 35% and a weight average molecular weight of 110,000 to 140,000 first SAN resin and (b 2 ) acrylonitrile content of 20 It is composed of a second SAN resin of ˜35% and a weight average molecular weight of 80,000 to 100,000, wherein the first SAN resin (b 1 ) of the total SAN resin (B) is used in 10 to 70 parts by weight and the second SAN resin (b 2 ) Is used in 90 to 30 parts by weight.

본 발명에 있어서 상기 성분 (b1) 및 (b2)로 이루어지는 SAN 수지(B)는 전체 수지 조성물에 대하여 60∼85 중량부로 사용되는 것이 바람직하다. SAN 수지 사용함량이 60 중량부 이하에서는 유동성이 저하되며, 85 중량부 이상에서는 본 발명에서 요구하는 내충격성이 우수한 ABS 수지를 수득하기 어렵다.SAN resin (B) composed of the components (b 1) and (b 2) in the invention is preferably used in 60 to 85 parts by weight relative to the total resin composition. When the SAN resin content is 60 parts by weight or less, the fluidity is lowered, and when it is 85 parts by weight or more, it is difficult to obtain an ABS resin having excellent impact resistance required by the present invention.

본 발명의 열가소성 수지 조성물은 상기 기초수지 (A)+(B)에 에틸렌비스스테아로아마이드(C)를 첨가제로 배합하여 얻어진다. 본 발명의 열가소성 수지 조성물에 있어서 성분(C)은 상기 기초수지 (A)+(B) 100 중량부에 대하여 1∼7 중량부로 투입되는 것이 바람직한데 (C)의 투입량이 상기 범위를 벗어날 경우에는 유동성, 내충격성 효과가 불충분하게 나타나며 사출성형물의 변색 및 가스실버가 발생할 가능성이 있다.The thermoplastic resin composition of this invention is obtained by mix | blending ethylene bis stearamide (C) with the said base resin (A) + (B) as an additive. In the thermoplastic resin composition of the present invention, the component (C) is preferably added in an amount of 1 to 7 parts by weight based on 100 parts by weight of the base resin (A) + (B). The fluidity and impact resistance effect is insufficient, and there is a possibility of discoloration of the injection molding and gas silver.

또한 본 발명의 열가소성 수지 조성물은 상기 g-ABS 수지(A), SAN 수지(B) 및 에틸렌비스스테아로아마이드(C)를 혼합함에 있어 각각의 용도에 따라 선택적으로 특정한 힌더드 페놀계 산화방지제, 포스파이트계 산화방지제, 금속 스테아레이트계 활제, 실리콘계 충격보강제, 할스계 광안정제와 아민계 대전방지제, 무기물 첨가제, 안료 및/또는 염료 등을 더 첨가하여 용융 혼련공정을 거쳐 사출 성형하여 제조될 수 있다. 상기와 같은 선택적인 첨가제는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있다.In addition, the thermoplastic resin composition of the present invention, in the mixing of the g-ABS resin (A), the SAN resin (B) and ethylene bis stearamide (C), optionally hindered phenol-based antioxidants, It can be prepared by injection molding through melt kneading process by further adding phosphite-based antioxidant, metal stearate-based lubricant, silicone-based impact modifier, Hals-based light stabilizer and amine-based antistatic agent, inorganic additive, pigment and / or dye, etc. have. Such optional additives may be easily implemented by those skilled in the art.

상기 수지 조성물 100 중량부에 대해서 힌더드 페놀계 산화방지제는 0.05 내지 2 중량부, 포스파이트계 산화방지제는 0.05 내지 2 중량부, 금속 스테아레이트계 활제는 0.1 내지 3 중량부, 실리콘계 충격보강제는 0.01 내지 1 중량부, 할스계 광안정제는 0.1 내지 2 중량부, 및/또는 아민계 대전방지제는 0.1 내지 2 중량부로 사용된다.The hindered phenolic antioxidant is 0.05 to 2 parts by weight, the phosphite antioxidant is 0.05 to 2 parts by weight, the metal stearate lubricant is 0.1 to 3 parts by weight, and the silicone impact modifier is 0.01 to 100 parts by weight of the resin composition. To 1 part by weight, Hals-based light stabilizer is 0.1 to 2 parts by weight, and / or amine antistatic agent is used in 0.1 to 2 parts by weight.

상기 힌더드 페놀계 산화방지제는 옥타딜-3-(4-하이드록시-3,5-디-터트-부틸페닐)프로피오네이트이고, 포스파이트계 산화방지제는 디스테아닐펜타에리트리톨디포스파이트이고, 금속 스테아레이트계 활제는 마그네슘 스테아레이트이고, 실리콘계 충격보강제는 폴리디메틸실록산이고, 할스계 광안정제는 비스(2,2,6,6,-테트라메틸-4-피페리디닐)세바케이트이고, 아민계 대전방지제는 N-하이드록시에틸-N (2-하이드록시 알킬)아민인 것이 바람직하다.The hindered phenolic antioxidant is octadyl-3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, and the phosphite antioxidant is disteanilpentaerythritol diphosphite The metal stearate lubricant is magnesium stearate, the silicone impact modifier is polydimethylsiloxane, the Hals light stabilizer is bis (2,2,6,6, -tetramethyl-4-piperidinyl) sebacate, The amine antistatic agent is preferably N-hydroxyethyl-N (2-hydroxy alkyl) amine.

본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

실시예Example

실시예 1∼4Examples 1-4

고무입경이 0.12 ㎛인 고무질 중합체를 유화 그라프트 중합하여 코어-쉘 형태를 갖는 제1 g-ABS 수지(a1) 및 고무입경이 0.32 ㎛인 고무질 중합체를 유화 그라프트 중합하여 코어-쉘 형태를 갖는 제2 g-ABS 수지(a2)로 구성된 g-ABS 수지(A), 아크릴로니트릴 함량이 28 중량%이고 중량 평균 분자량이 120,000인 제1 SAN 수지(b1)와 아크릴로니트릴 함량이 28 중량%이고 중량 평균 분자량이 90,000인 제2 SAN 수지(b2)로 구성된 SAN수지(B)에 에틸렌비스스테아로아마이드(C), 힌더드 페놀계산화방지제로 옥타딜-3-(4-하이드록시-3,5-디-터트-부틸페닐)프로피오네이트(D), 스테아레이트계 금속활제로 마그네슘 스테아레이트(E) 및 실리콘계 충격보강제로 디메틸폴리실록산(F)을 하기 표 1에 기재된 바와 같은 함량으로 첨가한 후 용융, 혼련 압출하여 펠렛을 제조하였다. 상기 압출은 L/D=29, 직경 45 ㎜인 이축압출기를 사용하였으며 실린더 온도는 210 ℃로 설정하였다. 제조된 펠렛으로 물성시편을 사출성형하여 물성을 측정하였으며 그 결과는 하기 표 2에 나타내었다.Emulsion graft polymerization of a rubbery polymer having a rubber particle diameter of 0.12 μm is carried out by emulsion graft polymerization of a first g-ABS resin (a 1 ) having a core-shell shape and rubbery polymer having a rubber particle diameter of 0.32 μm. A g-ABS resin (A) composed of a second g-ABS resin (a 2 ) having an acrylonitrile content of 28% by weight and a weight average molecular weight of 120,000, the first SAN resin (b 1 ) and an acrylonitrile content Ethylbisstearoamide (C) and a hindered phenolic antioxidant to octadil-3- (4-) in a SAN resin (B) composed of a second SAN resin (b 2 ) having a weight average molecular weight of 90,000 at 28% by weight. Hydroxy-3,5-di-tert-butylphenyl) propionate (D), magnesium stearate (E) as a stearate metal lubricant and dimethylpolysiloxane (F) as a silicone impact modifier are shown in Table 1 below. The pellets were prepared by adding the same content, followed by melting and kneading extrusion. The extrusion was a twin screw extruder L / D = 29, 45 mm in diameter and the cylinder temperature was set to 210 ℃. The physical properties of the prepared pellets were measured by injection molding, and the results are shown in Table 2 below.

실시예 1∼4 및 하기의 비교실시예 1∼5에서 제조된 수지 조성물의 각 물성의 측정 방법은 다음과 같다. 노치 아이조드 충격강도는 ASTM D256 (1/4", 1/8", 23 ℃)에 따라 측정하였고, 유동지수는 ASTM D1238 (5 ㎏, 200 ℃)에 따라 측정하였으며, 광택도는 ASTM D523 (측정각도 20°)에 따라 측정하였다.The measuring method of each physical property of the resin composition manufactured by Examples 1-4 and Comparative Examples 1-5 below is as follows. Notched Izod impact strength was measured according to ASTM D256 (1/4 ", 1/8", 23 ° C), flow index was measured according to ASTM D1238 (5 kg, 200 ° C), glossiness ASTM D523 (measured) Angle 20 °).

비교실시예 1Comparative Example 1

고무입경이 0.32 ㎛인 고무질 중합체를 유화 그라프트 중합한 제2 g-ABS 수지(a2)를 단독으로 사용한 것을 제외하고는 실시예 1과 동일하게 시편을 제조하였다.A specimen was prepared in the same manner as in Example 1, except that the second g-ABS resin (a 2 ) obtained by emulsion graft polymerization of a rubbery polymer having a rubber particle diameter of 0.32 μm was used alone.

비교실시예 2Comparative Example 2

고무입경이 0.12 ㎛인 고무질 중합체를 유화 그라프트 중합한 제1 g-ABS 수지(a1)를 단독으로 사용한 것을 제외하고는 실시예 1과 동일하게 시편을 제조하였다.A specimen was prepared in the same manner as in Example 1 except that the first g-ABS resin (a 1 ) obtained by emulsion graft polymerization of a rubbery polymer having a rubber particle diameter of 0.12 μm was used alone.

비교실시예 3Comparative Example 3

아크릴로니트릴 함량이 28 중량%이고 중량 평균 분자량이 120,000인 제1 SAN 수지(b1)를 단독으로 사용한 것을 제외하고는 실시예 1과 동일하게 시편을 제조하였다.A specimen was prepared in the same manner as in Example 1 except that the first SAN resin (b 1 ) having an acrylonitrile content of 28% by weight and a weight average molecular weight of 120,000 was used alone.

비교실시예 4Comparative Example 4

아크릴로니트릴 함량이 28 중량%이고 중량 평균 분자량이 90,000인 제2 SAN 수지(b2)를 단독으로 사용한 것을 제외하고는 실시예 1과 동일하게 시편을 제조하였다.A specimen was prepared in the same manner as in Example 1 except that the second SAN resin (b 2 ) having an acrylonitrile content of 28% by weight and a weight average molecular weight of 90,000 was used alone.

비교실시예 5Comparative Example 5

에틸렌비스스테아로아마이드(C)를 사용하지 않는 것을 제외하고는 실시예 1과 동일하게 시편을 제조하였다.A specimen was prepared in the same manner as in Example 1 except that ethylene bis stearamide (C) was not used.

상기 비교실시예의 방법에 의해 상기 실시예와 동일한 조건에서 제조된 펠렛으로 물성시편을 사출성형하여 실시예에서와 같은 방법으로 물성을 측정하였으며, 그 결과는 하기 표 2에 나타내었다.The physical properties of the specimens were injection molded into pellets prepared under the same conditions as in the above Examples, and the physical properties thereof were measured in the same manner as in the Examples, and the results are shown in Table 2 below.

구 분division 성 분(중량부)Component (parts by weight) g-ABS 수지(A)g-ABS resin (A) SAN 수지(B)SAN resin (B) 에틸렌비스스테아로아마이드(C)Ethylene Bisstearoamide (C) 산화방지제(D)Antioxidant (D) 금속활제(E)Metal lubricant (E) 충격보강제(F)Impact modifier (F) (a1)(a 1 ) (a2)(a 2 ) (b1)(b 1 ) (b2)(b 2 ) 실시예Example 1One 1010 2020 2525 4545 3.03.0 0.10.1 0.20.2 0.020.02 22 1010 2020 4545 2525 3.03.0 0.10.1 0.20.2 0.020.02 33 1515 1515 2525 4545 3.03.0 0.10.1 0.20.2 0.020.02 44 1010 2020 2525 4545 4.04.0 0.10.1 0.20.2 0.020.02 비교실시예Comparative Example 1One -- 3030 2525 4545 3.03.0 0.10.1 0.20.2 0.020.02 22 3030 -- 2525 4545 3.03.0 0.10.1 0.20.2 0.020.02 33 1010 2020 7070 -- 3.03.0 0.10.1 0.20.2 0.020.02 44 1010 2020 -- 7070 3.03.0 0.10.1 0.20.2 0.020.02 55 1010 2020 2525 4545 -- 0.10.1 0.20.2 0.020.02

구 분division 물 성Properties 노치 아이조드충격강도(1/4")(kgf·cm/cm)Notched Izod Impact Strength (1/4 ") (kgfcm / cm) 노치 아이조드충격강도(1/8")(kgf·cm/cm)Notched Izod Impact Strength (1/8 ") (kgfcm / cm) 유동 지수(g/10 min)Flow index (g / 10 min) 광택도(%)Glossiness (%) 실시예Example 1One 2424 3737 4.64.6 108108 22 2727 3939 3.83.8 105105 33 2323 3434 4.44.4 112112 44 2525 3939 4.94.9 112112 비교실시예Comparative Example 1One 2525 3838 3.43.4 9696 22 1717 2424 3.23.2 115115 33 2323 3535 2.42.4 103103 44 1919 2828 3.73.7 105105 55 2121 3232 3.23.2 101101

상기 표 2의 결과로부터 입경이 0.32 ㎛인 고무질 중합체를 유화 그라프트 중합한 제2 g-ABS 수지(a2)만을 사용한 비교실시예 1의 경우, 광택도가 저하되는 것으로 나타났으며 입경이 0.12 ㎛인 고무질 중합체를 유화 그라프트 중합한 제1 g-ABS 수지(a1)만을 사용한 비교실시예 2의 경우, 충격강도 및 유동지수가 저하된 것으로 나타났다.From the results in Table 2, in Comparative Example 1 using only the second g-ABS resin (a 2 ) obtained by emulsion graft polymerization of a rubbery polymer having a particle diameter of 0.32 μm, the gloss was lowered and the particle diameter was 0.12. In the case of Comparative Example 2 using only the first g-ABS resin (a 1 ) in which the rubbery polymer having a μm was emulsion-grafted polymerized, it was found that the impact strength and the flow index were lowered.

또한 SAN 수지로서 중량 평균 분자량이 120,000인 제1 SAN 수지(b1)만을 사용한 비교실시예 3의 경우는 충격강도는 우수하였으나 유동지수가 매우 낮게 나타났으며 SAN 수지로 중량 평균 분자량이 90,000인 제2 SAN 수지(b2)만을 사용한 비교실시예 4의 경우는 유동지수는 우수하였으나 충격강도가 매우 낮으로 나타났다.In addition, in Comparative Example 3 using only the first SAN resin (b 1 ) having a weight average molecular weight of 120,000 as the SAN resin, the impact strength was excellent, but the flow index was very low, and the SAN resin had a weight average molecular weight of 90,000. In Comparative Example 4 using only 2 SAN resin (b 2 ), the flow index was excellent, but the impact strength was very low.

또한 에틸렌비스스테아로아마이드(C)를 전혀 사용하지 않은 비교실시예 5의 경우 충격강도, 유동지수 및 광택도 모두가 저하되는 것으로 나타났다.In addition, in the case of Comparative Example 5 in which ethylene bis stearamide (C) was not used at all, the impact strength, the flow index, and the glossiness were all decreased.

본 발명은 고무 입자 크기가 서로 다른 2종의 고무질 중합체를 각각 유화 그라프트 중합하여 g-ABS 수지를 별도로 제조하고, 이들을 컴파운딩 공정중에 혼합 사용함으로써, 소입경 고무질 중합체가 갖는 외관품질의 우수성과 중입경 고무질 중합체가 갖는 물성 발란스를 동시에 갖고, 중량 평균 분자량이 각각 다른 2 종의 SAN 수지를 혼합하여 사용하여 적절한 물성 발란스를 가지며 이러한 상기 g-ABS 수지 및 SAN 수지에 에틸렌비스스테아로아마이드를 적정수준의 함량으로 첨가하여 사용함으로써 표면광택, 내충격성 및 유동성이 동시에 개선된 열가소성 수지 조성물을 제공하는 효과를 갖는다.According to the present invention, g-ABS resin is separately prepared by emulsion graft polymerization of two rubber polymers having different rubber particle sizes, and these are mixed and used in the compounding process, thereby improving the appearance quality of the small particle rubber polymer. Two kinds of SAN resins having the physical balance of the medium-sized rubbery polymer at the same time and having different weight average molecular weights are mixed to have proper physical balance and to titrate ethylenebisstearoamide to the g-ABS resin and the SAN resin. The addition and use of a level content has the effect of providing a thermoplastic resin composition with improved surface gloss, impact resistance and fluidity at the same time.

본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (2)

(A) (a1) 평균 입자 크기가 0.05∼0.20 ㎛인 소입경 고무질 중합체를 사용하여 유화 그라프트 중합법으로 제조된 제1 g-ABS 수지 및 (a2) 평균 입자 크기가 0.25∼0.40 ㎛인 중입경 고무질 중합체를 사용하여 유화 그라프트 중합법으로 제조된 제2 g-ABS 수지가 20 : 80 에서 80 : 20 중량%의 비율로 구성된 g-ABS 수지 15∼40 중량부;(A) (a 1 ) First g-ABS resin prepared by emulsion graft polymerization using a small particle rubbery polymer having an average particle size of 0.05 to 0.20 μm and (a 2 ) An average particle size of 0.25 to 0.40 μm 15 to 40 parts by weight of a second g-ABS resin prepared by an emulsion graft polymerization method using a phosphorus medium particle rubber polymer at a ratio of 20:80 to 80: 20% by weight; (B) (b1) 아크릴로니트릴 함량이 20∼35%이고 중량 평균 분자량이 110,000∼140,000인 제1 SAN 수지 10∼70 중량부 및 (b2) 아크릴로니트릴 함량이 20∼35%이고 중량 평균 분자량이 80,000∼100,000인 제2 SAN 수지 90∼30 중량부로 구성된 SAN 수지 60∼85 중량부; 및(B) (b 1) is 20-35% acrylonitrile content with an acrylic and a weight average molecular weight of 110000-140000 of claim 1 SAN resin and 10 to 70 parts by weight of (b 2) a content of 20-35% by weight of acrylonitrile and 60 to 85 parts by weight of a SAN resin composed of 90 to 30 parts by weight of a second SAN resin having an average molecular weight of 80,000 to 100,000; And (C) 구성성분 (A) 및 (B)의 전체 100 중량부에 대해서 에틸렌비스스테아로아마이드 1∼7 중량부;(C) 1 to 7 parts by weight of ethylenebisstearoamide relative to 100 parts by weight of the total of the components (A) and (B); 로 이루어지는 것을 특징으로 하는 표면광택, 내충격성 및 유동성이 우수한 열가소성 수지 조성물.Thermoplastic resin composition excellent in surface gloss, impact resistance and fluidity, characterized in that consisting of. 제1항에 있어서, 상기 제1 g-ABS 수지(a1)의 평균 입자 크기가 0.08∼0.18㎛이고, 상기 제2 g-ABS 수지(a2)의 평균 입자 크기가 0.28∼0.38 ㎛인 것을 특징으로 하는 열가소성 수지 조성물.According to claim 1, wherein the average particle size of the first g-ABS resin (a 1 ) is 0.08 ~ 0.18 ㎛, the average particle size of the second g-ABS resin (a 2 ) is 0.28 ~ 0.38 ㎛ The thermoplastic resin composition characterized by the above-mentioned.
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