KR930008194B1 - Thermoplastic resin composition - Google Patents

Thermoplastic resin composition Download PDF

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KR930008194B1
KR930008194B1 KR1019900009812A KR900009812A KR930008194B1 KR 930008194 B1 KR930008194 B1 KR 930008194B1 KR 1019900009812 A KR1019900009812 A KR 1019900009812A KR 900009812 A KR900009812 A KR 900009812A KR 930008194 B1 KR930008194 B1 KR 930008194B1
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weight
resin composition
polybutylene terephthalate
copolymerized
rubber
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KR1019900009812A
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KR920000870A (en
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김광태
김정락
박병식
임희석
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제일합섬 주식회사
이수환
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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
    • 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This new thermoplastic resin composition has good impact resistance at room and low temp., and can be use for housing of cars and electronics. The resin composition comprises 35-55 wt.% polycarbonate resin of 25000 Mw.; 35-45 wt.% polybutylene terephthalate copoly merized by ethylene propylene grafted by formula (I) and (II); 1-20 wt.% impact reinforcing agent copolymerized by at least one monomer of acrylic ester and metacrylic ester, and aromatic vinyl compd. in the presence of dien type rubber; 1-5 wt.% copolymerized polyolefin; 0.1-2 wt.% stabilizer; and 0.2-1 wt.% carbon black with above 500m3/g specific surface by BET method. The above copoly merization ratio of ethylene propylene rubber and polybutylene terephthalate is 10- 20:90-80.

Description

열가소성 수지 조성물Thermoplastic resin composition

본 발명은 자동차 전자전기 기기등의 외장판 및 하우징(housing)용에 이용될 수 있는 수지 조성물에 관한 것으로서, 더욱 상세하게는 상온 및 저온에서의 내충격성이 우수하며, 내약품성, 수치 안정성이 우수한 성형품을 사출 성형할 수 있는 열가소성 수지 조성물에 관한 것이다.The present invention relates to a resin composition that can be used for exterior plates and housings, such as automotive electronic and electrical equipment, and more particularly, excellent impact resistance at room temperature and low temperature, excellent chemical resistance, numerical stability A thermoplastic resin composition capable of injection molding a molded article.

일반적으로 자동차에서 범퍼(bumper), 패널(panel)등의 외장 부품등은 스틸(steel)로 이루어져 있으나 현재에는 경량화의 목적으로 플라스틱(plastic) 재료로 전환되고 있다. 또한 자동차에 사용되는 경우 내충격성과 내열성이 요구되어지고 있는바 플라스틱 재료중 이런 성질을 갖는 것을 폴리카보네이트(polycarbonate)등이 주목되고 있다.In general, exterior parts such as bumpers and panels in automobiles are made of steel, but are now converted to plastic materials for the purpose of light weight. In addition, when used in automobiles, impact resistance and heat resistance are required. Among plastic materials, polycarbonate and the like have attracted attention.

그러나 폴리카보네이트는 내약품성 및 유동성이 좋지않은 단점이 있기 때문에 다른 수지와 알로이(Alloy)화(化)하여 사용한다.However, since polycarbonate has disadvantages of poor chemical resistance and fluidity, it is used in combination with other resins (Alloy).

이런 알로이에는 포리카보네이트의 단점을 보완하기 위해 ABS 수지와 알로이를 하는 경우도 있지만 내열성 부족으로 문제가 되는 부분이 있으며 폴리카보네이트와 폴리부틸렌테레프탈레이트(polybutyleneterephthalate)의 알로이는 내약품성이 우수하나 내충격성이 떨어져 문제가 되고 있다.In order to compensate for the disadvantages of polycarbonate, some alloys may be made of ABS resin and alloy, but there is a problem due to lack of heat resistance, and alloys of polycarbonate and polybutyleneterephthalate have excellent chemical resistance but impact resistance. This is becoming a problem apart.

또한 일본공개 특허 39-20434의 폴리카보네이트, 폴리부틸렌테레프탈레이트, 폴리올레핀(polyolefin)의 수지 조성물은 내약품성, 내충격성은 우수하나 저온 내 충격성이 문제가 되고 있다. 일본공개 특허 55-9435는 저온 충격성을 보완하기 위해 폴리카보네이트 폴리부틸렌테레프탈레이트 및 MBS수지 조성물을 제조하였지만 내약품성이 다소 부족하였다.In addition, the resin compositions of polycarbonate, polybutylene terephthalate, and polyolefin of Japanese Patent Application Laid-Open No. 39-20434 have excellent chemical resistance and impact resistance, but have problems with low temperature impact resistance. Japanese Patent Laid-Open No. 55-9435 produced polycarbonate polybutylene terephthalate and MBS resin compositions to compensate for low temperature impact, but lacked chemical resistance somewhat.

또한 일본공개 특허 53-129246는 폴리카보네이트, 폴리부틸렌테레프탈레이트 MAS 수지를 이용한 3원계 조성물이 제안되었지만 MAS 수지에 기인된 분산성에 의한 외관 불량이 단점으로 나타났다.In addition, Japanese Patent Application Laid-Open No. 53-129246 proposes a ternary composition using polycarbonate and polybutylene terephthalate MAS resin, but a poor appearance due to dispersibility caused by MAS resin has been found to be a disadvantage.

그리고 미국특허 제4,654,400호에는 폴리카보네이트, 폴리부틸렌테레프탈레이트 코아-쉘(core-shell)형태의 충격강화제를 사용하였으며 그 입자의 크기도 0.21 m이내로 하는 수지 조성물을 특징으로 하였다.In US Pat. No. 4,654,400, polycarbonate, polybutylene terephthalate core-shell type impact modifier is used, and the particle size is 0.21. It characterized by the resin composition set to m or less.

따라서 본 발명은 저온 내충격성, 내약품성, 수치 안정성 및 외관이 우수한 수지 조성물에 관한 것으로서 폴리카보네이트, 알코올기 및 에스테르기가 붙어 있는 에틸렌푸로필렌 고무(ethylene propylene rubber)를 충격에 약한 폴리부틸렌테레프탈레이트에 공중합시킨 수지, 충격강화제로서는 디엔계 고무 존재하에 아크릴산 에스테르 및 메타크릴산 에스테르로된 것중에 선택된 1종 이상의 모노머(monomer) 및 방향족 비닐 화합물을 공중합시킨 코아-쉘 타입의 중합체, 폴리올레핀으로 이루어진 것을 특징으로한 수지 조성물이다.Accordingly, the present invention relates to a resin composition having excellent low-temperature impact resistance, chemical resistance, numerical stability, and appearance. Polybutylene terephthalate having a low impact on ethylene propylene rubber having polycarbonate, alcohol group, and ester group The resin and the impact-improving agent copolymerized in the above are composed of a core-shell polymer and a polyolefin copolymerized with one or more monomers and aromatic vinyl compounds selected from acrylic esters and methacrylic esters in the presence of diene rubber. It is a resin composition characterized by the above-mentioned.

더욱 상세히 설명하면 폴리카보네이트는 비스페놀A로 반응한 방향족 화합물이 좋으며 함량은 35~55중량%이며, 폴리부틸렌테레프탈레이트는 알코올기, 에스테르기가 붙은 에틸렌푸로필렌 고무로 공중합된 것을 사용하는 것이 바람직하다.In more detail, the polycarbonate is preferably an aromatic compound reacted with bisphenol A, and the content is 35 to 55% by weight, and the polybutylene terephthalate is preferably copolymerized with ethylene furopropylene rubber having alcohol group or ester group. .

특히 알코올기는 에탄올 석시니미드(ethanolsuccinimide)로서 에틸렌푸로필렌 고무에 그라프팅(grafting)되어 있으며, 구조식은

Figure kpo00001
이다.In particular, the alcohol group is grafted on ethylene furopropylene rubber as ethanolsuccinimide, and the structural formula is
Figure kpo00001
to be.

에스테르기는 디 부틸 석시네이트(dibutylsuccinate)로서 에틸렌푸로필렌에 그라프팅 되어 있으며, 구조식은

Figure kpo00002
이다.The ester group is grafted on ethylene furopropylene as dibutylsuccinate, and the structural formula is
Figure kpo00002
to be.

위의 알코올기 및 에스테르기로 그라프팅된 에틸렌푸로필렌 고무를 폴리부틸렌테레프탈레이트의 축중합반응에서 공중합시킨 것으로 공중합 비율은 그라프팅된 에틸렌푸로필렌 고무 : 폴리부틸렌테레프탈레이트가 10~20 : 80~90중량부이며, 공중합 폴리부틸렌테레프탈레이트는 35~45중량부%이다.The copolymerization ratio of the ethylene furopropylene rubber grafted with the alcohol group and the ester group is copolymerized in the polycondensation reaction of polybutylene terephthalate, and the copolymerization ratio is grafted ethylene furopropylene rubber: 10 to 20: 80 It is -90 weight part, and copolymerization polybutylene terephthalate is 35-45 weight part.

또한 충격강화제는 디엔계 고무 존재하에서 탄소수가 5~14의 아크릴산 에스테르 및 메타 크릴산 에스테르에서 선택된 1종 이상의 모노머 및 방향족 비닐 화합물을 공중합시킨 코아-쉘 형태의 공중합물로서, 좀 더 상세하게 설명하면 디엔계 고무로서는 폴리부타디엔(poly butadiene), 폴리이소프렌(polyisoprene)이며, 아크릴산 에스테르 및 메타크릴산 에스테르로서는 아크릴산 메틸, 아크릴산 부틸, 메타크릴산 메틸, 메타크릴산 부틸 등을 선택하는 것이 바람직하며 방향족 비닐 화합물로서는 스틸렌(styrene) α-메틸스틸렌(α-methyl styrene)을 선택할 수 있다. 상기 충격강화제로서는 오우(吳羽)화학의 KCA-102등이 상품화 되어 있다. 함량은 1~20중량%이다.In addition, the impact modifier is a core-shell copolymer obtained by copolymerizing at least one monomer and an aromatic vinyl compound selected from acrylic acid and methacrylic acid esters having 5 to 14 carbon atoms in the presence of diene rubber. As the diene rubber, polybutadiene and polyisoprene are used. As acrylic ester and methacrylic ester, methyl acrylate, butyl acrylate, methyl methacrylate, butyl methacrylate, and the like are preferably selected. As the compound, styrene α-methylstyrene can be selected. Oka Chemical KCA-102 is commercialized as the impact enhancer. The content is 1 to 20% by weight.

또한 폴리올레핀은 저밀도 폴리에틸렌, 고밀도 폴리에틸렌, 폴리푸로필렌, 공중합된 폴리푸로필렌을 사용하는 것이 바람직하며 그 함량은 1~50중량%를 사용할 수 있다.In addition, the polyolefin, it is preferable to use low density polyethylene, high density polyethylene, polyfuropropylene, copolymerized polyfuropropylene, the content may be 1 to 50% by weight.

그리고 무기 충진제, 안정제, 산화방지제, 카본블랙을 첨가하는 것이 바람직하다. 이때 안정제는 0.1~2중량%, 카본블랙은 0.2~1중량%를 사용할 수 있다. 폴리카보네이트는 120℃에서 4시간 건조하여 사용했으며 공중합된 폴리부틸렌테레프탈레이트는 120℃에서 3시간 건조하여 사용했다.In addition, it is preferable to add an inorganic filler, a stabilizer, an antioxidant, and carbon black. At this time, the stabilizer may be 0.1 to 2% by weight, carbon black may be used 0.2 to 1% by weight. Polycarbonate was used after drying for 4 hours at 120 ℃ and copolymerized polybutylene terephthalate was used for 3 hours at 120 ℃.

또한 다른 수지는 건조하지 않고 사용했으며 이중 나사 압출기(Twin Extuder)[직경 30mm 미국 APV사]에서 온도는 250℃~260℃, 350rpm으로하여 압출시켜 펠레트(pellet)화 하였다. 또한 펠레트를 5 OZ 성형기에서 실린더 온도(245~265℃), 사출압 60~70kg/㎠, 금형온도 80℃에서 성형하여 인장강도, 충격강도(23℃,-30℃), 용융지수를 측정하였다.In addition, other resins were used without drying, and the pellets were extruded at a temperature of 250 ° C. to 260 ° C. and 350 rpm in a twin screw extruder (diameter of 30 mm US APV). In addition, the pellet is molded at a cylinder temperature (245 ~ 265 ℃), injection pressure 60 ~ 70kg / ㎠, mold temperature 80 ℃ in a 5 OZ molding machine to measure tensile strength, impact strength (23 ℃, -30 ℃) and melt index. It was.

[실시예 1~5 및 비교실시예 1~5][Examples 1-5 and Comparative Examples 1-5]

실시예 및 비교실시예의 수지조성물 함량은 표 1과 같이 하였으며 그 물성을 평가한 값은 표 2와 같다.The resin composition contents of Examples and Comparative Examples were as shown in Table 1, the value of the physical properties are shown in Table 2.

[표 1]TABLE 1

Figure kpo00003
Figure kpo00003

* 폴리카보네이트(PC) : 제인화성(帝人化成) L-1250(분자량 25.000)* Polycarbonate (PC): deignification L-1250 (molecular weight 25.000)

폴리부틸렌테레프탈레이트 : 제일합섬제품, 25℃, 오크로클로로페놀을 용매로하여 극한 점도[η]=0.8Polybutylene terephthalate: Cheil Synthetic Products, 25 ℃, Intrinsic Viscosity [η] = 0.8 with ocrochlorophenol as solvent

공중합 PBT 1) : 에탄올 석시니미드로 그라프팅된 에틸렌푸로필렌 고무를 공중합시킨 폴리부틸렌테레프탈레이트.Copolymerization PBT 1): Polybutylene terephthalate copolymerized with ethylene propylene resin grafted with ethanol succinimide.

공중합 PBT 2) : 디부틸 석시네이트로 그라프팅된 에틸렌푸로필렌 고무를 공중합시킨 폴리부틸렌테레프탈레이트.Copolymerization PBT 2): Polybutylene terephthalate copolymerized with ethylene furopropylene rubber grafted with dibutyl succinate.

KCA 102 : 오우(吳羽)화학 아크릴계 탄성 중합체KCA 102: Oou Chemical Acrylic Elastomer

B-56 : 종연(鐘淵)화학 MBS계B-56: Jongyeon Chemical MBS

안정제 : 시바가이기사의 B220, B900Stabilizer: B220, B900

B2000 : B900=1 : 1로 혼합사용.B2000: B900 = 1: 1 mixed use.

카본블랙 : 전기(電氣)화학 BET법 비표면적 970m3/g인 것을 사용.Carbon black: Electrochemical BET method Specific surface area of 970 m 3 / g is used.

[표 2]TABLE 2

Figure kpo00004
Figure kpo00004

상기 실시예 및 비교예를 평가하는 것은 ASTM D638의 인장강도, 신도 ASTM D256의 충격강도를 평가하였으며 ASTM D1238으로 MI값을 측정하였다. 특히 저온 충격강도 초저온 항온 항습기에 4시간 동안 처리한 후 평가한 것임.Evaluating the Examples and Comparative Examples evaluated the tensile strength of the ASTM D638, the elongation of the impact of ASTM D256 and measured the MI value by ASTM D1238. In particular, it was evaluated after treatment for 4 hours in the low temperature impact strength ultra low temperature constant temperature and humidity chamber.

Claims (2)

분자량이 25,000인 폴리카보네이트 수지 35~55중량%, 하기식(Ⅰ) 및 (Ⅱ)로 그라프팅된 에틸렌푸로필렌 고무로 공중합된 폴리부틸렌 테레프탈레이트 35~45중량%, 디엔계 고무 존재하에 아크릴산 에스테르 및 메타크릴산 에스테르로된 1종 이상의 모노머 및 방향족 비닐 화합물을 공중합시킨 충격강화제 1~20중량%, 공중합된 폴리올레핀 1~5중량%, 안정제 0.1~2중량%,BET법 비표면적이 500m3/g이상되는 카본블랙 0.2~1중량%로 구성됨을 특징으로 하는 열가소성 수지 조성물.35 to 55% by weight of polycarbonate resin having a molecular weight of 25,000, 35 to 45% by weight of polybutylene terephthalate copolymerized with ethylene furopropylene rubber grafted with the following formulas (I) and (II), acrylic acid in the presence of diene rubber 1 to 20% by weight of impact modifier copolymerized with one or more monomers and esters of methacrylic acid esters and aromatic vinyl compounds, 1 to 5% by weight of copolymerized polyolefin, 0.1 to 2% by weight stabilizer, BET method specific surface area 500m 3 Thermoplastic resin composition, characterized in that composed of 0.2 to 1% by weight of carbon black / g or more.
Figure kpo00005
Figure kpo00005
 제 1 항에 있어서, 에틸렌푸로필렌 고무와 폴리부틸렌테레프탈레이트의 공중합비가 10~20 : 80~90중량%인 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to claim 1, wherein the copolymerization ratio of ethylene furopropylene rubber and polybutylene terephthalate is 10 to 20:80 to 90% by weight.
KR1019900009812A 1990-06-30 1990-06-30 Thermoplastic resin composition KR930008194B1 (en)

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