KR20210107990A - Method for producing a thermoplastic resin composition excellent in impact resistance and gloss - Google Patents

Method for producing a thermoplastic resin composition excellent in impact resistance and gloss Download PDF

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KR20210107990A
KR20210107990A KR1020200022612A KR20200022612A KR20210107990A KR 20210107990 A KR20210107990 A KR 20210107990A KR 1020200022612 A KR1020200022612 A KR 1020200022612A KR 20200022612 A KR20200022612 A KR 20200022612A KR 20210107990 A KR20210107990 A KR 20210107990A
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butadiene
thermoplastic resin
resin composition
weight
synthetic rubber
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KR1020200022612A
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Korean (ko)
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김충만
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김충만
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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C08L9/04—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C08L9/08—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/10—Latex

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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

A purpose of the present invention is to prepare a large particle diameter synthetic rubber latex with an average particle diameter of 04 ㎛ or more with excellent morphology and excellent polymerization stability and then prepare a thermoplastic resin composition with excellent impact resistance and gloss therefrom. In preparing the thermoplastic resin composition by mixing a graft polymer and a SAN resin, a graft polymer is prepared by emulsion graft polymerization of 40-55 parts by weight of a monomer mixture of one or two or more of aromatic vinyl-based monomers and unsaturated nitrile-based monomers in 40-60 parts by weight of a mixed latex, obtained by mixing 20-40 wt% of (A) a butadiene-based synthetic rubber latex with an average rubber particle diameter of 040 μm or more, prepared by using a polymer colloidal protective agent; and 60-80 wt% of (B) a butadiene-based synthetic rubber latex having an average particle diameter of 028-032 ㎛.

Description

내충격성 및 광택성이 우수한 열가소성 수지 조성물의 제조방법{Method for producing a thermoplastic resin composition excellent in impact resistance and gloss}Method for producing a thermoplastic resin composition excellent in impact resistance and gloss

본 발명은 열가소성 수지 조성물에 관한 것이다. 보다 구체적으로, 본 발명은 메틸메타아크릴레이트-아크릴로니트릴-부타디엔-스티렌 수지(이하, 투명 ABS 수지)에, 아세토글리세릴계 지방산과 미네랄 오일을 혼합함으로써 투명 ABS 수지의 투명성과 내충격성을 유지하면서 사출작업특성과 외관특성이 향상되어 작업안정성이 우수한 열가소성 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition. More specifically, the present invention is a methyl methacrylate-acrylonitrile-butadiene-styrene resin (hereinafter, transparent ABS resin), by mixing acetoglyceryl-based fatty acid and mineral oil while maintaining the transparency and impact resistance of the transparent ABS resin The present invention relates to a thermoplastic resin composition having improved injection operation characteristics and appearance characteristics and excellent operation stability.

ABS 수지는 스티렌의 가공성, 아크릴로니트릴의 강성 및 내약품성, 부타디엔의 내충격성 등 물성강도와 미려한 외관특성으로 인하여 자동차, 전기전자, 사무기기, 가전제품, 완구류 등 다양한 용도에 널리 사용되는 장점이 있으나 불투명한 이유ABS resin has the advantage of being widely used in various applications such as automobiles, electrical and electronic equipment, office equipment, home appliances, toys, etc. due to its physical strength and beautiful appearance characteristics such as the processability of styrene, the rigidity and chemical resistance of acrylonitrile, and the impact resistance of butadiene. but it is unclear why

로 용도에 제한을 받고 있는 단점이 있다.It has the disadvantage of being limited in its use.

ABS 수지가 불투명한 이유는 연속상인 매트릭스 수지와 분산상인 고무와의 굴절율 차이로 인하여 그 계면에서 빛이 굴절 및 산란하고 고무입자 크기에 따라 가시광선의 파장이 산란하기 때문이다. 따라서 ABS 수지에 투명성을 부여하기 위해서The reason why the ABS resin is opaque is that light is refracted and scattered at the interface due to the difference in refractive index between the matrix resin, which is a continuous phase, and the rubber, which is a disperse phase, and the wavelength of visible light is scattered according to the size of rubber particles. Therefore, in order to impart transparency to the ABS resin,

는 고무상의 굴절율과 연속상인 매트릭스 수지와의 굴절율을 일치시키고, 사용된 고무입자의 크기를 적절하게 조절하여 가시광선의 영역에서 빛의 산란을 최소화하여야 한다.should match the refractive index of the rubber phase with that of the continuous phase matrix resin, and appropriately adjust the size of the rubber particles used to minimize light scattering in the visible region.

이와 같은 투명 ABS는 주로 가전제품의 부품 등으로 사용되었으나 최근에는 그 용도가 기능성 소재로 확장되고 있다. 투명 ABS의 용도가 확장됨에 따라 세탁기 투명창 등 그 성형품의 크기가 커지고 있으며, 투명하다는 특성으로 인하여 사출Such transparent ABS was mainly used as parts of home appliances, but recently its use has been expanded to functional materials. As the use of transparent ABS expands, the size of the molded product such as the transparent window of a washing machine is increasing, and due to its transparency, injection

작업시 미세한 외관의 품질 저하에 대해서도 투명도 저하의 문제점이 발생하고 있다. 이러한 문제점을 개선하기 위하여,투명 ABS 수지의 투명성과 내충격성을 유지하면서도 작업안정성이 우수한 수지에 대한 요구가 증가하고 있다.There is also a problem of transparency deterioration even when the quality of the fine appearance is deteriorated during work. In order to improve this problem, the demand for a resin excellent in work stability while maintaining the transparency and impact resistance of the transparent ABS resin is increasing.

일반적으로 스티렌-아크릴로니트릴(이하, AS 수지)은 내화학성과 성형성이 우수한 반면 충격강도가 낮아 그 용도의 제한이 있고, 이러한 단점을 보완하기 위하여 충격보강제인 부타디엔 고무를 첨가하여 사용한다. 이러한 부타디엔 충격보강제In general, styrene-acrylonitrile (hereinafter, AS resin) has excellent chemical resistance and moldability, but has low impact strength, which limits its use. These butadiene impact modifiers

가 사용되면서 고온, 고속 사출시 고무와 금형간의 마찰에 의한 외관의 흐름자국이 발생하여 육안의 투명도를 저하시키는단점이 있다. 또한 고온·고속 사출시 첨가된 고무의 몰림현상으로 인하여, 외관의 핀홀(pinhole) 현상이 발생되기도 한다.During high-temperature and high-speed injection, there is a disadvantage of lowering the transparency of the naked eye due to the appearance of flow marks due to friction between the rubber and the mold. In addition, due to the rolling phenomenon of the added rubber during high-temperature and high-speed injection, an external pinhole phenomenon may occur.

이러한 작업특성을 향상시키기 위하여 금형의 구조변경 등 작업성을 향상시키기 위한 방법이 연구중이며, 일부는 상업화되고 있다.In order to improve these work characteristics, methods for improving workability such as structural change of molds are being studied, and some are being commercialized.

그러나 투명 ABS는 불투명한 일반 ABS와는 달리 외관에 문제가 있을 경우 육안으로 구분이 가능하며, 그 특성상 외장재로 많이 사용되므로 금형 수정 방법만으로는 그 한계가 있다.However, unlike general ABS that is opaque, transparent ABS can be identified with the naked eye if there is a problem with the appearance, and because of its nature, it is often used as an exterior material, so there is a limit to the mold modification method alone.

이에 본 발명자들은 상기 문제점을 근본적으로 해결하기 위하여, 투명 ABS 수지에 아세토글리세릴계 지방산과 미네랄 오일을 첨가하여 투명성을 향상시키고 작업시 발생하는 흐름자국 및 외관품질을 개선하여 작업안정성이 우수한 열가소성 수지를 개발하기에 이른 것이다.Therefore, in order to fundamentally solve the above problems, the present inventors added acetoglyceryl fatty acid and mineral oil to the transparent ABS resin to improve the transparency and improve the flow marks and appearance quality generated during operation to produce a thermoplastic resin with excellent work stability. is too early to develop.

본 발명의 목적은 투명성이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a thermoplastic resin composition having excellent transparency.

본 발명의 다른 목적은 투명성과 내충격성을 유지하면서도 사출작업특성과 외관특성이 향상되어 작업안정성이 우수한 열가소성 수지 조성물을 제공하는 것이다.Another object of the present invention is to provide a thermoplastic resin composition excellent in operation stability by improving injection operation characteristics and appearance characteristics while maintaining transparency and impact resistance.

본 발명의 상기 및 기타 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.All of the above and other objects of the present invention can be achieved by the present invention described below.

본 발명은 투명성과 내충격성을 유지하면서도 사출작업특성과 외관특성이 향상되어 작업안정성이 우수한 열가소성 수지조성물을 제공하는 발명의 효과를 갖는다.The present invention has the effect of providing a thermoplastic resin composition excellent in operation stability by improving injection operation characteristics and appearance characteristics while maintaining transparency and impact resistance.

본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진Simple modifications or changes of the present invention can be made by those skilled in the art.

청구함 참조see billed

Claims (7)

그라프트 중합체와 SAN 수지를 혼합하여 열가소성 수지 조성물을 제조함에 있어서, 그라프트 중합체는 고분자 콜로이드 보호제를 사용하여 제조한 평균 고무입자경이 040㎛ 이상인 부타디엔계 합성고무라텍스(A) 20-40중량%와 평균입자직경이 028-032㎛인 부타디엔계 합성고무라텍스 (B) 60-80중량%를 혼합한 혼합라텍스 45-60중량부에 방향족 비닐계 단량체, 불포화 니트릴계 단량체 중의 1종 또는 2종 이상인 단
량체 혼합물 40-55중량부를 유화 그라프트 중합시킴으로써 제조함을 특징으로 열가소성 수지 조성물의 제조방법.
In preparing the thermoplastic resin composition by mixing the graft polymer and the SAN resin, the graft polymer contains 20-40 wt% of a butadiene-based synthetic rubber latex (A) having an average rubber particle diameter of 040 μm or more, prepared using a polymer colloidal protective agent, and Butadiene-based synthetic rubber latex (B) having an average particle diameter of 028-032㎛ 45-60 parts by weight of mixed latex mixed with 60-80% by weight, provided that one or two or more types of aromatic vinyl monomers and unsaturated nitrile monomers
A method for producing a thermoplastic resin composition, characterized in that it is prepared by emulsion graft polymerization of 40-55 parts by weight of the mer mixture.
 제1항에 있어서, 부타디엔계 합성고무라텍스(A) 제조시 사용되는 고분자 콜로이드 보호제의 함유량은 부타디엔계 고무 100중량부에 대하여 001-015중량부인 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.The method according to claim 1, wherein the content of the colloidal polymer protective agent used in manufacturing the butadiene-based synthetic rubber latex (A) is 001-015 parts by weight based on 100 parts by weight of the butadiene-based rubber. 제2항에 있어서, 고분자 콜로이드 보호제로는 카르복실메틸세룰로오스, 카르복실에틸셀룰로오스, 폴리비닐알콜, 폴리아마이드, 소디움알지네이트, 폴리비닐메틸에테르 중에서 선택된 1종 이상을 사용함을 특징으로 하는 열가소성 수지 조성물의 제조방법.The thermoplastic resin according to claim 2, wherein the polymer colloidal protective agent is at least one selected from carboxymethyl cellulose, carboxyethyl cellulose, polyvinyl alcohol, polyamide, sodium alginate, and polyvinyl methyl ether. A method for preparing the composition. 제1항에 있어서, 단량체 혼합물 중의 방향족 비닐계 단량체의 함량은 68-73중량% 불포화 니트릴계 단량체의 함량은 27-32중량%인 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.The method according to claim 1, wherein the content of the aromatic vinyl-based monomer in the monomer mixture is 68-73 wt% and the content of the unsaturated nitrile-based monomer is 27-32 wt%. 제1항에 있어서, 합성고무라텍스의 성분인 부타디엔계 고무로는 부타디엔 단일 중합체 또는 부타디엔-스티렌 공중합체, 부타디엔-아크릴로니트릴 공중합체 등의 부타디엔 공중합체를 사용함을 특징으로 하는열가소성 수지 조성물의 제조방법.The method of claim 1, wherein the butadiene-based rubber, which is a component of the synthetic rubber latex, is a butadiene homopolymer, a butadiene-styrene copolymer, or a butadiene copolymer such as a butadiene-acrylonitrile copolymer. Preparation of a thermoplastic resin composition Way. 제1항에 있어서, 방향족 비닐계 단량체로는 스티렌, α-메틸스티렌, 비닐톨루엔, 할로겐화스티렌 중에서 선택된 1종 이상을 사용함을 특징으로 하는 열가소성 수지 조성물의 제조방법.The method according to claim 1, wherein at least one selected from among styrene, α-methylstyrene, vinyltoluene, and halogenated styrene is used as the aromatic vinyl-based monomer. 제1항에 있어서, 불포화 니트릴계 단량체로는 아크릴로니트릴, 메타크릴로니트릴 중에서 선택된 1종 이상을 사용함을 특징으로 하는 열가소성 수지 조성물의 제조방법.
The method according to claim 1, wherein at least one selected from acrylonitrile and methacrylonitrile is used as the unsaturated nitrile-based monomer.
KR1020200022612A 2020-02-25 2020-02-25 Method for producing a thermoplastic resin composition excellent in impact resistance and gloss KR20210107990A (en)

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