KR20040054899A - Polypropylene resin composition with superior scratch resistance and impact strength - Google Patents
Polypropylene resin composition with superior scratch resistance and impact strength Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
Description
본 발명은 내스크래치성 및 충격강도가 우수한 자동차 내장재용 폴리프로필렌 수지 조성물에 관한 것으로서, 더욱 상세하게는 프로필렌-에틸렌 블록 공중합체에 올레핀계 엘라스토머, 유기과산화물 및 가교조제를 첨가하고 침상의 실리카 또는 판상의 탈크, 변성 폴리프로필렌 등을 첨가하여 성형품 표면에 손상을 일으키는 내스크래치성이 우수하고 내열성, 저온 충격 특성, 강성 등의 물성뿐만 아니라 성형 가공성이 우수함으로써 자동차, 가전 제품의 부품으로 유용하며, 특히 제품의 외관 품질이 중요한 자동차의 내장 부품 등에 매우 적합하게 이용할 수 있는 폴리프로필렌 수지 조성물에 관한 것이다.The present invention relates to a polypropylene resin composition for automobile interior having excellent scratch resistance and impact strength, and more particularly, to an propylene-ethylene block copolymer, to which an olefin elastomer, an organic peroxide and a crosslinking aid are added, and a needle-like silica or plate It is useful as parts of automobiles and home appliances by adding talc and modified polypropylene, and having excellent scratch resistance to damage the surface of molded products, and excellent molding processability as well as physical properties such as heat resistance, low temperature impact properties, and rigidity. The present invention relates to a polypropylene resin composition which can be suitably used for interior parts of automobiles and the like, in which appearance quality of products is important.
종래의 프로필렌계 수지는 성형성, 내충격성, 내약품성 등이 뛰어나고 저 비중 및 저가의 장점을 가지고 있기 때문에 자동차의 범퍼 등의 외장재와 각종 필러 등의 내장재 용도로 폭 넓게 사용되고 있다. 그러나, 글러브 박스(Glove Box),콘솔(Console), 필러 트림(Pillar Trim)과 같은 자동차 내장재의 경우 안전성 및 미적 효과를 동시에 만족시킬 수 있는 충격강도와 내스크래치성의 발란스가 월등히 개선된 재료의 개발이 요구되고 있는 실정이다.Conventional propylene-based resins are widely used for exterior materials such as automobile bumpers and interior materials such as various fillers because they have excellent moldability, impact resistance, chemical resistance, and the like, and have advantages of low specific gravity and low cost. However, in the case of automobile interior materials such as glove box, console, and pillar trim, the development of materials with significantly improved impact strength and scratch resistance balance to satisfy safety and aesthetic effects at the same time This situation is required.
지금까지 글러브 박스, 콘솔, 필러 트림과 같은 자동차 내장재로 개발된 폴리프로필렌계 수지 조성물 중에는 내충격성 및 강성 등의 물성 측면에서 양호한 제품은 있으나 충격강도가 높을수록 내스크래치성이 열등해지는 단점을 갖고 있다. 그런 까닭에 내충격성과 내스크래치성을 동시에 요구되는 경우에는 별도의 페인트 작업이 필요하게 되며 이는 원가상승이 수반하게 된다. 대한민국 특허 출원번호 제 2000-64690호에서 충격강도와 내스크래치성이 우수한 폴리프로필렌 수지 조성물을 제안한 바 있으나, 이 경우 가교가 지나치면 고분자량의 엘라스토머가 생성되어 내스크래치성은 개선되는 반면 가공시 플로우 마크 발생으로 인한 외관 품질이 저하되는 단점을 지니고 있으며 가교가 부족하면 스크래치성능이 개선되지 않는 문제점이 있었다.Polypropylene resin compositions developed as automotive interior materials such as glove boxes, consoles, and filler trims are good products in terms of physical properties such as impact resistance and stiffness, but the higher the impact strength, the lower the scratch resistance. . Therefore, when impact resistance and scratch resistance are required at the same time, a separate paint work is required, which is accompanied by a cost increase. In Korea Patent Application No. 2000-64690, a polypropylene resin composition having excellent impact strength and scratch resistance has been proposed, but in this case, when crosslinking is excessive, a high molecular weight elastomer is produced, which improves scratch resistance while processing flow marks. It has a disadvantage in that the appearance quality is deteriorated due to the occurrence and there is a problem that the scratch performance is not improved if the crosslinking is insufficient.
따라서, 충격강도, 강성 등의 기계적 성질, 플로우 마크 등의 가공성이 우수할 뿐만 아니라 내스크래치성이 우수한 수지 조성물의 개발은 자동차산업에 있어서 매우 중요하게 요구되고 있는 긴급한 과제로 대두되고 있다.Therefore, the development of a resin composition not only excellent in mechanical properties such as impact strength and rigidity, flow marks and the like but also excellent in scratch resistance has emerged as an urgent problem that is very important in the automobile industry.
이에, 본 발명자들은 종래 문제점을 해결하기 위하여, 프로필렌-에틸렌 블록 공중합체에 올레핀계 엘라스토머, 유기과산화물 및 가교조제를 첨가하고 침상의 실리카 또는 판상의 탈크, 변성 폴리프로필렌 등을 첨가하여 성형품 표면에 손상을 일으키는 내스크래치성이 우수하고 내열성, 저온 충격 특성, 강성 등의 물성 뿐만 아니라 성형 가공성이 우수함으로써 자동차, 가전 제품의 부품으로 매우 유용한 폴리프로필렌 수지 조성물개발함으로써 본 발명을 완성하였다.In order to solve the conventional problems, the present inventors add olefin-based elastomers, organic peroxides and crosslinking aids to propylene-ethylene block copolymers, and add acicular silica or plate-like talc, modified polypropylene, and the like to damage the surface of the molded article. The present invention has been completed by developing a polypropylene resin composition which is very useful for parts of automobiles and home appliances by having excellent scratch resistance and excellent molding processability as well as physical properties such as heat resistance, low temperature impact characteristics and rigidity.
따라서, 본 발명은 내스크래치성 및 충격강도가 우수한 자동차 내장재용 폴리프로필렌 수지 조성물을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a polypropylene resin composition for automobile interior having excellent scratch resistance and impact strength.
본 발명은The present invention
프로필렌 중합체 70 ∼ 100 중량%와 프로필렌-에틸렌 공중합체 0 ∼ 30 중량%로 구성된 프로필렌-에틸렌 블록공중합체 30 ∼ 70 중량%;30 to 70 wt% of a propylene-ethylene block copolymer composed of 70 to 100 wt% of a propylene polymer and 0 to 30 wt% of a propylene-ethylene copolymer;
에틸렌-프로필렌 공중합체 고무 또는 에틸렌-α-올레핀 공중합체로 구성된 올레핀계 엘라스토마가 5 ∼ 30중량%;5 to 30% by weight of an olefin elastomer composed of an ethylene-propylene copolymer rubber or an ethylene-α-olefin copolymer;
유기과산화물 0.01 ∼ 0.2중량%;0.01 to 0.2% by weight of organic peroxide;
가교조제 0.06 ∼ 1.2중량%;0.06 to 1.2% by weight of crosslinking aid;
평균입경이 0.5 ∼ 10 ㎛의 침상형태의 실리카 단독 혹은 탈크, 황산바륨, 탄산칼슘 올라스토나이트 중에서 선택된 기타 무기충진제가 혼합되어 있는 무기충진제 5 ∼ 40 중량%; 및5 to 40% by weight of an inorganic filler having a needle-like silica having an average particle diameter of 0.5 to 10 µm or a mixture of other inorganic fillers selected from talc, barium sulfate, and calcium carbonate stononite; And
불포화카르본산 및 이의 유도체로 그라프트하여 그라프트율이 0.5 ∼ 5 중량%의 변성 폴리프로필렌 수지 1 ∼ 7 중량%가 함유되어 있는 폴리프로필렌 수지조성물을 그 특징으로 한다.It is characterized by a polypropylene resin composition which is grafted with unsaturated carboxylic acid and derivatives thereof and contains 1 to 7% by weight of a modified polypropylene resin having a graft ratio of 0.5 to 5% by weight.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 프로필렌-에틸렌 블록 공중합체에 올레핀계 엘라스토머, 유기과산화물 및 가교조제를 첨가하고 침상의 실리카 또는 판상의 탈크, 변성 폴리프로필렌 등을 첨가하여 성형품 표면에 손상을 일으키는 내스크래치성이 우수하고 내열성, 저온 충격 특성, 강성 등의 물성 뿐만 아니라 성형 가공성이 우수함으로써 자동차, 가전 제품의 부품으로 매우 유용한 폴리프로필렌 수지 조성물에 관한 것이다.The present invention is excellent in scratch resistance and heat resistance by adding olefin elastomer, organic peroxide and crosslinking aid to the propylene-ethylene block copolymer, and adding needle-like silica or plate-like talc, modified polypropylene to damage the surface of the molded article. The present invention relates to a polypropylene resin composition which is very useful for parts of automobiles and home appliances due to excellent molding processability as well as physical properties such as low temperature impact characteristics and rigidity.
본 발명에 따른 수지 조성물에 있어서 폴리프로필렌 중합체는 프로필렌 모노머를 주성분으로 하는 프로필렌 중합체와 에틸렌이 함유된 프로필렌-에틸렌 공중합체로 구성된 결정성 폴리머이며, 프로필렌 중합체 단독 혹은 프로필렌-에틸렌 공중합체를 일부 혼합하여 사용하기도 한다. 프로필렌 중합체는13C-NMR로 측정한 펜타드 분율(mmmm분율)에 있어서 mmmm분율의 값이 96% 이상, 바람직하기로는 96.5 % 이상, 더욱 바람직하기로는 97% 이상이다. mmmm분율이 96% 미만이면 강성, 내열성 등이 떨어지게 된다. 또한, 프로필렌 중합체는 135 ℃ 데카린 중에서 측정한 극한점도[η]가 1.0 ∼ 3.0 ㎗/g이다. [η]가 1.0 ㎗/g 미만이면 충격강도가 떨어지고, 3.0 ㎗/g을 초과하면 성형성이 저하되므로 바람직하기로는 1.5 ∼ 2.5 ㎗/g이다. 또한, 프로필렌-에틸렌 공중합체는 크실렌 추출물의 135 ℃ 데카린 중에서의 극한점도[η]가 3.0 ㎗/g 이상이 바람직하다. 극한점도[η]가 3.0 ㎗/g 미만이면 충격강도가 저하된다. 보다 바람직한 극한점도[η]는 3.5㎗/g 이상, 특히 4.0 ㎗/g 이상이다. 또한, 에틸렌의 함량은 3 ∼ 20 중량% 이며 바람직하게는 5 ∼ 15 중량%이 좋다. 에틸렌 함량이 3 중량% 미만이면 충격강도 저하의 문제점이 있으며, 20 중량% 초과하면 내스크래치성과 강성 저하등의 문제점이 있다.In the resin composition according to the present invention, the polypropylene polymer is a crystalline polymer composed of a propylene polymer containing propylene monomer as a main component and a propylene-ethylene copolymer containing ethylene, and a mixture of propylene polymer alone or a part of propylene-ethylene copolymer Also used. The propylene polymer has a value of mmmm fraction of 96% or more, preferably 96.5% or more, and more preferably 97% or more in the pentad fraction (mmmm fraction) measured by 13 C-NMR. If the mmmm fraction is less than 96%, the stiffness and heat resistance will be degraded. Moreover, the intrinsic viscosity [(eta)] measured in 135 degreeC decalin of the propylene polymer is 1.0-3.0 dl / g. If [η] is less than 1.0 dl / g, the impact strength is lowered, and if it exceeds 3.0 dl / g, moldability is lowered, so it is preferably 1.5 to 2.5 dl / g. Moreover, as for the propylene ethylene copolymer, intrinsic viscosity [(eta)] in 135 degreeC decalin of xylene extract has preferable 3.0 dl / g or more. If the intrinsic viscosity [η] is less than 3.0 dl / g, the impact strength is lowered. More preferable intrinsic viscosity [eta] is 3.5 dl / g or more, especially 4.0 dl / g or more. In addition, the content of ethylene is 3 to 20% by weight, preferably 5 to 15% by weight. If the ethylene content is less than 3% by weight, there is a problem of lowering the impact strength, and if it exceeds 20% by weight, there is a problem of scratch resistance and stiffness.
또한, 프로필렌 중합체와 프로필렌-에틸렌 공중합체의 구성비는 70 ∼ 100 : 30 ∼ 0의 중량비, 더욱 바람직하기로는 80 ∼ 100 : 20 ∼ 0 중량비의 것이 충격강도와 유동성 발란스 면에서 바람직하다. 즉, 프로필렌 중합체의 경우는 내충격성이 부족하며, 프로필렌-에틸렌 공중합체는 성형성, 강성, 내열성 등이 부족하다. .In addition, the propylene polymer and the propylene-ethylene copolymer have a weight ratio of 70 to 100: 30 to 0, more preferably 80 to 100: 20 to 0, and a weight ratio is preferable in terms of impact strength and fluid balance. In other words, the propylene polymer lacks impact resistance, and the propylene-ethylene copolymer lacks moldability, rigidity, heat resistance, and the like. .
폴리프로필렌계 수지 조성물 중에 프로필렌-에틸렌 블록공중합체의 배합 비율은 전체 조성량의 30 ∼ 70 중량%, 바람직하기로는 45 ∼ 65 중량%이다. 이때, 70 중량% 초과하면 충격강도가 낮아지고, 30% 미만이 되면 성형성이 저하한다.The blending ratio of the propylene-ethylene block copolymer in the polypropylene resin composition is 30 to 70% by weight, preferably 45 to 65% by weight of the total composition. At this time, when it exceeds 70% by weight, the impact strength is lowered, and when it is less than 30%, moldability is lowered.
한편, 본 발명에 다른 폴리프로필렌 수지 조성물 중 고무성분은 에틸렌-프로필렌 공중합체 고무와 에틸렌-α-올레핀 공중합체가 각각 단독 혹은 블렌드로 구성된 올레핀계 엘라스토마로, 이의 함량은 5 ∼ 30 중량%, 바람직하기로는 15 ∼ 25 중량%이다. 만일 30 중량%를 초과하면 강성 및 성형성이 떨어지고, 5 중량% 미만이 되면 충격강도가 저하한다.Meanwhile, the rubber component of the polypropylene resin composition according to the present invention is an olefin elastomer composed of ethylene-propylene copolymer rubber and ethylene-α-olefin copolymer alone or in a blend, the content of which is 5 to 30% by weight, Preferably it is 15-25 weight%. If it exceeds 30% by weight, the rigidity and formability are inferior, and when it is less than 5% by weight, the impact strength is lowered.
에틸렌프로필렌 공중합체 고무(EPR)에 있어서 230 ℃의 용융지수(MI)가 0.1 ∼ 50 g/10min, 바람직하기로는 1.0 ∼ 30 g/10min이다. MI가 0.1 g/10min 미만이면 분산불량을 일으켜 플로우마크가 발생한다. 한편, 50 g/10min을 초과하면 내충격성이 저하하는 문제가 있다. EPR 중의 프로필렌 함유량이 20 ∼ 70 중량% 바람직하기로는 40 ∼ 60 중량%이다. 프로필렌 함유량이 20 중량% 미만이면, 충격강도가 저하되고, 70 중량% 초과하면 강성이 저하되기 때문이다. 또한, 에틸렌-α-올레핀 공중합체는 일반적으로 에틸렌 옥텐-1 공중합체(EOM)이 사용되며, 이때 사용되는 EOM의 경우 C8(옥텐) 함유량은 15 ∼ 45 중량%, 바람직하기로는 25 ∼ 35 중량%이며, 무니(Mooney)점도 ML 1+4(121 ℃)는 1 ∼ 50 ㎗/g, 바람직하기로는 1.5 ∼ 35 ㎗/g 이며, 밀도는 0.86 ∼ 0.91 g/㎤, 바람직하기로는 0.87 ∼0.90 g/㎤이다. 이때, 옥텐의 함유량이 15 중량% 미만이면 충격강도가 저하되고, 45 중량% 초과하면 강성이 저하되며, 무늬점도가 1 ㎗/g 미만이면 플로우 마크 발생 및 기계적 물성 저하되고, 50 ㎗/g 초과하면 충격강도가 저하되며, 밀도가 0.86 g/㎤ 미만이면 강성이 저하되고, 0.91 g/㎤ 초과하면 충격강도가 저하되므로 바람직하지 못하다.In ethylene propylene copolymer rubber (EPR), melt index (MI) of 230 degreeC is 0.1-50 g / 10min, Preferably it is 1.0-30 g / 10min. If the MI is less than 0.1 g / 10min, a dispersion mark is caused, resulting in a flow mark. On the other hand, when it exceeds 50 g / 10min, there exists a problem that impact resistance falls. The propylene content in the EPR is 20 to 70% by weight, preferably 40 to 60% by weight. It is because impact strength falls that propylene content is less than 20 weight%, and rigidity falls when it exceeds 70 weight%. In addition, the ethylene-α-olefin copolymer is generally used an ethylene octene-1 copolymer (EOM), in the case of the EOM used is C 8 (octene) content of 15 to 45% by weight, preferably 25 to 35 Weight%, Mooney viscosity ML 1 + 4 (121 ° C.) is 1-50 dl / g, preferably 1.5-35 dl / g, density is 0.86-0.91 g / cm 3, preferably 0.87- 0.90 g / cm 3. At this time, when the content of octene is less than 15% by weight, the impact strength is lowered, and when the content of octene is more than 45% by weight, the rigidity is lowered. The lower the impact strength, the lower the density, if the density is less than 0.86 g / cm 3, the rigidity is lowered, if the density exceeds 0.91 g / cm 3 it is not preferable because the impact strength is lowered.
폴리프로필렌 수지 조성물 중 유기과산화물로는 반감기가 1분이고 분해온도가 150 ∼ 270 ℃ 인 것이 바람직하다. 이는 플로우 마크가 발생하지 않으면서 내스크래치성이 향상되어야 하기 때문이다. 유기과산화물의 함량은 0.01 ∼ 0.2 중량%, 더욱 바람직하기로는 0.02 ∼ 0.1중량%이며, 이를 배합함과 동시에 가교조제와의 배합비를 고려할 필요가 있다. 이의 함량이 0.01 중량% 미만이면 반응성이 떨어지게 되어 우수한 물성을 얻을 수 없게 되고 0.2 중량%를 초과하면 반응성은 높아지는 반면 유동성 변화가 매우 심하다.The organic peroxide in the polypropylene resin composition preferably has a half life of 1 minute and a decomposition temperature of 150 to 270 ° C. This is because scratch resistance must be improved without generating a flow mark. The content of the organic peroxide is 0.01 to 0.2% by weight, more preferably 0.02 to 0.1% by weight, and at the same time, it is necessary to consider the blending ratio with the crosslinking aid. If the content thereof is less than 0.01% by weight, the reactivity decreases, so that excellent physical properties cannot be obtained. If the content thereof exceeds 0.2% by weight, the reactivity is increased while the flowability is very severe.
또한, 폴리프로필렌 수지 조성물 중 가교조제로 디비닐화합물, 말레이미드(Maleimide) 화합물, 퀴논다이옥심(Quinone dioxim) 화합물 등이 바람직하며, 이를 0.06 ∼ 1.2 중량%로 배합하고, 유기과산화물과의 배합비[(가교조제)/(유기과산화물)]는 4 ∼ 10 : 1(중량비)을 만족하여야 한다. 유기과산화물이 0.05 중량% 미만 혹은 배합비가 3미만인 경우 분해반응이 우선되어 물성이 열세하게 되고 가교조제가 1.5 중량% 초과 혹은 배합비가 12를 초과하면 물성 향상을 기대할 수 없다.In the polypropylene resin composition, a divinyl compound, a maleimide compound, a quinone dioxim compound, etc. are preferable as a crosslinking aid, and are blended in an amount of 0.06 to 1.2% by weight and blended with an organic peroxide [ (Crosslinking aid) / (organic peroxide)] should satisfy 4 to 10: 1 (weight ratio). If the organic peroxide is less than 0.05% by weight or the blending ratio is less than 3, the decomposition reaction is prioritized, and the physical properties are inferior. If the crosslinking aid is more than 1.5% by weight or the blending ratio is more than 12, physical properties cannot be expected to be improved.
본 발명에 사용된 무기 충진제로는 평균입경이 0.5 ∼ 10 ㎛의 침상형태의 실리카(1)가 단독 사용되거나 이외에 평균입도가 0.5 ∼ 7 ㎛ 범위의 탈크, 황산바륨, 탄산칼슘 올라스토나이트 등(2)이 일부 혼합하여 사용가능하며, 특히 평균입경이 7 ㎛ 이하의 탈크가 더욱 바람직하다. 상기 실리카의 평균입경이 0.5 ㎛ 미만일 경우 분산 불량으로 기계적 물성이 저하되고, 10 ㎛ 초과하면 내충격성이 저하되며, 상기 탈크의 평균입경이 0.5 ㎛ 미만이면 분산 불량으로 기계적 물성이 저하되고, 7 ㎛ 초과하면 내충격성이 저하된다. 이때, (2)의 경우는 통상 (1)의 0 ∼ 25 중량%가 사용되며, 25 중량%를 초과하게 되면 스크래치성능이 떨어진다.As the inorganic filler used in the present invention, needle-like silica (1) having an average particle diameter of 0.5 to 10 µm is used alone, or in addition to talc, barium sulfate, calcium carbonate, and the like having an average particle size of 0.5 to 7 µm ( 2) can be used by mixing a part, and especially the talc whose average particle diameter is 7 micrometers or less is more preferable. When the average particle diameter of the silica is less than 0.5 μm, the mechanical properties are lowered due to poor dispersion, and when the average particle diameter is greater than 10 μm, the impact resistance is decreased. When the average particle diameter of the talc is less than 0.5 μm, the mechanical properties are degraded due to poor dispersion, and 7 μm. If it exceeds, impact resistance will fall. At this time, in the case of (2), 0 to 25% by weight of (1) is normally used, and when it exceeds 25% by weight, scratch performance is lowered.
이러한 무기충진제는 전체 수지 조성물 중에 5 ∼ 40 중량% 범위 내에서 함유되는데, 그 함량이 5 중량% 미만이면 강성 및 내열성이 저하하고 40 중량% 초과하면 충격강도가 저하한다.Such an inorganic filler is contained within the range of 5 to 40% by weight in the total resin composition, when the content is less than 5% by weight, the rigidity and heat resistance is lowered, and when the content exceeds 40% by weight, the impact strength is lowered.
한편, 상기 조성성분 외에 극성기 함유 폴리프로필렌을 사용하는데, 폴리프로필렌과 실리카, 무기충진제와의 결합력을 증가시켜 스크래치성능을 강화시키기 위하여 첨가된다. 본 발명의 극성기 함유 수지는 측쇄에 카르복실기가 그라프트된 변성 폴리프로필렌(modified PP)을 사용한다.On the other hand, in addition to the above components, a polar group-containing polypropylene is used, which is added to enhance the scratching performance by increasing the bonding force between polypropylene and silica and an inorganic filler. The polar group-containing resin of the present invention uses a modified polypropylene (modified PP) in which a carboxyl group is grafted to the side chain.
본 발명의 변성 폴리프로필렌은 폴리프로필렌에 불포화카르본산 또는 그 유도체를 그라프트시킨 것이다. 이때, 그라프트율이 0.5 ∼ 5.0 중량%, 바람직하기로는 1.5 ∼ 5.0 중량%인 것이 사용된다. 만일, 그라프트율이 0.5 중량% 미만이면 스크래치의 향상이 일어나지 않게 되며, 5.0 중량%가 초과되면 강성 및 충격강도의 물성저하가 일어난다. 또한, 그라프트 반응시 사용 가능한 불포화카르본산 또는 그 유도체를 구체적으로 예시하면 말레인산, 아크릴산, 메타아크릴산, 무수말레인산, 디메틸올파라옥틸페놀 중에서 선택한 1종 또는 2종 이상의 것으로, 폴리프로필렌 수지를 그라프트화하여 사용할 수 있다.The modified polypropylene of the present invention is obtained by grafting unsaturated carboxylic acid or a derivative thereof to polypropylene. At this time, a graft ratio of 0.5 to 5.0% by weight, preferably 1.5 to 5.0% by weight is used. If the graft rate is less than 0.5% by weight, the improvement of the scratch does not occur, and when 5.0% by weight is exceeded, the physical properties of the stiffness and the impact strength occur. In addition, examples of unsaturated carboxylic acids or derivatives thereof that can be used in the graft reaction include one or two or more selected from maleic acid, acrylic acid, methacrylic acid, maleic anhydride, and dimethylol paraoctylphenol, and grafting the polypropylene resin. Can be used.
특히, 본 발명의 변성 폴리프로필렌 수지는 전체 폴리프로필렌 수지 조성에 대하여 1 ∼ 7 중량% 바람직하기로는 1 ∼ 5 중량%이다. 이때, 그 함량이 상기 범위보다 낮은 경우에는 스크래치성능향상에 효과를 주기 어려워지게 되고, 높은 경우에는 충격성 및 강성에 물성 저하를 야기할 수 있다.In particular, the modified polypropylene resin of the present invention is 1 to 7% by weight, preferably 1 to 5% by weight based on the total polypropylene resin composition. At this time, when the content is lower than the above range, it becomes difficult to give an effect on improving scratch performance, and when it is high, it may cause a decrease in physical properties in impact and stiffness.
본 발명에서 이와 같은 조건으로 최종적으로 제립된 제품의 MI는 3 ∼ 40으로서, MI가 3 미만인 경우 생산성의 저하 및 최종제품에 플로우 마크(flow mark)가 발생할 수 있고, MI가 40 초과한 경우에는 강성, 충격강도 등에서 원하는 물성을 얻기가 어렵다.In the present invention, the MI of the product finally granulated under such conditions is 3 to 40. When the MI is less than 3, a decrease in productivity and a flow mark may occur in the final product, and when the MI exceeds 40, It is difficult to obtain desired physical properties in terms of stiffness and impact strength.
본 발명에서 첨가될 수 있는 첨가제는 통상적인 것으로, 예를 들면 산화방지제 , 중화제, 핵제, 대전방지제 등이며 이는 적정 함량 범위 내에서 함유된다. 여기서 산화방지제로는 페놀계 산화방지제, 포스파이트계 산화방지제, 티오디프로피오네이트 시너지스트 등이 사용될 수 있고 중화제로는 칼슘 스테아레이트, 산화아연 등이 사용될 수 있으며 이들 또는 다른 첨가제들은 이 분야에서 통상의 지식을 가진 자에 의해서 용이하게 사용될 수 있다.Additives that may be added in the present invention are conventional, for example antioxidants, neutralizing agents, nucleating agents, antistatic agents and the like, which are contained within an appropriate content range. Here, as the antioxidant, phenol-based antioxidants, phosphite-based antioxidants, thiodipropionate synergists, etc. may be used, and as neutralizing agents, calcium stearate, zinc oxide, etc. may be used, and these or other additives may be used in this field. It can be easily used by those skilled in the art.
본 발명의 폴리프로필렌 수지 조성물의 제조방법은 특히 한정되지 않는다. 예를 들어 본 발명의 폴리프로필렌 수지 조성물은 상기 구성성분들을 통상의 기계적 혼련법에 의하여 제조하는 것이 가능하다. 구체적으로 예를 들면 반바리 믹서, 싱글스크류 압출기, 트윈스크류 압출기, 다륜스크류 압출기 등의 일반적인 용융 혼련련기를 이용하는 방법을 채용할 수 있다. 또한, 혼련 온도는 180 ∼ 270 ℃에서 행하는 것이 바람직하다.The manufacturing method of the polypropylene resin composition of this invention is not specifically limited. For example, the polypropylene resin composition of the present invention can produce the above components by a conventional mechanical kneading method. Specifically, for example, a method using a general melt kneading machine such as a short-barrier mixer, a single screw extruder, a twin screw extruder, a multi-screw screw extruder, or the like can be adopted. Moreover, it is preferable to perform kneading temperature at 180-270 degreeC.
본 발명의 조성물에 대한 성형 가공법의 경우 압출성형, 중공성형, 사출성형, 시트성형 등으로 특히 한정되는 것은 없으나 사출성형이 가장 적합하다.The molding process for the composition of the present invention is not particularly limited to extrusion molding, blow molding, injection molding, sheet molding, etc., but injection molding is most suitable.
이하, 본 발명은 다음 실시예에 의거하여 더욱 상세히 설명하겠는바, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.
실시예 1 ∼ 4 및 비교예 1 ∼ 6Examples 1-4 and Comparative Examples 1-6
다음 표 1과 같은 조성과 함량으로 가스켓 조성물을 제조하였다.Next, a gasket composition was prepared in the same composition and content as Table 1 below.
주) PP-1: 용융지수 8 g/min, mmmm분율:98.3%PP-1: Melt index 8 g / min, mmmm fraction: 98.3%
PP-2: 용융지수 14.5 g/min, mmmm분율:96.4%PP-2: Melt index 14.5 g / min, mmmm fraction: 96.4%
PP-3: 용융지수 27 g/min, 에틸렌 60중량%, 크실렌추출물 15 중량%, 극한점도[η]: 3.6 ㎗/gPP-3: melt index 27 g / min, ethylene 60 wt%, xylene extract 15 wt%, intrinsic viscosity [η]: 3.6 dl / g
PP-4: 용융지수 27 g/min, 에틸렌 60중량%, 크실렌추출물 10 중량%, 극한점도[η]: 4.3 ㎗/gPP-4: melt index 27 g / min, ethylene 60 wt%, xylene extract 10 wt%, intrinsic viscosity [η]: 4.3 dl / g
EPR-1: 용융지수 3.5 g/min, 코모노머 31중량%EPR-1: melt index 3.5 g / min, comonomer 31% by weight
EPR-2: 용융지수 3.5 g/min, 코모노머 35중량%EPR-2: Melt index 3.5 g / min, comonomer 35% by weight
EOM-1: 무니점도 23, 코모노머 24 중량%EOM-1: Mooney viscosity 23, comonomer 24 wt%
PO-1: 1,3-비스(t-부틸퍼록시 이소프로필)벤젠PO-1: 1,3-bis (t-butylperoxy isopropyl) benzene
PO-2: 2,5-디메틸 2,5-디(t-부틸퍼록시)헥산PO-2: 2,5-dimethyl 2,5-di (t-butylperoxy) hexane
CA-1: 디-비닐 벤젠CA-1: Di-vinyl benzene
CA-2: P-퀴논 디-옥심CA-2: P-quinone di-oxime
S-1: 평균입경 6.7 ㎛의 침상 실리카S-1: acicular silica with an average particle diameter of 6.7 mu m
T-1: 평균입경 2.6 ㎛의 탈크T-1: Talc with an average particle diameter of 2.6 mu m
MPP: 극성기 그라프트율 1.5 중량%, COOH기 함유 수지MPP: Polar group graft ratio 1.5 weight%, COOH group containing resin
시험예Test Example
본 발명에서 제작한 수지를 이용하여 제조된 성형재료는 그 물성 및 가공성 등을 조사하기 위해 다음에 언급한 절차에 따라 MFR, 충격강도, 굴곡강도, 연필경도 및 플로우 마크를 평가하였다.In order to investigate the physical properties and processability of the molding material produced using the resin produced in the present invention, MFR, impact strength, flexural strength, pencil hardness, and flow mark were evaluated according to the procedure mentioned below.
1) 고유점도1) intrinsic viscosity
프로필렌 단독 중합체 및 프로필렌-에틸렌 공중합체는 135 ℃에서 데칼린에 완전히 용해하여 사용하였다. 우베홀드 점도계(Ubbeholde viscometer)를 이용하여 0.1 ∼ 0.5 ㎗/g의 다양한 농도를 갖는 용액의 점도를 측정하였다. 환산점도(Reduced viscosity)는 제로 농도로 외삽하여 얻었다.The propylene homopolymer and propylene-ethylene copolymer were used completely dissolved in decalin at 135 ° C. The Ubbeholde viscometer was used to measure the viscosity of solutions having various concentrations from 0.1 to 0.5 dl / g. Reduced viscosity was obtained by extrapolating to zero concentration.
2)2) 1313 C-NMR에 의해 측정된 이소타트크릭 펜타드(isotatcric pentad) 분율Isotatcric pentad fraction measured by C-NMR
프로필렌 유닛에서 일정하게 시리즈로 연결된 프로필렌 단량체의 분율을13C-NMR에 의해 측정하였다.The fraction of propylene monomers connected in series in the propylene unit was measured by 13 C-NMR.
3) 멜트인덱스(MFR)3) Melt Index (MFR)
ASTM D1238에 따라 멜트인덱스는 230 ℃, 2.16 kg의 하중에서 측정하였다.According to ASTM D1238 the melt index was measured at 230 ° C. and a load of 2.16 kg.
4) 굴곡탄성율4) Flexural modulus
ASTM D790에 따라 측정하였다.It was measured according to ASTM D790.
5) 아이조드(Izod) 충격강도5) Izod impact strength
ASTM D256에 따라 상온(23 ℃)에서 노트케드(Notched) 시험편으로 측정하였다.According to ASTM D256, measured with a Notched test specimen at room temperature (23 ℃).
6) 무니(Mooney) 점도6) Mooney viscosity
ASTM D1646에 따라 121 ℃에서 측정하였다.It was measured at 121 ° C. according to ASTM D1646.
7) 연필경도7) Pencil Hardness
JIS K5401-1969에 따라 상온(23 ℃)에서 측정하였다It was measured at room temperature (23 ° C) according to JIS K5401-1969.
8) 플로우마크(Flowmark) 육안 관찰8) Visual observation of Flowmark
◎ : 플로우마크가 전혀 관찰되지 않음.(Double-circle): A flow mark is not observed at all.
○ : 플로우마크가 1 ∼ 2개 희미하게 관찰됨.(Circle): 1-2 flowmarks are observed faintly.
△ : 플로우마크가 3 ∼ 6개 존재하며 조금 선명히 관찰됨.(Triangle | delta): Three to six flow marks exist and it is observed a little clearly.
× : 플로우마크가 6개 이상 존재하며 아주 뚜렷하게 관찰됨.×: 6 or more flow marks exist and are observed very clearly.
상기 표 2에서 보여주는 결과로부터 실시예 1 내지 4의 수지 조성물이면 어느 것이나 내충격성, 강성, 내스크래치성을 보유하는 성형품을 얻을 수 있었다. 그렇지만 비교예 1 및 2의 경우와 같이 가교조제의 도입이 없거나 작은 경우에는 내스크래치성이 떨어지며, 비교예 3은 가교조제가 과도하게 사용된 경우 플로우마크가 현저하게 나타났다. 비교예 4의 실리카 화합물이 첨가되지 않은 경우에도 내스크래치성이 떨어졌다. 비교예 5의 경우는 극성기 함유 폴리프로필렌이 없는 경우는 충격강도 및 굴곡탄성율이 저하하며, 비교예 6은 EPR의 과다사용으로 충격강도를 제외한 전체적인 물성저하를 가져옴을 알 수 있었다.From the results shown in Table 2, any of the resin compositions of Examples 1 to 4 could be obtained a molded article having impact resistance, rigidity, and scratch resistance. However, as in the case of Comparative Examples 1 and 2, there is no scratch resistance when there is no introduction or small amount of the crosslinking aid, and in Comparative Example 3, the flow mark is remarkable when the crosslinking aid is excessively used. The scratch resistance was inferior even when the silica compound of Comparative Example 4 was not added. In the case of Comparative Example 5, the impact strength and flexural modulus were lowered in the absence of the polar group-containing polypropylene. In Comparative Example 6, it was found that the overall physical properties were reduced except the impact strength due to excessive use of EPR.
이상에서 설명한 바와 같이, 본 발명에 따른 폴리프로필렌 수지 조성물은 열가소성 수지로 내충격성, 강성, 내열성 등의 물리적 특성이 우수할 뿐만 아니라 내스크래치성이 우수하여 요구 물성이 서로 다른 글러브 박스(Glove Box),콘솔(Console), 필러 트림(Pillar Trim) 등의 자동차 내장재 용도에 매우 유용할 것으로 기대된다. 또한, 내스크래치성 개선을 위한 코팅처리 삭제로 인하여 경제적인 장점도 가진다.As described above, the polypropylene resin composition according to the present invention is a thermoplastic resin, and not only has excellent physical properties such as impact resistance, rigidity, heat resistance, etc., but also has excellent scratch resistance, and thus requires different glove boxes. It is expected to be very useful for automotive interior applications such as console, pillar trim, etc. In addition, there is an economic advantage due to the removal of the coating treatment for improving the scratch resistance.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2036947A1 (en) * | 2007-09-14 | 2009-03-18 | Borealis Technology Oy | Polyolefin compounds with improved properties |
| KR100957310B1 (en) * | 2008-07-11 | 2010-05-12 | 현대모비스 주식회사 | Composition of polypropylen resin having low shrinkage and diemsionalstability |
| KR101522580B1 (en) * | 2013-12-23 | 2015-05-26 | 동국실업 주식회사 | Resin Composition |
| KR101984552B1 (en) * | 2017-11-30 | 2019-05-31 | 지에스칼텍스 주식회사 | Polypropylene resin composition with improved scratch resistance and molded automotive parts prepared thereby |
| CN111892748A (en) * | 2020-07-23 | 2020-11-06 | 江西广源化工有限责任公司 | Composite mineral powder for reducing plastic size shrinkage rate and preparation method and application thereof |
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2002
- 2002-12-18 KR KR1020020081232A patent/KR20040054899A/en not_active Application Discontinuation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2036947A1 (en) * | 2007-09-14 | 2009-03-18 | Borealis Technology Oy | Polyolefin compounds with improved properties |
| KR100957310B1 (en) * | 2008-07-11 | 2010-05-12 | 현대모비스 주식회사 | Composition of polypropylen resin having low shrinkage and diemsionalstability |
| KR101522580B1 (en) * | 2013-12-23 | 2015-05-26 | 동국실업 주식회사 | Resin Composition |
| KR101984552B1 (en) * | 2017-11-30 | 2019-05-31 | 지에스칼텍스 주식회사 | Polypropylene resin composition with improved scratch resistance and molded automotive parts prepared thereby |
| US11795311B2 (en) | 2017-11-30 | 2023-10-24 | Gs Caltex Corporation | Polypropylene resin composition with improved scratch resistance and vehicle molded parts manufactured therefrom |
| CN111892748A (en) * | 2020-07-23 | 2020-11-06 | 江西广源化工有限责任公司 | Composite mineral powder for reducing plastic size shrinkage rate and preparation method and application thereof |
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