KR19980051328A - Thermoplastic resin composition having flame resistance excellent in impact resistance - Google Patents

Thermoplastic resin composition having flame resistance excellent in impact resistance Download PDF

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KR19980051328A
KR19980051328A KR1019960070220A KR19960070220A KR19980051328A KR 19980051328 A KR19980051328 A KR 19980051328A KR 1019960070220 A KR1019960070220 A KR 1019960070220A KR 19960070220 A KR19960070220 A KR 19960070220A KR 19980051328 A KR19980051328 A KR 19980051328A
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weight
rubber
resin composition
monomer
thermoplastic resin
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KR100241115B1 (en
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장복남
이규철
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유현식
제일모직 주식회사
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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

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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

본 발명의 열가소성 수지 조성물은 (A)(a1) 고무상 중합체 35 내지 65중량%에 방향족비닐계 단량체 30 내지 50중량%, 상기 방향족비닐계 단량체와 공중합 가능한 단량체 5 내지 20중량%, 및 가공성 및 내열성을 부가하는 단량체 0 내지 15중량%를 첨가하여 그라프트 중합시킨 공중합체 수지 20 내지 50중량%, 및 (a2) 방향족비닐계 단량체 60 내지 80 중량%에 상기 방향족 비닐계 단량체와 공중합 할 수 있는 단량체 40 내지 20 중량% 및 가공성 및 내열성을 부가하는 단량체 0 내지 30 중량%를 첨가하여 공중합 시킨 공중합체 수지 80 내지 50 중량% 로 이루어진 고무변성 스티렌계 수지 100중량부에 대하여 (B) 비스(2,3-디브로모에틸에테르)테트라브로모비스페놀 A 3 내지 15 중량부, (C) 안티몬계 화합물 0.5 내지 5 중량부, 및 (D) 실록산계 화합물 0.001 내지 0.2 중량부를 혼합시킨 내충격성이 우수한 난연성 수지 조성물이다. 본 발명의 수지 조성물은 각각의 용도에 따라 무기물 첨가제, 열안정제, 산화방지제, 광안정제, 안료 및/또는염료가 부가될 수 있다.The thermoplastic resin composition of the present invention (A) (a 1 ) 35 to 65% by weight of the rubbery polymer 30 to 50% by weight of the aromatic vinyl monomer, 5 to 20% by weight of the copolymerizable monomer with the aromatic vinyl monomer, and processability And 20 to 50% by weight of the copolymer resin graft-polymerized by adding 0 to 15% by weight of the monomer which adds heat resistance, and (a 2 ) 60 to 80% by weight of the aromatic vinyl monomer to be copolymerized with the aromatic vinyl monomer. (B) Bis to 100 parts by weight of a rubber-modified styrene resin composed of 40 to 20% by weight of a monomer and 80 to 50% by weight of a copolymer resin copolymerized by adding 0 to 30% by weight of a monomer which adds processability and heat resistance 3 to 15 parts by weight of (2,3-dibromoethyl ether) tetrabromobisphenol A, (C) 0.5 to 5 parts by weight of the antimony compound, and (D) 0.001 to 0.2 parts by weight of the siloxane compound The impact resistance is excellent flame retardant resin composition. In the resin composition of the present invention, an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye may be added according to each use.

mj/50-27mj / 50-27

Description

내충격성이 우수한 난연성을 갖는 열가소성 수지 조성물Thermoplastic resin composition having flame resistance excellent in impact resistance

발명의 분야Field of invention

본 발명은 내충격성이 우수한 난연성을 갖는 열가소성 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition having flame retardancy excellent in impact resistance.

보다 구체적으로 본 발명은 그라프트 공중합체 수지 및 공중합체 수지로 이루어진 고무변성 스티렌계 수지, 난연제로서 비스(2,3-디브로모에틸에테르)테트라브로모비스페s놀 A, 안티몬계 화합물, 및 실록산계 화합물로 이루어진 충격강도 및 가공성이 양호한 난연성 열가소성 수지 조성물에 관한 것이다.More specifically, the present invention relates to a rubber-modified styrene resin composed of a graft copolymer resin and a copolymer resin, bis (2,3-dibromoethyl ether) tetrabromobisfesnol A, an antimony compound, and a flame retardant. It relates to a flame retardant thermoplastic resin composition having a good impact strength and workability made of a siloxane compound.

본 발명에 의한 열가소성 수지 조성물은 그 수지 조성물의 각각의 용도에 따라 무기물 첨가제, 열안정제, 산화방지제, 염료 또는 안료가 필요한 양으로 부가될 수 있다.The thermoplastic resin composition according to the present invention may be added in the required amount of an inorganic additive, a heat stabilizer, an antioxidant, a dye or a pigment according to each use of the resin composition.

발명의 배경Background of the Invention

일반적으로 고무변성 스티렌계 수지는 가공성이 양호하고 충격강도와 같은기계적 물성이 매우 우수하며 외관이 양호하여 전기제품, 사무기기 등의 여러가지 용도로 흔히 사용되어 왔다. 그러나 개인용 컴퓨터, 팩스 등과 같이 열을 많이 발산하는 제품에 사용될 경우는 연소성이 있다는 단점이 있다.In general, rubber-modified styrene resins have been widely used in various applications such as electrical appliances and office equipment because of their good processability, excellent mechanical properties such as impact strength, and good appearance. However, when used in a product that emits a lot of heat, such as personal computers, faxes, there is a disadvantage that there is a combustibility.

따라서 이 연소성을 방지하고자 고무변성 스티렌계 수지 조성물에 할로겐계 화합물을 난연제로 첨가하여 난연성 고무변성 스티렌계 수지 조성물로 사용되어왔다. 통상적으로 이 할로겐계 화합물은 안티몬계 화합물과 함께 사용되어 UL94 V-0 난연물성을 수지 조성물에 부여하는 것이 당해 기술에서는 잘 알려져있다.Therefore, in order to prevent this combustibility, a halogen-based compound has been added to the rubber-modified styrene resin composition as a flame retardant, and has been used as a flame-retardant rubber-modified styrene resin composition. Usually, it is well known in the art that this halogen compound is used together with an antimony compound to impart UL94 V-0 flame retardant properties to the resin composition.

그러나 고무변성 스티렌계 수지 조성물에 V-2 난연물성을 부여하는 상업화된 난연제는 드물다. 이 난연제로는 헥사브로모사이크로도데칸이 알려져 있으나, 이 화합물은 일반적인 가공온도에서 열안정성이 저하되어 열변색을 일으키기 때문에 유채색제품에 사용하기에는 적절하지 못하고 무채색 수지 제품에만 한정적으로 사용되고 있다.However, commercially available flame retardants which impart V-2 flame retardant properties to rubber modified styrene resin compositions are rare. Hexabromocyclododecane is known as a flame retardant, but this compound is not suitable for use in achromatic products because it is deteriorated due to thermal stability at a general processing temperature and is used only in achromatic resin products.

따라서 본 발명자들은 상기와 같은 문제점을 해결하고자 헥사브로모사이크로도데칸 보다 열안정성이 양호한 비스(2,3-디브로모에틸에테르)테트라브로모비스페놀 A를 안티몬계 화합물과 고무변성 스티렌 수지의 난연제로 사용하고 충격강도의 손실을 최소화하는 실록산계 화합물을 첨가하여, 기계적 물성의 저하를 방지하고 우수한 난연성을 갖는 고무면성 스티렌계 수지 조성물을 개발하기에 이르렀다.Therefore, the inventors of the present invention have solved the above problems with bis (2,3-dibromoethyl ether) tetrabromobisphenol A having better thermal stability than hexabromocyclododecane as a flame retardant of an antimony compound and a rubber-modified styrene resin. By adding a siloxane-based compound which is used as a and minimizes the loss of impact strength, it has led to the development of a rubber-cotton styrene resin composition which prevents the deterioration of mechanical properties and has excellent flame retardancy.

Claims (9)

고무상 중합체 35 내지 65중량%에 방향족비닐계 단량체 30 내지 50 중량%, 상기 방향즉비닐계와 공중합 가능한 단량체 5 내지 20 중량%, 및 가공성 및 내열성을 부가하는 단량체 0 내지 15 중량%를 첨가하야 그라프트 중합시킨 그라프트 공중합체 수지 20 내지 50 중량%, 및30 to 50% by weight of the aromatic vinyl monomer, 5 to 20% by weight of the monomer copolymerizable with vinyl, and 0 to 15% by weight of the monomer adding processability and heat resistance should be added to 35 to 65% by weight of the rubbery polymer. 20 to 50% by weight of graft copolymerized resin, and (a2) 방향족비닐계 단량체 60 내지 80 중량%에 상기 방향족비닐계 단량체와 공중합 할 수 있는 단량체 40 내지 20 중량%, 및 가공성 및 내열성을 부가하는 단량체 0 내지 30 중량%를 첨가하여 공중합시킨 공중합체 수지 80 내지50 중량%로 이루어진 고무변성 스티렌계 수지 100 중량부;(a 2 ) air copolymerized by adding 60 to 80% by weight of an aromatic vinyl monomer to 40 to 20% by weight of a monomer copolymerizable with the aromatic vinyl monomer and 0 to 30% by weight of a monomer which adds processability and heat resistance. 100 parts by weight of a rubber-modified styrene resin made of 80 to 50% by weight of a copolymer resin; (B) 상기 고무변성 스티렌계 수지 100 중량부에 대하여 하기 일반식(I)으로 표시되는 비스(2,3-디브르도에릴에테르)테트라브르므비스페놀 A 3 내지 15 중량부;(B) 3 to 15 parts by weight of bis (2,3-dibrodoeryl ether) tetrabrombisphenol A represented by the following general formula (I) with respect to 100 parts by weight of the rubber-modified styrene resin; (C) 상기 고무변성 스티렌계 수지 100 중량부에 대하여 안티몬계 화합물 0.5내지 5 중량부; 및(C) 0.5 to 5 parts by weight of the antimony compound based on 100 parts by weight of the rubber-modified styrene resin; And (D) 상기 고무변성 스티렌계 수지 100 중량부에 대하여 실록산계 화합물 0.001 내지 0.2 중량부; 로 구성되는 것을 특징으로 하는 내충격성이 우수한 난연성을 갖는 열가소성 수지 조성물.(D) 0.001 to 0.2 parts by weight of siloxane compound based on 100 parts by weight of the rubber-modified styrene resin; A thermoplastic resin composition having flame retardancy excellent in impact resistance, characterized by comprising. 제 1 항에 있어서, 상기 고무상 중합체(a1)가 디엔계 고무, 디엔계 고무에 수소를 첨가한 포화고무, 이소플렌 고무, 클로로프렌 고무, 아크릴계 고무 및 에틸렌/프로필렌/디엔단량체 삼원공중합체(EPDM)로 이루어지는 군으로부터 선택되는 것을 특징으로 하는 내충격성이 우수한 난연성을 갖는 열가소성 수지 조성물.According to claim 1, wherein the rubber polymer (a 1 ) is a diene rubber, a saturated rubber added hydrogen to the diene rubber, isoprene rubber, chloroprene rubber, acrylic rubber and ethylene / propylene / diene monomer terpolymer ( EPDM) is selected from the group consisting of a thermoplastic resin composition having a flame resistance excellent in impact resistance. 제 1 항에 있어서, 상기 방향족비닐계 단량체(a1, a2)가 스티렌, α-메틸스티렌, p-메틸스티렌, p-염화스티렌, p-브롬화스티렌, 및 2,4,5-트리브롬화스티렌으로 이루어진 군으로부터 선택되는 것을 특징으로 하는 내충격성이 우수한 난연성을 갖는 열가소성 수지 조성물.The method of claim 1, wherein the aromatic vinyl monomers (a 1 , a 2 ) are styrene, α-methylstyrene, p-methylstyrene, p-styrene chloride, p-bromide, and 2,4,5-tribrominated A thermoplastic resin composition having flame retardancy excellent in impact resistance, which is selected from the group consisting of styrene. 제 1 항에 있어서, 상기 방향족비닐계 단량체와 공중합 할 수 있는 단량체는시안화비닐계 및 불포화니트릴계 화합물 중에서 선택되는 것을 특징으로 하는 내충격성이 우수한 난연성을 갖는 열가소성 수지 조성물.The thermoplastic resin composition of claim 1, wherein the monomer copolymerizable with the aromatic vinyl monomer is selected from vinyl cyanide and unsaturated nitrile compounds. 제 1 항에 있어서, 상기 가공성 및 내열성을 부가하는 단량체(a1, a2)는 아크릴산, 메타크릴산, 무수말레인산, 및 N-치환말레이드로 이루어진 군으로부터 선택되는 것을 특징으로 하는 내충격성이 우수한 난연성을 갖는 열가소성 수지 조성물.The impact resistance of claim 1, wherein the monomers (a 1 , a 2 ) adding processability and heat resistance are selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleade. Thermoplastic resin composition having excellent flame retardancy. 제 1 항에 있어서, 상기 고무변성 스티렌계 수지(A)가 아크릴로니트릴/부타디 엔/스티렌 공중합체 수지(ABS), 아크릴로니트릴/아크릴 고무/스티렌 공중합체수지(AAS), 아크릴로니트릴,/에틸렌프로필렌 고무/스티렌 공중합체 수지(AES),및 고충격 폴리스티렌 수지(HIPS)로 이루어지는 군으로부터 선택되는 것을 특징으로 하는 내충격성이 우수한 난연성을 갖는 열가소성 수지 조성물.The method of claim 1, wherein the rubber modified styrene resin (A) is acrylonitrile / butadiene / styrene copolymer resin (ABS), acrylonitrile / acrylic rubber / styrene copolymer resin (AAS), acrylonitrile , / Ethylene propylene rubber / styrene copolymer resin (AES), and a high impact polystyrene resin (HIPS) selected from the group consisting of thermoplastic resin composition having excellent flame resistance excellent flame resistance. 제 1 항에 있어서, 상기 안티몬계 화합물이 삼산화안티몬 또는 오산화안티몬인 것을 특징으로 하는 내충격성이 우수한 난연성을 갖는 열가소성 수지 조성물.The thermoplastic resin composition of claim 1, wherein the antimony compound is antimony trioxide or antimony pentoxide. 제 1 항에 있어서, 상기 실록산계 화합물(D)이 하기 구조식의 폴리디메틸 실록산인 것을 특징으로 하는 내충격성이 우수한 난연성을 갖는 열가소성 수지 조성물:The thermoplastic resin composition of claim 1, wherein the siloxane compound (D) is polydimethyl siloxane of the following structural formula: (상기 식에서 n은 20 내지 1000 임)Wherein n is from 20 to 1000 제 1 항에 있어서, 상기 수지 조성물이 무기물 첨가제, 열안정제, 산화방지제, 광안정제, 안료 및/또는 염료를 더 포함하는 것을 특징으로 하는 난연성을 갖는 열가소성 수지 조성물.The thermoplastic resin composition of claim 1, wherein the resin composition further comprises an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye.
KR1019960070220A 1996-12-23 1996-12-23 A retard resin composition with excellant compactability KR100241115B1 (en)

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KR100463171B1 (en) * 2002-08-13 2004-12-23 주식회사 엘지화학 Rubber-modified styrene resin composition
KR100654534B1 (en) * 2005-12-30 2006-12-05 제일모직주식회사 Flame retardant thermoplastic resin composition
KR100715745B1 (en) * 2000-04-21 2007-05-08 테크노 폴리머 가부시키가이샤 Transparent Butadiene-Based Rubber-Reinforced Resin and Composition Containing the Same

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KR100346608B1 (en) * 1994-12-29 2002-11-23 주식회사 엘지화학 Styrene-based fire retardant resin composition

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KR100715745B1 (en) * 2000-04-21 2007-05-08 테크노 폴리머 가부시키가이샤 Transparent Butadiene-Based Rubber-Reinforced Resin and Composition Containing the Same
KR100463171B1 (en) * 2002-08-13 2004-12-23 주식회사 엘지화학 Rubber-modified styrene resin composition
KR100654534B1 (en) * 2005-12-30 2006-12-05 제일모직주식회사 Flame retardant thermoplastic resin composition

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