KR101438912B1 - Flame resisting thermoplastic elastomer composition for weather strip - Google Patents
Flame resisting thermoplastic elastomer composition for weather strip Download PDFInfo
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Abstract
본 발명은 자동차 웨더스트립용 난연 열가소성 탄성체 조성물에 관한 것으로, 보다 상세하게는 α-올레핀계 성분들이 2종류 이상 공중합된 고무와 장쇄분기를 가진 고용융 지수의 폴리프로필렌을 혼합한 난연 열가소성 탄성체 조성물을 제조함으로써 난연성이 향상되고, 표피층에 미세발포 처리를 통해 외관의 질감을 부여할 수 있으며, 내후성 및 내마모성을 향상시키고 웨더스트립 표피층뿐만 아니라 자동차용 내장 인스트루먼트 판넬 및 도어 트림의 표피층 등에 활용될 수 있는 자동차 웨더스트립용 난연 열가소성 탄성체 조성물에 관한 것이다. The present invention relates to a flame retardant thermoplastic elastomer composition for automotive weather strips, and more particularly, to a flame retardant thermoplastic elastomer composition comprising a rubber copolymerized with at least two? -Olefin components and a polypropylene having a long- It is possible to improve the flame retardancy and to improve the weatherability and abrasion resistance of the skin layer by applying micro-foaming treatment to the skin layer and to improve the weatherability and abrasion resistance of the automobile interior trim panel and door trim Flame retardant thermoplastic elastomer composition for weather strips.
Description
본 발명은 자동차 웨더스트립용 난연 열가소성 탄성체 조성물에 관한 것이다.
The present invention relates to a flame retardant thermoplastic elastomer composition for automotive weather strips.
웨더스트립(Weather strip)은 차체와 도어의 접합부에 장착되어 외부의일반 이물질 유입을 막고, 고속 주행 시 바람소리 유입을 막으며, 차체 진동으로부터 도어의 흔들림을 막는 등의 다양한 기능을 가지고 있다. 일반적으로 자동차에 적용되는 웨더스트립의 캐리어부 표피층은 에틸렌 프로필렌 디엔 모노머(Ethylene propylene diene monomer, EPDM) 소재와 서모 플라스틱 올레핀(Thermo plastic olefin, TPO) 소재로 구성되어 있고 자동차 내장용 인스트루먼트 판넬 및 도어트림부는 폴리염화비닐(Polyvinyl chloride, PVC), 열가소성 폴리우레탄(Thermoplastic polyurethane, TPU) 및 열가소성 폴리올레핀(Thermoplastic polyolefin, TPO) 소재 등을 이용하고 있다.The weather strip is attached to the junction of the vehicle body and the door to prevent inflow of general foreign substances, prevents wind noise from entering at high speeds, and prevents the door from shaking from the body vibration. In general, the carrier layer of the weather strip used for automobiles is composed of ethylene propylene diene monomer (EPDM) and thermo plastic olefin (TPO) materials. The instrument panel panel and door trim Parts such as polyvinyl chloride (PVC), thermoplastic polyurethane (TPU) and thermoplastic polyolefin (TPO) materials.
종래 이러한 열가소성 탄성체 조성물에 관해 한국공개특허 제2012-0055420호에는 EPDM 고무와 함께 고 용융지수를 갖는 장쇄분기를 함유한 폴리프로필렌을 매트릭스 수지로 하여 가교제, 가교조제, 발포제, 나노크리스탈 스트럭쳐 엘라스토머, 산화방지제, 무기충전제, 폴리프로필렌계 왁스 및 프로세스 오일을 함유하는 웨더스트립용 조성물에 관해 제안되어 있다. 그러나 상기 재질은 난연성이 취약하고 발포층과 미발포층이 2개의 다른 재질로 구성되어 성형 공법상의 원가 상승과 외관 분리 등의 한계가 있다.Conventional thermoplastic elastomer compositions are disclosed in Korean Patent Publication No. 2012-0055420 in which polypropylene containing a long-chain branch having a high melt index together with EPDM rubber is used as a matrix resin and a crosslinking agent, a crosslinking aid, a foaming agent, a nanocrystal structure elastomer, An anti-static agent, an inorganic filler, a polypropylene wax and a process oil. However, the material is poor in flame retardancy, and the foamed layer and the unfoamed layer are composed of two different materials, which has limitations such as cost increase in the molding method and separation of the appearance.
따라서 이를 해결하기 위한 열가소성 소재의 난연성 향상과 공정의 단순화 등에 대한 연구가 필요한 실정이다.
Therefore, it is necessary to study the improvement of the flame retardancy of thermoplastic materials and the simplification of the process.
이에, 본 발명자들은 종래 기술의 문제점을 해결하기 위해 연구 노력한 결과, α-올레핀계 성분들이 2종류 이상 공중합된 고무와 장쇄분기를 가진 고용융 지수의 폴리프로필렌을 함유한 조성물을 제조함으로써 기존 대비 공정의 단순화, 고급감 구현 및 난연성 특성을 만족할 수 있다는 사실을 알게되어 발명을 완성하였다.The present inventors have made efforts to solve the problems of the prior art, and as a result, they have found that by preparing a composition containing a rubber having at least two kinds of copolymerized? -Olefin components and a polypropylene having a high melt index And the flame retardant property can be satisfied. Thus, the present invention has been completed.
따라서 본 발명은 α-올레핀계 성분들이 2종류 이상 공중합된 고무와 장쇄분기 함유 폴리프로필렌을 함유한 자동차 웨더스트립용 난연 열가소성 탄성체 조성물을 제공하는데 그 목적이 있다.
SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a flame retardant thermoplastic elastomer composition for automotive weather strips, which contains a rubber in which two or more kinds of? -Olefin-based components are copolymerized and a long-chain branched polypropylene.
상기한 과제 해결을 위하여, 본 발명은 α-올레핀계 성분들이 2종류 이상 공중합된 고무 50~80 중량% 및 장쇄분기 함유 폴리프로필렌 20~50 중량%를 포함하는 매트릭스 수지 100 중량부에 대하여 제 1 난연제 10~20 중량부; 제 2 난연제 10~50 중량부; 제 3 난연제 5~15 중량부; 나노크레이 5~15 중량부; 가교제 0.6~1.3 중량부; 가교조제 0.3~1 중량부; 나노크리스탈 스트럭처 엘라스토머 3~5 중량부; 멜트 텐션 강화제 0.1~0.4 중량부; 발포제 0.2~0.4 중량부; 폴리프로필렌계 왁스 0.3~0.6 중량부; 실리콘 마스터 배치 1~5 중량부; 내열노화방지제 0.2~0.6 중량부; 무기충전제 1~5 중량부; 및 고점도 파라핀 오일 20~40 중량부;를 포함하는 자동차 웨더스트립용 난연 열가소성 탄성체 조성물을 제공한다.
In order to solve the above problems, the present invention provides a process for producing a rubber composition comprising 100 parts by weight of a matrix resin comprising 50 to 80% by weight of a rubber copolymerized with two or more? -Olefin components and 20 to 50% 10 to 20 parts by weight of a flame retardant; 10 to 50 parts by weight of a second flame retardant; 5 to 15 parts by weight of a third flame retardant; 5 to 15 parts by weight of a nanoclay; 0.6 to 1.3 parts by weight of a crosslinking agent; 0.3 to 1 part by weight of a crosslinking auxiliary; 3 to 5 parts by weight of a nano-crystal structure elastomer; 0.1 to 0.4 parts by weight of a melt tension enhancer; 0.2 to 0.4 parts by weight of a foaming agent; 0.3 to 0.6 parts by weight of a polypropylene wax; 1 to 5 parts by weight of a silicon master batch; 0.2 to 0.6 parts by weight of a heat aging inhibitor; 1 to 5 parts by weight of an inorganic filler; And 20 to 40 parts by weight of a highly viscous paraffin oil.
본 발명에 따르면, α-올레핀계 성분들이 2종류 이상 공중합된 고무와 장쇄분기를 가진 고용융 지수의 폴리프로필렌을 혼합한 난연 열가소성 탄성체 조성물을 제조함으로써 난연성이 향상되었으며, 표피층에 미세발포 처리를 통해 외관의 질감을 부여하여 고급감을 구현할 수 있다.According to the present invention, the flame retardant thermoplastic elastomer composition prepared by mixing two or more kinds of copolymerized α-olefin-based components with a polypropylene having a long-chain branch and a high melt index has been prepared, and the flame retardancy is improved. It is possible to realize a sense of quality by giving a texture of appearance.
또한 본 발명의 난연 열가소성 탄성체 조성물은 기존대비 공정이 단순화되고, 내후성 및 내마모성을 향상시키는 효과가 있으며, 웨더스트립 표피층뿐만 아니라 자동차용 내장 인스트루먼트 판넬 및 도어 트림의 표피층 등에 유용하게 적용할 수 있다.
Further, the flame retardant thermoplastic elastomer composition of the present invention has an effect of simplifying the process compared to the conventional process, improving weatherability and abrasion resistance, and can be applied not only to the weather strip skin layer but also to the interior instrument panel for automobiles and the skin layer of door trim.
도 1 은 기존 재질로 이루어진 자동차용 바디사이트 웨더스트립을 나타낸 사진이다.
도 2는 기존 재질로 이루어진 자동차용 내장 인스트루먼트 판넬 및 도어 트림을 나타낸 사진이다.
도 3은 자동차용 웨더스트립의 구조를 개략적으로 나타낸 단면도이다.
도 4는 본 발명에 따른 난연 열가소성 탄성체 조성물은 함유한 인스트루먼터 판넬 소재(좌)와 웨더스트립 소재(우)의 단면을 개략적으로 나타낸 단면도이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing an automotive body site weather strip made of a conventional material.
2 is a photograph showing a built-in instrument panel and a door trim made of a conventional material.
3 is a cross-sectional view schematically showing the structure of a weather strip for an automobile.
4 is a cross-sectional view schematically showing a cross section of an instrument panel material (left) and a weather strip material (right) containing the flame retardant thermoplastic elastomer composition according to the present invention.
이하에서는 본 발명을 하나의 구현예로써 더욱 자세하게 설명한다.Hereinafter, the present invention will be described in more detail as an embodiment.
본 발명은 α-올레핀계 성분들이 2종류 이상 공중합된 고무, 장쇄분기 함유 폴리프로필렌, 제 1 난연제, 제 2 난연제, 제 3 난연제, 나노크레이, 가교제, 가교조제, 나노크리스탈 스트럭처 엘라스토머, 멜트 텐션 강화제, 발포제, 폴리프로필렌계 왁스, 실리콘 마스터 배치, 내열노화방지제, 무기충전제, 고점도 파라핀 오일을 포함하는 자동차 웨더스트립용 난연 열가소성 탄성체 조성물을 특징으로 한다.The present invention relates to a rubber composition comprising at least two kinds of α-olefin-based components copolymerized with rubber, a long-chain branched polypropylene, a first flame retardant, a second flame retardant, a third flame retardant, a nanoclay, a crosslinking agent, a crosslinking assistant, a nanocrystal structure elastomer, , A foaming agent, a polypropylene wax, a silicone master batch, a heat resistant antioxidant, an inorganic filler, and a highly viscous paraffin oil.
본 발명의 바람직한 구현예에 따르면, 상기 α-올레핀계 성분들이 2종류 이상 공중합된 고무는 50 ~ 80 중량%를 사용하는 것이 바람직하며, 가장 바람직하기로는 60 중량%를 사용할 수 있다. 이때 함량이 50 중량% 보다 적으면 경도 상승에 따른 감성 품질이 저하되는 단점이 있으며, 80 중량% 보다 많으면 발포 성능 및 내마모성이 저하되는 문제점이 발생 할 수 있다. 또한 α-올레핀계 성분들이 2종류 이상 공중합된 고무로 가장 바람직하기로는 에틸렌 프로필렌 디엔 모노머(EPDM)을 사용하는 것이 좋다. According to a preferred embodiment of the present invention, it is preferable to use 50 to 80% by weight, and most preferably 60% by weight, of the rubber in which two or more kinds of the? -Olefin-based components are copolymerized. If the content is less than 50% by weight, the quality of sensibility deteriorates due to the increase in hardness. If the content is more than 80% by weight, foaming performance and abrasion resistance may be deteriorated. Further, it is preferable to use an ethylene propylene diene monomer (EPDM) as the rubber in which two or more? -Olefin-based components are copolymerized.
본 발명의 바람직한 구현예에 따르면, 상기 장쇄분기 함유 폴리프로필렌은 범용 폴리프로필렌에 비해 녹는점(Tm) 부근에서 점도 변화가 크지 않기 때문에 발포 시 기포의 붕괴 및 융착을 억제하여 발포 성능을 향상시킬 수 있다. 또한 상기 장쇄분기 함유 폴리프로필렌은 20 ~ 50 중량%를 사용하는 것이 바람직하며, 가장 바람직하기로는 40 중량%를 사용할 수 있다. 이때 함량이 20 중량% 보다 적으면 상기에서 언급한 발포 시 기포의 붕괴 및 융착을 억제하는 효과가 저하될 수 있으며, 50 중량% 보다 많으면 발포 시 기포의 붕괴 및 융착을 억제하는 효과를 더 기대하기 어렵고, 경도 상승에 따른 감성 품질 저하의 문제가 발생할 수 있는 단점이 있다.According to a preferred embodiment of the present invention, the long-chain branch-containing polypropylene has a melting point ( Tm ) It is possible to suppress foam collapse and fusion at the time of foaming and improve foaming performance. The long-chain branched polypropylene is preferably used in an amount of 20 to 50% by weight, and most preferably 40% by weight. If the content is less than 20% by weight, the effect of suppressing the collapse and fusion of the bubbles during foaming may be deteriorated. If the content is more than 50% by weight, the effect of suppressing collapse and fusion of bubbles during foaming is more expected There is a disadvantage that a problem of deterioration of sensibility may occur due to an increase in hardness.
본 발명의 바람직한 구현예에 따르면, 난연제는 최소한의 첨가량으로 최대의 난연 효과를 발현하기 위해 3종의 서로 다른 난연제를 사용하는데, 상기 제 1 난연제는 10 ~ 20 중량부를 사용하는 것이 바람직하다. 이때 함량이 10 중량부 보다 적으면 난연성(V-0)을 확보하기 어려운 단점이 있으며, 20 중량부 보다 많으면 압출 시 표면 불량 발생 및 가격 상승의 원인이 될 수 있다. 또한 상기 제 1 난연제는 바람직하기로는 디카브로모디페닐 에탄(Decabromodiphenyl ethane)을 사용하는 것이 좋다.According to a preferred embodiment of the present invention, the flame retardant uses three different flame retardants in order to exhibit the maximum flame retardant effect with a minimum addition amount, and it is preferable to use 10 to 20 parts by weight of the first flame retardant. If the content is less than 10 parts by weight, it is difficult to ensure flame retardancy (V-0). If the content is more than 20 parts by weight, surface defects may occur and the price may increase during extrusion. The first flame retardant is preferably decabromodiphenyl ethane.
본 발명의 바람직한 구현예에 따르면, 상기 제 2 난연제는 10 ~ 50 중량부를 사용하는 것이 바람직하다. 이때 함량이 10 중량부 보다 적으면 제1 난연제의 난연성 시너지 효과 감소의 원인이 될 수 있으며, 50 중량부 보다 많으면 제1 난연제와의 시너지 효과가 더 상승되기 보다는 압출 시 분해 반응으로 수분이 발생하여 난연성이 저하될 수 있다. 또한 상기 제 2 난연제는 수산화마그네슘(Magnesium hydroxide)을 사용하는 것이 바람직하다.According to a preferred embodiment of the present invention, 10 to 50 parts by weight of the second flame retardant is preferably used. If the content is less than 10 parts by weight, the flame retardant synergistic effect of the first flame retardant may be reduced. If the content is more than 50 parts by weight, the synergistic effect with the first flame retardant is not increased, The flame retardancy may be lowered. The second flame retardant is preferably magnesium hydroxide.
본 발명의 바람직한 구현예에 따르면, 상기 제 3 난연제는 5 ~ 15 중량부를 사용하는 것이 바람직하다. 이때 함량이 5 중량부 보다 적으면 제1난연제, 또는 제2 난연제 첨가량의 증가를 초래하는 단점이 있으며, 15 중량부 보다 많으면 난연성 상승 효과 보다는 제품 가격이 급격하게 상승될 수 있다. 또한 상기 제 3 난연제는 바람직하기로는 암모늄 폴리인산(Ammonium Polyphosphate)을 사용하는 것이 좋다.According to a preferred embodiment of the present invention, 5 to 15 parts by weight of the third flame retardant is preferably used. If the content is less than 5 parts by weight, the amount of the first flame retardant or the second flame retardant is increased. If the content is more than 15 parts by weight, the price of the product may be increased sharply rather than the flame retardancy increasing effect. The third flame retardant is preferably an ammonium polyphosphate.
본 발명의 바람직한 구현예에 따르면, 상기 나노크레이는 5 ~ 15 중량부를 사용하는 것이 바람직하다. 이때 함량이 5 중량부 보다 적으면 난연성이 저하되는 단점이 있으며, 15 중량부 보다 많으면 미분산에 따른 표면 불량이 발생할 수 있다. According to a preferred embodiment of the present invention, 5 to 15 parts by weight of the nanoclay is preferably used. If the content is less than 5 parts by weight, the flame retardancy is deteriorated. If the content is more than 15 parts by weight, surface defects due to fine dispersion may occur.
본 발명의 바람직한 구현예에 따르면, 상기 가교제는 0.6 ~ 1.3 중량부를 사용하는 것이 바람직하고, 상기 가교제는 반감기 온도 170 ℃의 과산화물 가교제인 2,5-디메틸-2,5-디-터셜리 부틸 퍼옥시 헥산(2,5-Dimethyl-2,5-di-(tert-butylperoxy)-hexane)을 사용하는 것이 바람직하다. 또한 상기 가교조제는 0.3 ~ 1 중량부를 사용할 수 있으며, 상기 가교조제는 N,N'-m-페닐렌디말레이미드를 사용하는 것이 바람직하다.According to a preferred embodiment of the present invention, the cross-linking agent is preferably used in an amount of 0.6 to 1.3 parts by weight, and the cross-linking agent is a 2,5-dimethyl-2,5-di-tert- It is preferable to use 2,5-dimethyl-2,5-di- (tert-butylperoxy) -hexane. The crosslinking assistant may be used in an amount of 0.3 to 1 part by weight, and the crosslinking assistant is preferably N, N'-m-phenylene dimaleimide.
본 발명의 바람직한 구현예에 따르면, 상기 나노크리스탈 스트럭처 엘라스토머는 3 ~ 5 중량부를 사용하는 것이 바람직하고, 균일한 발포 셀을 형성하는 특징이 있으며, 바람직하기로는 프로필렌 올레핀 코폴리머를 사용하는 것이 좋다. According to a preferred embodiment of the present invention, the nanocrystal structure elastomer is preferably used in an amount of 3 to 5 parts by weight, and is characterized in that it forms a uniform foamed cell, and preferably a propylene olefin copolymer is used.
본 발명의 바람직한 구현예에 따르면, 상기 멜트 텐션 강화제는 0.1 ~ 0.4 중량부를 사용하는 것이 바람직하며, 상기 멜트 텐션 강화제는 형성된 셀의 붕괴를 억제하는 특징이 있는 스타이렌 아크릴로나이트릴(styrene acrylonitrile, SAN)로 코팅된 폴리테트라플루오로에틸렌(polytetrafluoroethylene, PTFE)를 사용하는 것이 바람직하다. According to a preferred embodiment of the present invention, the melt tension enhancer is preferably used in an amount of 0.1 to 0.4 part by weight, and the melt tension enhancer is preferably styrene acrylonitrile having a property of inhibiting collapse of the formed cell, SAN) coated with polytetrafluoroethylene (PTFE) is preferably used.
본 발명의 바람직한 구현예에 따르면, 상기 발포제는 0.2 ~ 0.4 중량부를 사용할 수 있으며, 입자크기가 2~5㎛인 폴리 에틸렌이 코팅된 아조디카르본아미드(Azodicarbonamide), p,p'-옥시비스(벤젠술포닐하이드라지드)(p,p'-oxibis (benzene sulfonylhydrazide)) 또는 이들의 혼합물을 사용하는 것이 바람직하다. According to a preferred embodiment of the present invention, the foaming agent may be used in an amount of 0.2 to 0.4 parts by weight, and may be azodicarbonamide coated with polyethylene having a particle size of 2 to 5 μm, p, p'-oxybis ( Benzene sulfonyl hydrazide) (p, p'-oxibis (benzene sulfonylhydrazide)) or a mixture thereof is preferably used.
본 발명의 바람직한 구현예에 따르면, 자동차 웨더스트립용 제품의 표면 스크래치성 개선과 내마모성을 증가시키기 위해 상기 폴리프로필렌계 왁스를 사용하는데, 이때 함량은 0.3 ~ 0.6 중량부를 사용할 수 있다. According to a preferred embodiment of the present invention, the polypropylene wax is used in order to improve surface scratch resistance and abrasion resistance of a product for automotive weather strips, wherein the content may be 0.3 to 0.6 parts by weight.
그 밖에도 당 분야에서 통상적으로 사용되는 상기 실리콘 마스터 배치는 1 ~ 5 중량부, 상기 내열노화방지제는 0.2 ~ 0.6 중량부, 상기 고점도 파라핀 오일은 20 ~ 40 중량부를 사용할 수 있는데, 상기 내열노화방지제는 테트라키스(3,5-디-터셜리-부틸-4-하이드록시페닐)프로피오네이트를 사용하는 것이 바람직하다. 또한 상기 무기충전제는 1 ~ 5 중량부를 사용할 수 있으며, 이때 상기 무기충전제는 입자 크기가 1~10㎛인 탄산칼슘을 사용하는 것이 바람직하다. In addition, the silicone masterbatch may be used in an amount of 1 to 5 parts by weight, 0.2 to 0.6 parts by weight of the heat resistant antioxidant, and 20 to 40 parts by weight of the high viscosity paraffin oil, Tetrakis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferably used. The inorganic filler may be used in an amount of 1 to 5 parts by weight, and the inorganic filler may be calcium carbonate having a particle size of 1 to 10 μm.
이상에서 설명한 바와 같은 조성성분을 포함하는 본 발명의 자동차 웨더스트립용 난연 열가소성 탄성체 조성물은 웨더스트립 표피층뿐만 아니라 자동차용 내장 인스트루먼트 판넬 및 도어 트림의 표피층 등에 유용하게 적용할 수 있다.The flame retardant thermoplastic elastomer composition for automotive weather strips of the present invention comprising the composition components as described above can be applied not only to the weather strip skin layer but also to the interior instrument panel for automobiles and the skin layer of door trim.
또한 상기 난연 열가소성 탄성체 조성물은 1) 난연성의 확보, 2) 표피층에 미세발포 처리를 통한 외관 질감 부여(스웨이드 촉감 부여), 3) 기존의 내후성 개선(변색), 4) 마모성 향상, 5) 기존 대비 공정의 단순화, 6) 고급감 구현 등의 효과를 기대할 수 있다.
In addition, the flame retardant thermoplastic elastomer composition is excellent in flame retardant thermoplastic elastomer composition in terms of: 1) ensuring flame retardancy; 2) imparting an appearance texture (imparting suede feel) to the skin layer through microfoaming; 3) improving weather resistance (discoloration) Simplification of the process, and (6) implementation of a sense of quality.
이하, 본 발명을 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 다음 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
실시예 1, 2 및 비교예 1, 2Examples 1 and 2 and Comparative Examples 1 and 2
하기 표 1의 조성으로 자동차 웨더스트립용 난연 열가소성 탄성체 조성물을 제조하였다.A flame retardant thermoplastic elastomer composition for automotive weather strips was prepared with the composition shown in Table 1 below.
상기 조성물의 제조에 사용되는 성분은 구체적으로 예시하면 하기와 같다.Specific examples of the components used in the preparation of the composition are as follows.
1)에틸렌 프로필렌 디엔 모노머(EPDM): 금호폴리켐사 KEP 24801) Ethylene propylene diene monomer (EPDM): Kumho Polychems KEP 2480
2)장쇄분기 폴리프로필렌: D114, Dow사2) long-chain branched polypropylene: D114, Dow
3)범용 폴리프로필렌: BP2000, 대한유화사 3) General purpose polypropylene: BP2000,
4)가교제(2,5-디메틸-2,5-디-(터셜리 부틸 퍼옥시) 헥산): Luperox 101-50D, Atochem사 4) Crosslinking agent (2,5-dimethyl-2,5-di- (tertiarybutylperoxy) hexane): Luperox 101-50D, Atochem
5)가교조제(N,N'?-페닐렌디말레이미드): TAC-50, DEGUSA사 5) Crosslinking aid (N, N'-phenylene dimaleimide): TAC-50, DEGUSA Inc.
6)발포제(p,p'-옥시비스(벤젠-술포닐하이드라지드)):EE188E, EIWA사6) Foaming agent (p, p'-oxybis (benzene-sulfonyl hydrazide)): EE188E, EIWA
7)나노크리스탈 스트럭처 엘라스토머(프로필렌 올레핀 코폴리머): Notio, Mitsui chemical사7) Nano-Crystal Structure Elastomer (Propylene Olefin Copolymer): Notio, Mitsui chemical
8)내열노화방지제(테트라키스(3,5-디-터셜리-부틸-4-하이드록시페닐)프로피오네이트): S1010, 송원산업사8) Heat aging inhibitor (tetrakis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate): S1010,
9)무기충전제(탄산칼슘): SF, 동호칼슘사9) Inorganic filler (calcium carbonate): SF, Dongho Calcium Co.
10)폴리프로필렌계 왁스: 500시리즈, 라이온켐텍사10) Polypropylene wax: 500 series, Lion Chemtech
11)파라핀계 오일: KL1100, SJC사11) Paraffin oil: KL1100, SJC Co.
12)제 1 난연제(Decabromodiphenyl ethane): Fire master 2100, Chemtura사12) First flame retardant (Decabromodiphenyl ethane): Fire master 2100, Chemtura
13)제 2 난연제(Magnesium hydroxide: PFR-5S, POSCO Chemtech사13) Secondary flame retardant (PFR-5S, manufactured by POSCO Chemtech Co.,
14)제 3 난연제(Ammonium Polyphosphate): 일양화학사14) Third flame retardant (Ammonium Polyphosphate):
15)나노크레이(methyl, dihydrogenatedtallow ammonium): Cloisite 93A, Southern Clay Products, Inc.15) methyl, dihydrogenated tallow ammonium: Cloisite 93A, Southern Clay Products, Inc.
16)실리콘 마스터배치: MB 002, DOW사16) Silicone master batch: MB 002, DOW company
17)멜트 텐션 강화제(PTFE): GCC KOREA사 AD-54117) Melt Tension Reinforcement (PTFE): GCC KOREA AD-541
실험예Experimental Example
[물성 측정][Measurement of physical properties]
상기 실시예 1, 2 및 비교예 1, 2에서 제조된 조성물의 내마모성, 난연성, 발포외관, 제품감촉 및 셀 크기 등을 측정하여 그 결과를 하기 표 2에 정리하여 나타내었다. 물성 측정방법을 구체적으로 설명하면 하기와 같다.The abrasion resistance, flame retardancy, foam appearance, product feel and cell size of the compositions prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured and the results are summarized in Table 2 below. The method for measuring the physical properties will be described in detail as follows.
[물성 측정방법][Measurement of physical properties]
1)내마모성은 1 kgf 하중에서 면범포를 마찰천으로 사용하여, 속도 50 r/min, 마찰거리 130 mm의 조건에서 시험하였다. 1) Abrasion resistance was tested at speed 50 r / min, the conditions of the friction distance 130 mm by using a rubbing cloth canvas surface at f 1 kg load.
2)난연성은 UL-94에 의거하여 시편 크기를 125mm(L) × 12.5mm(W) × 2mm(D)로 분젠버너를 이용하여 파란색 불꽃으로 10초간 연소 후 소화 시간 측정을 실시하였다.2) The flame retardancy was measured by burning the specimen with 125mm (L) × 12.5mm (W) × 2mm (D) using a Bunsen burner for 10 seconds in accordance with UL-94.
3)셀 크기는 SEM(전자주사현미경, 모델: S2400, HITACHI社)을 이용하여 측정하였다.3) The cell size was measured using SEM (electron microscope, model: S2400, HITACHI).
상기 표 2에 나타낸 바와 같이, 장쇄분기 함유 폴리프로필렌과 EPDM 소재를 함유한 상기 실시예 1 및 2의 조성물은 내마모성 및 난연성이 우수하고, 범용 폴리프로필렌을 사용한 비교예 1 및 2에 비해 셀 크기 분포가 좁아짐으로 인해 발포 외관과 제품 감촉이 향상된 것을 확인할 수 있다.As shown in Table 2 above, the compositions of Examples 1 and 2 containing the long-chain branch-containing polypropylene and the EPDM material were excellent in abrasion resistance and flame retardancy, and compared with Comparative Examples 1 and 2 using a general purpose polypropylene, It is confirmed that the appearance of foam and the feel of product are improved.
따라서 본 발명에 따른 자동차 웨더스트립용 난연 열가소성 탄성체 조성물은 1) 난연성의 확보, 2) 표피층에 미세발포 처리를 통한 외관 질감 부여(스웨이드 촉감 부여), 3) 기존의 내후성 개선(변색), 4) 마모성 향상, 5) 기존 대비 공정의 단순화, 6) 고급감 구현 등의 효과를 기대할 수 있다.Therefore, the flame retardant thermoplastic elastomer composition for automotive weather strips for automotive weather strips according to the present invention has the following characteristics: 1) ensuring flame retardancy; 2) imparting an appearance texture (imparting suede feeling) to the skin layer through micro- Abrasion resistance, 5) simplification of existing processes, and 6) a sense of quality.
Claims (10)
디카브로모디페닐 에탄(Decabromodiphenyl ethane)의 제 1 난연제 10~20 중량부;
수산화마그네슘의 제 2 난연제 10~50 중량부;
암모늄 폴리인산의 제 3 난연제 5~15 중량부;
나노크레이 5~15 중량부;
가교제 0.6~1.3 중량부;
가교조제 0.3~1 중량부;
나노크리스탈 스트럭처 엘라스토머 3~5 중량부;
스타이렌 아크릴로나이트로 코팅된 폴리테트라플루오로에틸렌의 멜트 텐션 강화제 0.1~0.4 중량부;
발포제 0.2~0.4 중량부;
폴리프로필렌계 왁스 0.3~0.6 중량부;
실리콘 마스터 배치 1~5 중량부;
내열노화방지제 0.2~0.6 중량부;
무기충전제 1~5 중량부; 및
고점도 파라핀 오일 20~40 중량부;
를 포함하는 자동차 웨더스트립용 난연 열가소성 탄성체 조성물.to 100 parts by weight of a matrix resin comprising 50 to 80% by weight of a rubber in which two or more? -olefin-based components are copolymerized and 20 to 50% by weight of a long-chain branched polypropylene,
10 to 20 parts by weight of a first flame retardant of decabromodiphenyl ethane;
10 to 50 parts by weight of a second flame retardant of magnesium hydroxide;
5 to 15 parts by weight of a third flame retardant of ammonium polyphosphoric acid;
5 to 15 parts by weight of a nanoclay;
0.6 to 1.3 parts by weight of a crosslinking agent;
0.3 to 1 part by weight of a crosslinking auxiliary;
3 to 5 parts by weight of a nano-crystal structure elastomer;
0.1 to 0.4 parts by weight of a melt tension enhancer of polytetrafluoroethylene coated with styrene acrylonitrile;
0.2 to 0.4 parts by weight of a foaming agent;
0.3 to 0.6 parts by weight of a polypropylene wax;
1 to 5 parts by weight of a silicon master batch;
0.2 to 0.6 parts by weight of a heat aging inhibitor;
1 to 5 parts by weight of an inorganic filler; And
20 to 40 parts by weight of a highly viscous paraffin oil;
And a flame retardant thermoplastic elastomer composition for automotive weather strips.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100216649B1 (en) | 1996-03-04 | 1999-09-01 | 사또 아끼오 | Foamable olefin thermoplastic elastomer compositions and foamed products thereof |
| KR20090058887A (en) * | 2007-12-05 | 2009-06-10 | 주식회사 엘지화학 | Flame retardant polypropylene composition with enhanced long term heat resistance |
| KR20100102479A (en) * | 2009-03-11 | 2010-09-24 | 현대자동차주식회사 | Weather strip compositions |
| KR20120055420A (en) * | 2010-11-23 | 2012-05-31 | 현대자동차주식회사 | Foamed thermoplastic elastomer composition for weather strip |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100216649B1 (en) | 1996-03-04 | 1999-09-01 | 사또 아끼오 | Foamable olefin thermoplastic elastomer compositions and foamed products thereof |
| KR20090058887A (en) * | 2007-12-05 | 2009-06-10 | 주식회사 엘지화학 | Flame retardant polypropylene composition with enhanced long term heat resistance |
| KR20100102479A (en) * | 2009-03-11 | 2010-09-24 | 현대자동차주식회사 | Weather strip compositions |
| KR20120055420A (en) * | 2010-11-23 | 2012-05-31 | 현대자동차주식회사 | Foamed thermoplastic elastomer composition for weather strip |
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