KR940006472B1 - Anti-flammable resin composition - Google Patents

Anti-flammable resin composition Download PDF

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KR940006472B1
KR940006472B1 KR1019910001778A KR910001778A KR940006472B1 KR 940006472 B1 KR940006472 B1 KR 940006472B1 KR 1019910001778 A KR1019910001778 A KR 1019910001778A KR 910001778 A KR910001778 A KR 910001778A KR 940006472 B1 KR940006472 B1 KR 940006472B1
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weight
parts
flame retardant
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styrene
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KR920016548A (en
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이언석
민경집
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주식회사 럭키
최근선
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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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • 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

Abstract

(A) 10-90 wt.pts. aromatic polycarbonate resin; (B) below 60 wt.pts. ABS resin comprising 5-60 wt.pts. butadiene rubber matrix, 20-80 wt.pts. styrene and 5-40 wt.pts. acrylonitrile; (C) 10-90 wt.pts. styrene based anti-flame copolymer contg. 5-50 wt.pts. bromostyrene cpd.; (D) 0.01-5 wt.pts. metal salts using as flame retardant for aromatic polycarbonate w.r.t. 100 wt.pts. of (A)+(B)+(C); (E) below 10 wt.pts. antimonium trioxide w.r.t. 100 wt.pts. of (A)+(B)+(C); (F) below 1 wt.pt. tetrafluoroethylene based polymer w.r.t. 100 wt.pts. of (A)+(B)+(C). The styrene based anti-flame copolymer comprises 5-50 wt.pts. bromostyrene cpd., 10-60 wt.pts. aromatic vinyl hydrocarbon and 10-60 unsatd. nitrile, and is prepd. by three steps of polymerization.

Description

난연 수지 조성물Flame Retardant Resin Composition

본 발명은 내열성 및 내충격성이 우수하고 내후성이 향상된 난연 수지 조성물에 관한 것으로 방향족 폴리카보네이트 수지, ABS 수지, 스티렌계 난연 공중합체 및 난연 첨가제로 구성된 조성물에 관한 것이다.The present invention relates to a flame retardant resin composition having excellent heat resistance and impact resistance and improved weather resistance, and relates to a composition composed of an aromatic polycarbonate resin, an ABS resin, a styrene flame retardant copolymer, and a flame retardant additive.

따라서, 본 발명에 의해 얻게 되는 성형품은 가전제품, 전지건자 제품 및 자동차 부품 등에 사용할 수 있다.Therefore, the molded article obtained by the present invention can be used for home appliances, battery maker products and automobile parts.

엔지니어링 분양에서 사용하기 위한 수지 조성물은 내열성이 우수한 기계적 물성을 갖추여야 하며, 가공 및 성형을 용이하게 할 수 있도록 우수한 유동특성을 가져야 한다. 특히, 화재의 위험이 있거나 열이 많이 발생하는 전기, 전자 부품으로 사용하기 위해서는 난연성을 갖추어야 하는데, 폴리카보네이트 수지와 ABS수지만의 합금 그 자체로는 쉽게 연소하는 성질이 있기 때문에 적용에 제약을 받게 된다. 일반적으로는 할로겐화물이 함유된 화합물이나 삼산화안티몬과 같은 무기산화물 계통의 금속화합물에서 선택되는 1종 이상의 성분을 첨가시켜서 난연성을 얻는 방법이 더 알려져 있다. 그러나, 이들 첨가제는 폴리카보네이트와 ABS 수지의 조성에 따라 5∼30중량부를 사용하여야만 효과가 있으나, 이로 인해 충격강도와 같은 기계적물성을 상당히 감소시키는 단점이 있고, 난연제의 종류에 따라 내후성, 내충격성, 내열성 및 가공성의 일부만을 만족시키거나, 사출물의 색상이 어두울 경우, 첨가된 난연제의 성분이 표출되어 부루밍(blooming) 현상이 발생하는 문제점 등을 지니고 있다.The resin composition for use in engineering sales should have excellent mechanical properties and excellent flow properties to facilitate processing and molding. In particular, in order to be used for electric or electronic parts that have a high risk of fire or heat, flame retardancy must be provided. However, since the alloy of polycarbonate resin and ABS resin itself burns easily, it is restricted from application. do. In general, a method of obtaining flame retardancy by adding at least one component selected from a compound containing a halide or an inorganic oxide-based metal compound such as antimony trioxide is known. However, these additives are effective only when the use of 5 to 30 parts by weight depending on the composition of the polycarbonate and ABS resin, which has the disadvantage of significantly reducing the mechanical properties such as impact strength, weather resistance, impact resistance depending on the type of flame retardant When only a part of heat resistance and processability are satisfied, or the color of the injection molding is dark, the components of the added flame retardant are exposed to have a problem of blooming.

이와 같은 문제점들을 해결하기 위하여 연구한 결과, 컴파운딩(compounding) 공정에서 다량의 난연제를 첨가하지 않고, 브로모스티렌을 함유하는 스티렌계 난연 공중합체와 방향족 폴리카보네이트 수지의 난연제로 사용되는 금속염을 소량 첨가함으로써 원하는 특성을 갖는 난연 폴리카보네이트 수지 조성물을 얻을 수있음을 발견하고, 본 발명을 완성하게 되었다.In order to solve these problems, a small amount of metal salts are used as flame retardants of styrene flame retardant copolymers containing bromostyrene and aromatic polycarbonate resins without adding a large amount of flame retardants in the compounding process. It was discovered that the flame retardant polycarbonate resin composition having the desired properties could be obtained by the addition, thereby completing the present invention.

본 발명은 내열성, 내후성 그리고 기계적 물성이 우수한 난연수지 조성물 제조에 그 목적이 있다.An object of the present invention is to prepare a flame retardant resin composition excellent in heat resistance, weather resistance and mechanical properties.

즉, 본 발명은 (A) 방향족 폴리카보네이트 수지 10∼90중량부,(B) 부타디엔 고무기질 5∼60중량부, 스티렌 20∼80중량부, 그리고 아크릴로니트릴 5∼40중량부로 구성된 ABS 수지 60중량부 이하,(C) 브로모스티렌 화합물 5∼50중량부를 함유하는 스티렌계 난연 공중합체 10∼90중량부,(D) 상기(A)+(B)+(C) 전조성물 100중량부에 대하여 방향족 폴리카보네이트 수지의 난연제로 사용되는 금속염 0.01∼5중량부,(E)(A)+(B)+(C) 전 조성물 100중량부에 대하여 삼산화안티몬 10중량부 이하, (F) (A)+(B)+(C) 전 조성물 100중량부에 대하여 테트라플루오로 에틸렌계 중합체 1중량부 이하로 구성된 난연 수지 조성물에 관한것이다.That is, the present invention is an ABS resin 60 composed of (A) 10 to 90 parts by weight of aromatic polycarbonate resin, (B) 5 to 60 parts by weight of butadiene rubber substrate, 20 to 80 parts by weight of styrene, and 5 to 40 parts by weight of acrylonitrile. 10 parts by weight or less, (C) 10 to 90 parts by weight of a styrene flame retardant copolymer containing 5 to 50 parts by weight of the bromostyrene compound, (D) to 100 parts by weight of the (A) + (B) + (C) precursor composition. 0.01 to 5 parts by weight of the metal salt used as the flame retardant of the aromatic polycarbonate resin, 10 parts by weight or less of antimony trioxide based on 100 parts by weight of the total composition (E) (A) + (B) + (C), and (F) (A It relates to a flame-retardant resin composition composed of 1 part by weight or less of tetrafluoro ethylene-based polymer with respect to 100 parts by weight of the composition +) (B) + (C).

본 발명에 사용된 방향족 폴리카보네이트는 일반적으로 디히드릭 페놀 화합물과 포스겐, 카보네이트 에스테르와 같은 카보네이트를 반응시켜 제조될 수 있다. 방향족 폴리카보네이트의 일반식은 다음과 같다.Aromatic polycarbonates used in the present invention can generally be prepared by reacting dihydric phenol compounds with carbonates such as phosgene and carbonate esters. The general formula of the aromatic polycarbonate is as follows.

Figure kpo00001
Figure kpo00001

여기서 A성분은 디히드릭 페놀로 부터 유도된 방향족 라디칼을 갖는 성분으로 구체적인 식은 다음과 같다.Here, component A is a component having an aromatic radical derived from dihydric phenol.

Figure kpo00002
Figure kpo00002

상기식에서 R1과 R2는 수소, 알킬 또는 페닐기이며, 알킨기의 탄소수는 1∼6이고, n은 40∼300의 정수이다.In the above formula, R 1 and R 2 are hydrogen, alkyl or phenyl group, carbon number of alkyne group is 1-6, n is an integer of 40-300.

방향족 폴리카보네이트의 제조에 사용되는 디히드릭 페놀은 방향족 핵의 탄소원자와 결합하고 있는 2개의 히드록시 라티칼로 구성된 단핵 또는 다핵 방향족 화합물이다.Dihydric phenols used in the production of aromatic polycarbonates are mononuclear or polynuclear aromatic compounds composed of two hydroxy radicals bonded with carbon atoms of the aromatic nucleus.

디히드릭 페놀의 예로서는 4,4-디히드록시페놀, 2,2-비스-(4-히드록시페닐)-프로판, 2,2-비스-(4-히드록시페닐)-펜탄, 2,4-(디히드록시디페닐)-메탄, 2,4- 비스-(4-히드록시페닐) -2-메틸부탄, 3,3 -비스-(4-히드록시페닐) -펜탄, 비스 - (4-히드록시-3,5-디클로로페닐)-메탄, 2,2-비스-(4-히드록시-3,5-디메틸페닐)-프로판, 1,1-비스 -(4-히드록시페닐)-시클로헥산, 2,2-비스-(3-클로로-4-히드록시페닐)-프로판, 2,2-비스-(3,5-디클로로-4-히드록시페닐)-프로판, 2,2-비스-(3,5-디브로모-4-히드록시페닐)-프로판 및 β,β-비스-(4-히드록시페닐)-p-디이소프로필벤젠이 있다. 특히, 바람직한 비스페놀은 비스페놀 A로 잘 알려진 2,2-비스-(4-히드록시페닐)-프로판이다.Examples of dihydric phenols include 4,4-dihydroxyphenol, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (4-hydroxyphenyl) -pentane, 2,4 -(Dihydroxydiphenyl) -methane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 3,3-bis- (4-hydroxyphenyl) -pentane, bis- (4 -Hydroxy-3,5-dichlorophenyl) -methane, 2,2-bis- (4-hydroxy-3,5-dimethylphenyl) -propane, 1,1-bis- (4-hydroxyphenyl)- Cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis -(3,5-dibromo-4-hydroxyphenyl) -propane and β, β-bis- (4-hydroxyphenyl) -p-diisopropylbenzene. Particularly preferred bisphenols are 2,2-bis- (4-hydroxyphenyl) -propane, well known as bisphenol A.

방향족 폴리카보네이트의 제조방법은 미합중국 특허 2964974, 2970137, 2991273, 2999835, 2999846, 3187605, 3208365, 3215668, 3248414, 3280078, 3334154, 4000184, 4131575, 독일 연방 공화국 특허 제902274 및 1546 호 등에 상세히 기술되어 있다. 폴리카보네이트는 분자량이 1,000∼200,000, 바람직하게는 20,000~100,000인 것을 사용한다.Methods of preparing aromatic polycarbonates are described in detail in US Pat. The polycarbonate has a molecular weight of 1,000 to 200,000, preferably 20,000 to 100,000.

이러한 방향족 폴리카보네이트 수지를 10∼90중량부, 바람직하게는 30∼80중량부를 사용한다.10-90 weight part, Preferably 30-80 weight part of such aromatic polycarbonate resin is used.

본 발명의 (B)성분의 ABS 수지는 일반적으로 아크릴로니트릴, 스티렌 및 부타디엔으로 부터 유도된 터폴리머이다. ABS 수지의 일반식은 다음과 같다.The ABS resin of the component (B) of the present invention is generally a terpolymer derived from acrylonitrile, styrene and butadiene. The general formula of the ABS resin is as follows.

Figure kpo00003
Figure kpo00003

상기식에서 x, y, z는 독립적으로 10∼1.500의 정수이다.In the above formula, x, y, z are independently an integer of 10 to 1.500.

세가지 단량체의 비율에 따라 중합체의 조성이 변함으로써 ABS 수지는 폭넓은 범위의 특성을 갖는다.As the composition of the polymer changes with the proportion of the three monomers, the ABS resin has a wide range of properties.

ABS 수지의 제조방법은 미합중국 특허 제2505349, 2550139, 2698313, 2713566, 2820773, 2908661, 4107232, 4173561, 4200702, 4206290, 4289687, 4355126, 4379440, 4456721, 4487886 및 4581403호 등에 자세히 실려있다.Methods of preparing ABS resins are described in detail in US Pat.

ABS 수지는 부타디엔 고무기질에 그라프트된 견고한 그라프트 중합체를 함유한다.The ABS resin contains a robust graft polymer grafted to butadiene rubber substrates.

대부분은 아크릴로니트릴 및 스티렌이 경질 스티렌-아크릴로니트릴(SAN) 매트릭스 중에 추가로 분산될 수 있는 폴리부타디엔 또는 고무상으로 그라프트된 완전한 터폴리머이며, 일반적으로 유화중합방법에 의해 제조된다. ABS 수지는 폴리카보네이트 수지와의 친화성 획득과 물성 균형을 위하여 아크릴로니트릴의 함량은 5∼40중량부, 스티렌 20∼80중량부, 부타디엔 고무기질 10∼60중량부로 구성된 것을 사용한다.Most are complete terpolymers grafted into polybutadiene or rubber phase, where acrylonitrile and styrene can be further dispersed in a hard styrene-acrylonitrile (SAN) matrix, and are generally prepared by emulsion polymerization. ABS resin is used in the acrylonitrile content of 5 to 40 parts by weight, 20 to 80 parts by weight of styrene, butadiene rubber substrate 10 to 60 parts by weight in order to obtain affinity with the polycarbonate resin and balance the physical properties.

이러한 ABS 수지를 60중량부 이하, 바람직하게는 10∼50중량부를 사용한다.The ABS resin is 60 parts by weight or less, preferably 10 to 50 parts by weight.

본 발명의 주요 성분중의 하나인 (C)성분의 브로모스티렌을 함유하는 스티렌계 난연 공중합체 중합공정에 의해 제조한다.It manufactures by the styrene type flame-retardant copolymer polymerization process containing the bromostyrene of (C) component which is one of the main components of this invention.

제1단계에서는 브로모스티렌 화합물을 단량체에 비해 소량 첨가시켜 중합체에 스티렌과 아크릴로니트릴과 브로모스티렌 화합물의 배열이 랜덤이 되게 함과 동시에 급격한 반응으로 부터 라텍스 안정성을 유지하며, 제2단계에서는 브로모스티렌 화합물을 단량체에 비해 과량 첨가시켜 전체적으르 랜덤 공중합체를 이루도록 하며, 제3단계에서는 브로모스티렌 화합물의 잔류 단량체 제거를 위하여 스티렌과 아크릴로니트릴을 소량 첨가하는 것을 특징으로 한다.In the first step, a small amount of bromostyrene compound is added to the monomer to randomize the arrangement of styrene, acrylonitrile, and bromostyrene compound to the polymer, while maintaining latex stability from a sudden reaction. The bromostyrene compound is added in excess of the monomer to form a random copolymer as a whole. In the third step, a small amount of styrene and acrylonitrile are added to remove residual monomer of the bromostyrene compound.

이하, 스티렌계 난연 공중합체의 제조공정을 상세하게 설명하면 다음과 같다. 제1단계에서는 교반이 가능한 반응기에 유화 형성을 위한 유화제와 이온 교환수를 넣고, 방향족 비닐 탄화수소 5∼30중량부, 불포화니트릴 5∼30중량부, 브로모스티렌 화합물 2∼20중량부, 연쇄 이동제를 넣은 후 온도를 상승시켜 반응기 내부온도가 40∼80℃에 도달하면 개시제를 반응기에 넣어 약 1시간 동안 중합 반응시킨다.Hereinafter, the manufacturing process of the styrene-based flame retardant copolymer in detail. In the first step, an emulsifier for forming an emulsion and ion-exchanged water are placed in a reactor capable of stirring, 5-30 parts by weight of an aromatic vinyl hydrocarbon, 5-30 parts by weight of an unsaturated nitrile, 2-20 parts by weight of a bromostyrene compound, and a chain transfer agent. After the addition of the reactor, the temperature was increased, and when the reactor internal temperature reached 40 to 80 ° C, an initiator was added to the reactor and polymerized for about 1 hour.

여기서 유화 형성을 위한 유화제로는 라우릴 황산 나트륨, 올레인산 칼륨, 올레인산 나트륨, 지방산 나트륨 또는 칼륨, 로진산 나트륨 또는 칼륨, 고분자 알킬 또는 알킬 디설페이트 및 설포네이트 알칼리 금속염 또는 암모늄이다. 방향족 비닐 탄화수소는 스티렌, α-메틸 스티렌, α-메틸 비닐톨루엔, 비닐톨루엔 o-에틸스티렌, p-에틸스티렌을 들 수 있다. 불포화니트릴의 예로는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴, 또는 두가지 이상의 혼합물을 들 수 있다. 개시제로는 벤조일 퍼옥사이드, 메타부틸히드로퍼옥사이드, 아세틸퍼옥사이드, 큐멘히드로퍼옥사이드시 나트륨, 과황산 암모늄, 과황산 칼슘 등이다.The emulsifiers for forming an emulsion here are sodium lauryl sulfate, potassium oleate, sodium oleate, sodium or potassium fatty acids, sodium or potassium rosin, high molecular alkyl or alkyl disulfates and sulfonate alkali metal salts or ammonium. Aromatic vinyl hydrocarbons include styrene, α-methyl styrene, α-methyl vinyltoluene, vinyltoluene o-ethylstyrene, and p-ethylstyrene. Examples of unsaturated nitriles include acrylonitrile, methacrylonitrile, ethacrylonitrile, or mixtures of two or more. Initiators include benzoyl peroxide, metabutyl hydroperoxide, acetyl peroxide, cumene hydroperoxide sodium, ammonium persulfate, calcium persulfate and the like.

2단계 중합은 유화제, 이온교환수, 중합개시제, 연쇄이동제, 방향족 비닐 탄화수소 5∼30중량부, 불포화니트릴 5∼30중량부, 브로모스티렌 화합물 5∼30중량부, 전부를 교반이 가능한 용기내에서 교반시키면서 2시간동안 연속적으로 반응기에 주입한다. 브로모스티렌 화합물의 제1단계와 제2단계 주입량의 비는 1 : 9∼5 : 5가 바람직하다.In the two-stage polymerization, an emulsifier, ion-exchanged water, a polymerization initiator, a chain transfer agent, 5-30 parts by weight of an aromatic vinyl hydrocarbon, 5-30 parts by weight of an unsaturated nitrile, 5-30 parts by weight of a bromostyrene compound, all in a container capable of stirring It is injected into the reactor continuously for 2 hours with stirring at. The ratio of the injected amount of the first step and the second step of the bromostyrene compound is preferably 1: 9-5: 5.

상기 1단계, 2단계에서 사용된 브로모스티렌 화합물의 예로는 브로모스티렌, 디브로모스티렌, 트리브로모스티렌, 테트라브로모스티렌, 펜타브로모스티렌 등을 들 수 있다.Examples of the bromostyrene compound used in steps 1 and 2 include bromostyrene, dibromostyrene, tribromostyrene, tetrabromostyrene, and pentabromostyrene.

제3단계 중합은 유화제, 이온교환수, 중합개시제, 연쇄이동제, 방향족 비닐 탄화수소 0.5∼10중량부, 불포화니트릴 0.5∼5중량부 전부를 교반이 가능한 용기에서 교반시키면서 2시간동안 연속적으로 반응기에 주입한다.In the third stage polymerization, the emulsifier, ion-exchanged water, polymerization initiator, chain transfer agent, 0.5-10 parts by weight of aromatic vinyl hydrocarbon, and 0.5-5 parts by weight of unsaturated nitrile are continuously injected into the reactor for 2 hours while stirring in a stirred container. do.

이러한 스티렌계 난연 공중합체를 10∼90중량부, 바람직하게는 25∼70중량부를 사용한다.10 to 90 parts by weight, preferably 25 to 70 parts by weight of such styrene flame retardant copolymer is used.

(D)성분인 방향족 폴리카보네이트의 난연제로 사용되는 금속염으로서는 유기 알칼리 금속염, 유기 알칼리 토금속염 또는 이들의 혼합물이 좋다. 이러한 금속염들은 많이 알려져 있고, 난연 폴리카보네이트 수지조성물로서 다량 사용되고 있다. 이들 금속염의 예로서는 소듐벤젠 설포네이트, 소듐 2,4,5-트리클로로벤젠설포네이트, 소듐 4,4'-디브로모비페닐-3-설포네이트, 디소듐나프탈렌-2,6-디설포네이트, 소듐 4,4'-디콜로로디페닐설파이드-3-설포네이트, 디소듐 4,4'-디클로로벤조페논-3,3'-디설포네이트, 소듐3,5-디콜로로티오펜-3-설포네이트, 2,4,5-트리클로로벤젠설포네이트의 포타슘염, 디페닐설폰-3-설폰산의 포타슘염, 소듐 디메틸 2,4,6-트리클로로-5-설포이소프탈레이트, 디소듐헥사플루오로글루타레이트 또는 이들의 혼합물이 있다.As a metal salt used as a flame retardant of aromatic polycarbonate which is (D) component, organic alkali metal salt, organic alkaline-earth metal salt, or a mixture thereof is preferable. Many such metal salts are known and are used in large amounts as flame retardant polycarbonate resin compositions. Examples of these metal salts include sodium benzene sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, sodium 4,4'-dibromobiphenyl-3-sulfonate, disodium naphthalene-2,6-disulfonate, Sodium 4,4'-dicholodiphenylsulfide-3-sulfonate, disodium 4,4'-dichlorobenzophenone-3,3'-disulfonate, sodium 3,5-dicholothiophene-3-sulfo , Potassium salt of 2,4,5-trichlorobenzenesulfonate, potassium salt of diphenylsulfone-3-sulfonic acid, sodium dimethyl 2,4,6-trichloro-5-sulfoisophthalate, disodium hexa Fluoroglutarate or mixtures thereof.

이러한 금속염을 (A)+(B)+(C) 전 수지 조성물 중량기준으로 0.01∼5중량부, 바람직하게는 0.1∼1중량부를 사용한다.Such metal salt is used in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight based on the total weight of the resin composition (A) + (B) + (C).

(E)성분의 삼산화안티몬은 난연효과를 향상시킬 목적으로 사용하는데, 이의 사용량은 전 수지 조성물(A)+(B)+(C) 중량기준으로 10중량부 이하, 바람직하게는 1∼5중량부를 사용한다.The antimony trioxide of (E) component is used for the purpose of improving a flame retardant effect, The usage-amount thereof is 10 weight part or less, Preferably it is 1-5 weight part by weight of the whole resin composition (A) + (B) + (C). Use wealth

일반적으로 난연제를 첨가시켜서 난연성을 얻는 난연 수지 조성물에서는 삼산화안티몬을 소량 사용하는 경우 난연제와의 상승효과에 의한 우수한 난연효과를 기대할 수 없으며, 다량 사용은 폴리카보네이트 수지를 분해하여 분자량을 감소시키기 때문에 제반 물성을 떨어뜨리게 된다 그러나, 본 발명의 난연 폴리카보네이트 수지 조성물에서는 소량의 삼산화안티몬을 첨가시키더라도 우수한 난연성을 얻을 수 있는 것이 장점이다.In general, in the flame retardant resin composition obtained by adding a flame retardant, when using a small amount of antimony trioxide, excellent flame retardant effect due to synergistic effect with the flame retardant cannot be expected, and the use of a large amount decomposes the polycarbonate resin to reduce the molecular weight. However, the physical properties are lowered. However, in the flame-retardant polycarbonate resin composition of the present invention, an excellent flame retardancy can be obtained even if a small amount of antimony trioxide is added.

(F)성분의 테트라플루오르 에틸렌계 중합체는 폴리카보네이트 수지의 열안정성을 향상시키고, 삼산화안티몬과 같이 난연성을 높여주는 상승제(synergist)로서 첨가된다. 테트라플루오르 에틸렌계 중합체(테프론)는 (A)+(B)+(C) 전 수지 조성물 기준으로 1중량부 이하, 바림직하게는 0.05∼0.5중량부 사용한다.The tetrafluoroethylene polymer of the component (F) is added as a synergist that improves the thermal stability of the polycarbonate resin and improves the flame retardancy like antimony trioxide. The tetrafluoro ethylene polymer (Teflon) is used in an amount of 1 part by weight or less, preferably 0.05 to 0.5 parts by weight, based on the total resin composition (A) + (B) + (C).

본 발명의 수지 조성물은 통상적인 혼합기기, 예를 들면 트윈-스크류 압출기(Twin Screw Extruder),니더(Kneader), 반바리믹서(Banbary mixer)등을 이용하여 제조된다. 수지 조성물은 또한 안정제, 윤활제, 가공조제, 이형제, 대전방지제, 충전제, 유리섬유, 안료등의 통상적인 첨가제를 함유할 수도 있다.The resin composition of the present invention is prepared using a conventional mixing device, for example, Twin Screw Extruder, Kneader, Banbary mixer and the like. The resin composition may also contain conventional additives such as stabilizers, lubricants, processing aids, mold release agents, antistatic agents, fillers, glass fibers, pigments and the like.

이하, 본 발명의 난연 수지 조성물에 대하여 실시예를 들어 상세하게 설명하기로 한다. 실시예 및 비교예에서 사용된 폴리카보네이트, ABS 수지 및 스티렌계 난연 공중합체는 다음과 같다.Hereinafter, the flame retardant resin composition of the present invention will be described in detail with reference to Examples. Polycarbonate, ABS resin and styrene-based flame retardant copolymers used in Examples and Comparative Examples are as follows.

i) PC Lexan 121, 저점도grade(G.E.)i) PC Lexan 121, low viscosity grade (G.E.)

ii) ABS : 이 성분은 40중량부의 폴리부타티엔 기질에 2.5 : 1의 중량비로 그라프트된 스티렌-아크릴로니트릴 60중량부를 함유한다.ii) ABS: This component contains 60 parts by weight of styrene-acrylonitrile grafted in a weight ratio of 2.5: 1 on a 40 parts by weight polybutadiene substrate.

iii) 반응형 난연 SAN : 1단계 중합은 이온교환수 100중량부, 라우릴황산나트륨 1중량부, 스티렌 25중량부, 아크릴로니트릴 10중량부, 트리브로모스티렌 10중량부 및 t-도데실메르캅탄 0.2중량부를 반응기에 넣고 교반을 하면서 반응기 내부온도를 상승시킨다. 반응기의 내부온도가 60℃에 도달하면 과황산칼륨 0.3중량부를 주입하여 1시간 동안 반응시킨다. 2단계 중합에서는 교반이 가능한 용기에 이온교환수 100중량부,라우릴황산나트륨 1중량부, 스티렌 15중량부, 아크릴로니트릴 6중량부, 트리브로모스티렌 30중량부, t-도데실메르캅탄 0.2중량부 및 과황산칼륨 0.3중량부를 주입 교반하여 에멀젼 상태로 만든 다음, 2시간에 걸쳐반응기에 연속 투입한다. 제3단계 중합반응에서는 교반이 가능한 용기에 이온교환수 50중량부, 라우릴황산나트륨 0.1중량부, 스티렌 3중량부, 아크릴로니트릴 2중량부 및 과황산칼륨 0.005중량부를 주입하여 교반시켜 에멀젼 상태로 만든 다음, 2시간 동안 반응기에 연속 투입시킨다. 이후 2시간 동안 더 중합을 계속하여 반응형 난연 SAN수지를 얻게 된다.iii) Reactive flame-retardant SAN: One-step polymerization is 100 parts by weight of ion-exchanged water, 1 part by weight of sodium lauryl sulfate, 25 parts by weight of styrene, 10 parts by weight of acrylonitrile, 10 parts by weight of tribromostyrene and t-dodecylmer 0.2 parts by weight of captan is added to the reactor and the temperature inside the reactor is increased while stirring. When the internal temperature of the reactor reaches 60 ℃, 0.3 parts by weight of potassium persulfate is injected and reacted for 1 hour. In the two-stage polymerization, 100 parts by weight of ion-exchanged water, 1 part by weight of sodium lauryl sulfate, 15 parts by weight of styrene, 6 parts by weight of acrylonitrile, 30 parts by weight of tribromostyrene, and t-dodecyl mercaptan 0.2 The parts by weight and 0.3 parts by weight of potassium persulfate were injected and stirred into an emulsion, and then continuously added to the reactor over 2 hours. In the third stage polymerization reaction, 50 parts by weight of ion-exchanged water, 0.1 parts by weight of sodium lauryl sulfate, 3 parts by weight of styrene, 2 parts by weight of acrylonitrile and 0.005 parts by weight of potassium persulfate are added to the vessel, which can be stirred, into an emulsion state. After making, it is continuously added to the reactor for 2 hours. The polymerization is then continued for 2 hours to obtain a reactive flame retardant SAN resin.

[실시예 1]Example 1

방향족 폴리카보네이트 70중량부, ABS 15중량부, 반응형 난연 SAN 15중량부, 난연 조제로서 삼산화안티몬을 전조성물 중량기준으로 2.5중량부, 테프론을 전조성물 중량기준으로 0.1중량부, 윤활제가 전조성물 중량기준으로 0.5중량부로 구성된 수지 혼합물을 헨셀 믹서(Henshell mixer)로 1분간 균일하게 혼합한 후, 트윈 스크류 압출기를 이용하여 실린더 온도를 230∼260℃로 유지하여 압출한 다음, 다이에 걸어 압출된 침상 물질을 냉각시킨 후, 절단하여 이를 펠렛(Pellet) 상으로 얻는다.70 parts by weight of aromatic polycarbonate, 15 parts by weight of ABS, 15 parts by weight of reactive flame retardant SAN, 2.5 parts by weight of antimony trioxide as a precursor, 0.1 part by weight of Teflon as a precursor, and a lubricant as a flame retardant After mixing the resin mixture composed of 0.5 parts by weight by weight uniformly for 1 minute with a Henshell mixer, and extruded by using a twin screw extruder at a cylinder temperature of 230 ~ 260 ℃, and extruded on a die After cooling the needle-like material, it is cut and obtained as pellet phase.

이에 대한 물성, 난연성 및 내후성을 측정하기 위하여 먼저 상기 펠렛을 100∼120℃에서 제습형 건조기나 열풍 건조기를 이용하여 약 4시간 동안 예비 건조 시킨후, 2.5온스 사출기를 이용하여 실린더 온도 240∼260℃에서 ASTM 규정에 의거하여 물성 및 난연 시편을 제작하였다.In order to measure the physical properties, flame retardancy and weather resistance, the pellets were first preliminarily dried at 100 to 120 ° C. for about 4 hours using a dehumidifying dryer or hot air dryer, and then the cylinder temperature was 240 to 260 ° C. using a 2.5 ounce injection machine. The physical properties and flame retardant specimens were prepared in accordance with ASTM.

상기와 같이 제작된 시편에 대한 물성 측정을 ASTM 규정에 의거하여 실시하였고, 난연성 시험을 UL-94의 난연 시험 규정에 따른 시험장치, 조건, 방법을 준수하였다. 난연도의 판정은 UL-94의 V-0, V-1, V-2 판정 기준을 그대로 적용하였다. 또한, 제작된 시편의 내후성 시험을 위해 아트라스(Atlas)사의 내후성 시험기에서 300시간 조사후 칼라 변색을 측정하였다. 결과는 표 1에 나타내었다.The physical properties of the specimens prepared as described above were measured in accordance with ASTM regulations, and the flame retardancy test was conducted in accordance with the test apparatus, conditions, and methods according to the flame retardancy test regulations of UL-94. The determination of the flame retardance applied the criteria of UL-094's V-0, V-1, and V-2. In addition, for the weather resistance test of the fabricated specimens were measured for color discoloration after irradiation for 300 hours in the weather tester of Atlas (Atlas). The results are shown in Table 1.

[실시예 2]Example 2

실시예 1의 성분 이외에 소듐 2,4,5-트리클로로벤젠 설포네이트를 0.5중량부 첨가하는 것을 제외하고는 실시예 1과 동일한 조성 및 방법에 의해 물성, 난연성 및 내후성 시험을 하여 결과를 표 1에 나타내었다.Except for the addition of 0.5 parts by weight of sodium 2,4,5-trichlorobenzene sulfonate in addition to the components of Example 1, the physical properties, flame retardancy and weather resistance tests were carried out by the same composition and method as in Example 1, and the results are shown in Table 1 Shown in

[실시예 3]Example 3

실시예 2의 성분중 ABS를 10중량부, 반응형 난연 SAN을 20중량부로 변화시키고, 삼산화안티몬을 첨가하지 않는 것을 제외하고는 실시예 1과 동일한 방법에 의해 물성, 난연성 및 내후성 시험을 하여 결과를 표1에 나타내었다.The physical properties, flame retardancy and weather resistance test were carried out in the same manner as in Example 1 except that 10 parts by weight of ABS and 20 parts by weight of reactive flame retardant SAN were added, and no antimony trioxide was added. Is shown in Table 1.

[실시예 4]Example 4

실시예 1의 성분중 폴리카보네이트를 50중량부, ABS를 25중량부, 반응형 난연 SAN을 25중량부, 삼산화안티몬을 3중량부로 함량을 변화시키고, 소듐 2,4,5-트리클로로벤젠 설포네이트를 0.5중량부 첨가하였다. 나머지 조성과 시험 방법은 실시예 1과 동일하게 하여 결과를 표 1에 나타내었다.Among the components of Example 1, 50 parts by weight of polycarbonate, 25 parts by weight of ABS, 25 parts by weight of reactive flame retardant SAN, 3 parts by weight of antimony trioxide, and sodium 2,4,5-trichlorobenzene sulfo 0.5 parts by weight of nate was added. The remaining composition and test method were the same as in Example 1, and the results are shown in Table 1.

[실시예 5]Example 5

실시예 4의 성분중 ABS를 35중량부, 반응형 난연 SAN은 15중량부로 함량을 변화시키는 것을 제외하고는 실시예 1과 동일한 방법에 의해 시험을 행하여 결과를 표 1에 나타내었다.Except for changing the content to 35 parts by weight of ABS and 15 parts by weight of the reactive flame-retardant SAN of the components of Example 4, the test was carried out in the same manner as in Example 1 and the results are shown in Table 1.

[비교예 1]Comparative Example 1

실시예 1의 성분중 ABS를 30중량부로 변화시키고, 반응형 난연 SAN과 삼산화안티몬을 첨가하지 않는 것을 제외하고는 실시예 1과 동일한 방법에 의하여 시험을 행하여 결과를 표 1에 나타내었다.Except for changing the ABS to 30 parts by weight of the component of Example 1, and the test was carried out in the same manner as in Example 1 except that the reactive flame retardant SAN and antimony trioxide was not added, the results are shown in Table 1.

[비교예 2]Comparative Example 2

비교예 1의 성분 이외에 난연제로서 테트라비스페놀 A 카보네이트 올리고머를 8중량부, 난연조제로서 삼산화안티몬을 3중량부 첨가하는 것을 제외하고는 실시예 1과 동일한 조건 및 실험 방법으로 시험을 행하여 결과를 표 1에 나타내었다.Except for the addition of 8 parts by weight of tetrabisphenol A carbonate oligomer as a flame retardant, and 3 parts by weight of antimony trioxide as a flame retardant, in addition to the components of Comparative Example 1, the test was conducted under the same conditions and experimental methods as in Example 1 Shown in

[비교예 3]Comparative Example 3

비교예 1의 성분 이외에 소듐 2,4,5-트리클로로벤젠 설포네이트를 0.5중량부, 삼산화안티몬을 3중량부 첨가하는 것을 제외하고는 실시예 1과 동일한 조건 및 실험 방법으로 시험을 행하여 결과를 표 1에 나타내었다.Except for adding 0.5 parts by weight of sodium 2,4,5-trichlorobenzene sulfonate and 3 parts by weight of antimony trioxide in addition to the components of Comparative Example 1, the test was conducted under the same conditions and experimental methods as in Example 1 Table 1 shows.

[표 1]TABLE 1

Figure kpo00004
Figure kpo00004

1. BR-PC : 테트라브로모 비스페놀 A 카보네이트 올리고머(상품명 : BC-58, Great Lakes)BR-PC: Tetrabromo bisphenol A carbonate oligomer (Brand name: BC-58, Great Lakes)

2. STB : 소듐 2,4,5一트리클로로벤젠 설포네이트2. STB: Sodium 2,4,5 one trichlorobenzene sulfonate

3. Teflon : 테트라플루오르 폴리에틸렌(상품명 : Teflon 6J, Du Pont)3.Teflon: tetrafluoropolyethylene (trade name: Teflon 6J, Du Pont)

4. 윤활제 : 아크릴산 에틸렌 코폴리머(상품명 : AC-540, Allied Chem, Company)4. Lubricant: Ethylene acrylate copolymer (trade name: AC-540, Allied Chem, Company)

5. 내후성 시험기 : (Weather-O-Meter)에 300시간 조사후의 결과임.5. Weathering tester: Result after 300 hours of irradiation in (Weather-O-Meter).

Claims (6)

[A]방향족 폴리카보네이트 수지 10∼90중량부,[B]부타디엔 고무기질 5∼60중량부, 스티렌 20∼80중량부, 아크릴로니트릴 5∼40중량부로 구성된 ABS 수지 60중량부 이하, [C]브로모스티렌 화합물 5∼50중량부를 함유하는 스티렌계 난연 공중합체 10∼90중량부, [D](A),(B) 및 (C) 전 조성물 100중량부 기준으로 방향족 폴리카보네이트의 난연제로 사용되는 금속염 0.01∼5중량부, [E](A),(B) 및 (C) 전 조성물 100중량부 기준으로 방향족 폴리카보네이트의 난연제로 사용되는 금속염 0.01∼5중량부, [E](A,B) 및 (C) 전 조성을 100중량부 기준으로 삼산화안티몬 10중량부 이하, [F](A),(B),(C) 전 조성물 100중량부 기준으로 테트라 플루오르에틸렌계 중합체 1중량부 이하로 구성되는 난연 수지 조성물.[A] 10 to 90 parts by weight of aromatic polycarbonate resin, 5 to 60 parts by weight of [B] butadiene rubber substrate, 20 to 80 parts by weight of styrene, 5 to 40 parts by weight of acrylonitrile, 60 parts by weight or less, [C ] 10 to 90 parts by weight of a styrenic flame retardant copolymer containing 5 to 50 parts by weight of bromostyrene compound, and 100 parts by weight of [D] (A), (B) and (C) the composition as a flame retardant of aromatic polycarbonate 0.01 to 5 parts by weight of the metal salt used, 0.01 to 5 parts by weight of the metal salt used as the flame retardant of the aromatic polycarbonate based on 100 parts by weight of the entire composition of [E] (A), (B) and (C), [E] (A 10 parts by weight or less of antimony trioxide based on 100 parts by weight of the total composition of B, and (C), and 1 part by weight of tetrafluoroethylene polymer based on 100 parts by weight of the total composition of [F] (A), (B) and (C). A flame-retardant resin composition comprised below. 제1항에 있어서 스티렌계 난연 공중합체가 브로모스티렌 화합물 5∼50중량부, 방향족 비닐탄화수소 10∼60중량부, 불포화니트릴 10∼60중량부가 구성되고, 3단계 중합반응에 의해 제조됨을 특징으로 하는 난연 수지 조성물.The styrene flame retardant copolymer is composed of 5 to 50 parts by weight of bromostyrene compound, 10 to 60 parts by weight of aromatic vinyl hydrocarbon, 10 to 60 parts by weight of unsaturated nitrile, and is prepared by a three-step polymerization reaction. Flame retardant resin composition. 제1항에 있어서 브로모스티렌 화합물이 브로모스티렌, 디브로모스티렌, 트리브로모스티렌, 테트라브로모스티렌, 펜타브로모스티렌인 난연 수지 조성물.The flame retardant resin composition according to claim 1, wherein the bromostyrene compound is bromostyrene, dibromostyrene, tribromostyrene, tetrabromostyrene, or pentabromostyrene. 제1항에 있어서 방향족 폴리카보네이트 수지의 난연제인 금속염이 유기 알칼리 금속, 유기 알칼리 토금속 또는 이들의 혼합물인 난연 수지 조성물.The flame retardant resin composition according to claim 1, wherein the metal salt which is a flame retardant of the aromatic polycarbonate resin is an organic alkali metal, an organic alkaline earth metal or a mixture thereof. 제2항에 있어서 방향족 비닐탄화수소가 스티렌, α-메틸 톨루엔, 비닐 톨루엔, o-에틸 스티렌, p-에틸 스티렌인 난연 수지 조성물.The flame retardant resin composition according to claim 2, wherein the aromatic vinyl hydrocarbons are styrene, α-methyl toluene, vinyl toluene, o-ethyl styrene, and p-ethyl styrene. 제2항에 있어서 불포화니트릴이 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴 또는 이들의 혼합물인 난연 수지 조성물.The flame retardant resin composition according to claim 2, wherein the unsaturated nitrile is acrylonitrile, methacrylonitrile, ethacrylonitrile or a mixture thereof.
KR1019910001778A 1991-02-01 1991-02-01 Anti-flammable resin composition KR940006472B1 (en)

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