KR100439798B1 - Olefin-based resin composition - Google Patents
Olefin-based resin composition Download PDFInfo
- Publication number
- KR100439798B1 KR100439798B1 KR10-2002-0008690A KR20020008690A KR100439798B1 KR 100439798 B1 KR100439798 B1 KR 100439798B1 KR 20020008690 A KR20020008690 A KR 20020008690A KR 100439798 B1 KR100439798 B1 KR 100439798B1
- Authority
- KR
- South Korea
- Prior art keywords
- ethylene
- weight
- propylene
- resin composition
- rubber
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 올레핀계 수지 조성물에 관한 것으로서, 더욱 상세하게는 수지 조성물 총량에 대하여 결정성 에틸렌-프로필렌 공중합체로는 에틸렌-프로필렌 공중합체(에틸렌-프로필렌 고무 7 ∼ 12 중량%) 20 ∼ 40 중량%과 에틸렌-프로필렌 공중합체(에틸렌-프로필렌 고무 25 ∼ 35 중량%) 40 ∼ 50 중량%, 에틸렌-α-올레핀 공중합 고무로는 에틸렌-프로필렌 고무 5 ∼ 10 중량%과 에틸렌-옥텐 고무 5 ∼ 10 중량%, 미세 탈크 5 ∼ 20 중량%, 변성수지 1 ∼ 2 중량% 및 첨가제를 포함함으로써 강성, 성형성, 내충격성, 내열성, 도장성 등이 우수하고, 이와 같은 제반 특성을 유지하면서 특히 성형수축율과 열팽창계수가 작아서 치수안정성이 우수하고 유동성이 크게 향상된 자동차 외장용 올레핀계 수지 조성물에 관한 것이다.The present invention relates to an olefin resin composition, and more specifically, to the total amount of the resin composition, the crystalline ethylene-propylene copolymer includes 20 to 40% by weight of an ethylene-propylene copolymer (7 to 12% by weight of ethylene-propylene rubber); 40-50 weight% of ethylene propylene copolymers (25-35 weight% of ethylene-propylene rubber), 5-10 weight% of ethylene-propylene rubbers and 5-10 weight% of ethylene-octene rubbers as an ethylene-alpha-olefin copolymer rubber By including 5 to 20% by weight of fine talc, 1 to 2% by weight of modified resin and additives, it is excellent in stiffness, formability, impact resistance, heat resistance, paintability, and the like. The present invention relates to an olefin resin composition for automobile exteriors having a low coefficient and having excellent dimensional stability and greatly improved fluidity.
Description
본 발명은 올레핀계 수지 조성물에 관한 것으로서, 더욱 상세하게는 수지 조성물 총량에 대하여 결정성 에틸렌-프로필렌 공중합체로는 에틸렌-프로필렌 공중합체(에틸렌-프로필렌 고무 7 ∼ 12 중량%) 20 ∼ 40 중량%과 에틸렌-프로필렌 공중합체(에틸렌-프로필렌 고무 25 ∼ 35 중량%) 40 ∼ 50 중량%, 에틸렌-α-올레핀 공중합 고무로는 에틸렌-프로필렌 고무 5 ∼ 10 중량%과 에틸렌-옥텐 고무 5 ∼ 10 중량%, 미세 탈크 5 ∼ 20 중량%, 변성수지 1 ∼ 2 중량% 및 첨가제를 포함함으로써 강성, 성형성, 내충격성, 내열성, 도장성 등이 우수하고, 이와 같은 제반 특성을 유지하면서 특히 성형수축율과 열팽창계수가 작아서 치수안정성이 우수하고 유동성이 크게 향상된 자동차 외장용 올레핀계 수지 조성물에 관한 것이다.The present invention relates to an olefin resin composition, and more specifically, to the total amount of the resin composition, the crystalline ethylene-propylene copolymer includes 20 to 40% by weight of an ethylene-propylene copolymer (7 to 12% by weight of ethylene-propylene rubber); 40-50 weight% of ethylene propylene copolymers (25-35 weight% of ethylene-propylene rubber), 5-10 weight% of ethylene-propylene rubbers and 5-10 weight% of ethylene-octene rubbers as an ethylene-alpha-olefin copolymer rubber By including 5 to 20% by weight of fine talc, 1 to 2% by weight of modified resin and additives, it is excellent in stiffness, formability, impact resistance, heat resistance, paintability, and the like. The present invention relates to an olefin resin composition for automobile exteriors having a low coefficient and having excellent dimensional stability and greatly improved fluidity.
일반적으로 열가소성 수지, 특히 폴리프로필렌 수지는 비중이 낮고 타 수지에 비하여 낮은 가격임에도 불구하고 기계적 물성 및 성형성이 우수하여 범용 플라스틱 제품의 가공은 물론 자동차, 전자, 항공산업 등 공업적으로도 널리 사용되고 있는 수지이다. 그러나, 폴리프로필렌 수지는 유리전이온도가 0 ℃ 정도로 낮아 에틸렌을 코모노머로 도입시킨 블록-코-폴리프로필렌이라 하더라도 저온충격강도가 낮다는 단점을 가지고 있다. 따라서, 자동차 범퍼 커버 등의 저온내충격성을 요구하는 자동차용 소재로는 부적합하다. 이러한 단점을 보완하기 위하여 결정성의 블록-코-폴리프로필렌에 올레핀계의 고무를 혼합하여 저온내충격성을 향상시킨 수지 조성물이 많이 사용되고 있다.In general, thermoplastic resins, especially polypropylene resins, are low in specific gravity and low in price compared to other resins, so they have excellent mechanical properties and formability, so they are widely used not only for processing general-purpose plastic products but also for automobile, electronics, and aerospace industries. It is a resin. However, the polypropylene resin has a disadvantage in that the low-temperature impact strength is low even in the case of block-co-polypropylene in which ethylene is introduced into the comonomer due to the low glass transition temperature. Therefore, it is unsuitable for automotive materials requiring low temperature impact resistance such as automobile bumper covers. In order to compensate for these disadvantages, resin compositions having improved low temperature impact resistance by mixing olefinic rubbers with crystalline block-co-polypropylene have been widely used.
결정성 폴리프로필렌 수지와 올레핀계 고무를 주원료로 하는 올레핀계 수지 조성물은 비중이 작고 내충격성, 내열성, 기계적 강도가 우수하며 가격이 저렴하고 기타의 다른 원료 즉 폴리카보네이트/폴리부틸렌 테레프탈레이트 알로이, 폴리카보네이트/아크릴로니트릴-부타디엔-스타이렌 공중합체 알로이, 아크릴로니트릴-부타디엔-스타이렌 공중합체, 폴리아미드 수지, 폴리우레탄 등을 대체하여 자동차의 내외장 부품 등으로 사용되고 있다.The olefin resin composition mainly comprising crystalline polypropylene resin and olefin rubber has a low specific gravity, excellent impact resistance, heat resistance, mechanical strength, low cost, and other raw materials such as polycarbonate / polybutylene terephthalate alloy, Polycarbonate / Acrylonitrile-Butadiene-Styrene Copolymer Replaces alloy, acrylonitrile-butadiene-styrene copolymer, polyamide resin, polyurethane, etc., and is used as interior and exterior parts of automobiles.
올레핀계 수지 조성물의 제조시 다량의 올레핀계 고무 성분을 폴리프로필렌에 혼련시키면 조성물의 유동성이 나빠지게 되고, 웰드라인이 약하게 되어 대형사출물의 성형성이 나빠지고 사출물의 외관이 불량하게 된다. 또한, 조성물의 주원료인 올레핀계 고무와 폴리프로필렌이 모두 비극성 수지이므로 도장성이 불량한 문제점이 있다. 또 하나의 문제로서 이와 같이 제조된 조성물은 저온내충격성이 강화되는 대신 강성이 저하된다는 약점을 가지고 있어 충진제의 첨가를 통해 강성을 보강하기도 하나 충진제의 첨가로 인하여 내충격성이 저하되는 또 다른 단점이 있으므로 물성의 조화를 위하여 함량의 조절이 중요하다.In the preparation of the olefin resin composition, when a large amount of olefin rubber component is kneaded into polypropylene, the fluidity of the composition is poor, the weld line is weak, the moldability of the large injection molding is poor, and the appearance of the injection molding is poor. In addition, since both the olefinic rubber and the polypropylene, which are the main raw materials of the composition, are nonpolar resins, there is a problem of poor paintability. As another problem, the composition prepared as described above has a weak point that the rigidity is lowered instead of the low temperature impact resistance, so that the composition is reinforced, but the impact resistance is lowered due to the addition of the filler. Therefore, control of the content is important for the harmony of the physical properties.
공지의 방법으로는 결정성의 폴리프로필렌을 주성분으로 사용하고 있으며 프로필렌이 92 ∼ 95 중량%와 에틸렌이 5 ∼ 8 중량%의 에틸렌-프로필렌 고무의 함량이 7 ∼ 12 중량%이고, 용융지수가 20 ∼ 40 g/10분 정도의 에틸렌-프로필렌 공중합수지를 사용하며 올레핀계 고무는 에틸렌-프로필렌으로 이루어져 있고, 프로필렌의 함량은 25 ∼ 45 중량%의 고무를 사용하며 강성을 높이기 위해 탈크를 사용하고 탈크의 평균 입자크기는 2 ∼ 4 ㎛의 미세탈크를 사용하고 있다. 상기 성분을 혼합하기 위해 혼련기나 압출기를 사용하여 기계적으로 용융혼련하게 된다. 이 경우 조성물의 충격강도를 높이기 위하여 고가의 올레핀계 고무를 다량 사용하게 되고 강성을 높이기 위해 다량의 탈크를 사용하게 되어 성형성의 저하를 초래하게 된다. 공지의 유럽특허 EP 0557124A1은 높은 용융지수와 고결정성의 에틸렌-프로필렌 공중합체를 55 ∼ 75 %, 30 ∼ 100 ℃ 정도의 용융온도를 갖는 결정성 에틸렌 코폴리머를 25 ~ 45 %, 5 ㎛ 이하의 평균 입자 크기를 갖는 미세탈크 1 ∼ 25 %를 사용하여 초고경질의 조성물을 제조하였으나, 연질, 반경질, 경질의 소재로는 부적당하다. 이와 관련된 공지의 특허로는 EP0531154A2, EP059662A1, EP0496625A2 등이 있다.As a known method, crystalline polypropylene is used as a main component, and the content of ethylene-propylene rubbers of 92 to 95 wt% of propylene and 5 to 8 wt% of ethylene is 7 to 12 wt%, and the melt index is 20 to Ethylene-propylene copolymer resin of about 40 g / 10 minutes is used. The olefinic rubber is composed of ethylene-propylene. The content of propylene is 25 to 45% by weight of rubber, and talc is used to increase rigidity. The average particle size uses fine talc of 2 to 4 µm. In order to mix the components it is mechanically kneaded using a kneader or an extruder. In this case, a large amount of expensive olefin-based rubber is used to increase the impact strength of the composition, and a large amount of talc is used to increase the rigidity, resulting in deterioration of moldability. The known European patent EP 0557124A1 has a crystalline ethylene copolymer having a high melt index and a high crystalline ethylene-propylene copolymer of 55 to 75% and a melting temperature of about 30 to 100 ° C. Ultrahard compositions were prepared using 1-25% of microtalcs with an average particle size, but are inadequate for soft, semi-hard, and hard materials. Known patents in this regard include EP0531154A2, EP059662A1, EP0496625A2, and the like.
이에, 본 발명자들은 상기와 같은 점을 감안하여 연구한 결과, 성형성, 내충격성, 내열성, 치수안정성 등의 물성을 개선한 올레핀계 수지 조성물을 발명하고자 결정성 에틸렌-프로필렌 공중합체의 제조시 에틸렌-프로필렌 고무의 함량을 극히 높인 에틸렌-프로필렌 공중합체와 에틸렌-프로필렌 고무의 함량을 7 ∼ 12 %로 제조한 에틸렌-프로필렌 공중합체를 사용하고 충격을 보강하기 위해 에틸렌-α-올레핀 공중합 고무를 사용하고 강성의 보강을 위해 미세 탈크를 사용하며 도장성을 개선코자 극성기가 함유된 변성수지를 사용하고 내열성과 내후성을 개선키 위해 적절한 첨가제 첨가하여 올레핀계 수지 조성물를 제조하였다. 특히, 결정성 수지가 갖는 일반적인 문제점 중의 하나인 성형시 큰 수축율과 제품으로 사용시 큰 열팽창계수로부터 야기되는 치수안정성의 저하를 개선키 위해 적절한 점도와 조성을 갖는 에틸렌-프로필렌 고무를 사용하여 적절한 크기의 입자로 분산시키고 결정성 에틸렌-프로필렌 공중합체의 결정성과 무기 필러의 함량을 조절하여 치수 안정성이 우수한 올레핀계 수지 조성물의 제조방법을 발명하게 되었다.Accordingly, the present inventors have studied in view of the above point, in order to invent an olefin resin composition having improved physical properties such as moldability, impact resistance, heat resistance, dimensional stability, etc. Ethylene-propylene copolymer with extremely high content of -propylene rubber and ethylene-propylene copolymer made from 7 to 12% of ethylene-propylene rubber are used, and ethylene-α-olefin copolymer rubber is used to reinforce the impact. In order to improve the stiffness, fine talc was used, and modified resin containing polar groups was used to improve paintability, and an olefin resin composition was prepared by adding an appropriate additive to improve heat resistance and weather resistance. Particularly sized particles using ethylene-propylene rubbers with appropriate viscosity and composition to improve the reduction of dimensional stability resulting from large shrinkage in molding and large thermal expansion coefficients in product use, which is one of the common problems with crystalline resins. The present invention has been invented a method for producing an olefin resin composition having excellent dimensional stability by dispersing the resin in a crystalline ethylene-propylene copolymer and controlling the content of the crystalline ethylene-propylene copolymer.
따라서, 본 발명은 대형제품의 사출성형시 성형성, 내충격성, 내열성, 인장강도, 강성 등의 제반 물성이 우수하면서 유동성을 향상시키고 성형수축율과 열팽창계수를 작게 하여 치수안정성을 크게 향상시키는 올레핀계 수지 조성물을 제공하는데 그 목적이 있다.Therefore, the present invention is an olefin system which improves the dimensional stability by improving the fluidity and reducing the molding shrinkage and thermal expansion coefficient, while having excellent physical properties such as moldability, impact resistance, heat resistance, tensile strength, and rigidity during injection molding of large products. The purpose is to provide a resin composition.
본 발명은 수지 조성물 총량에 대하여 결정성 에틸렌-프로필렌 공중합체로는 에틸렌-프로필렌 공중합체(에틸렌-프로필렌 고무 7 ∼ 12 중량%) 20 ∼ 40 중량%과 에틸렌-프로필렌 공중합체(에틸렌-프로필렌 고무 25 ∼ 35 중량%) 40 ∼ 50 중량%, 에틸렌-α-올레핀 공중합 고무로는 에틸렌-프로필렌 고무 5 ∼ 10 중량%과 에틸렌-옥텐 고무 5 ∼ 10 중량%, 미세 탈크 5 ∼ 20 중량%, 변성수지 1 ∼ 2 중량% 및 첨가제를 포함하는 올레핀계 수지 조성물을 그 특징으로 한다.In the present invention, the crystalline ethylene-propylene copolymer is 20 to 40% by weight of the ethylene-propylene copolymer (7 to 12% by weight of the ethylene-propylene rubber) and the ethylene-propylene copolymer (the ethylene-propylene rubber to 25 to the total amount of the resin composition). 35 wt%) 40-50 wt%, 5-10 wt% of ethylene-propylene rubber, 5-10 wt% of ethylene-octene rubber, 5-20 wt% of fine talc, modified resin 1 as ethylene-α-olefin copolymer rubber It is characterized by the olefin resin composition containing-2 weight% and an additive.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명에서 사용한 결정성 에틸렌-프로필렌 공중합체는 에틸렌-프로필렌 고무의 함량을 7 ∼ 12 중량%로 제조한 에틸렌-프로필렌 공중합체 20 ∼ 40 중량%와 제조시 반응기 내에서 25 ∼ 35 중량%의 에틸렌-프로필렌 고무를 직접 제조한 에틸렌-프로필렌 공중합체 40 ∼ 50 %이 바람직하다. 반응기 내에서 다량의 에틸렌-프로필렌 고무를 직접 제조함으로 인해 결정성의 프로필렌 매트릭스에 에틸렌-프로필렌 고무가 균일한 입자로 분산되어 있어 우수한 충격강도를 갖고 있으며, 충격보강을 위해 부가로 첨부하는 고무의 함량을 현저히 줄일 수 있어 제품의 로트별 편차를 줄여 균일한 제품의 제조가 용이하다. 상기 결정성 에틸렌-프로필렌 공중합체 내에 함유된 에틸렌-프로필렌 고무의 함량이 7 ∼ 12 중량%인 고무의 조성은 에틸렌 20 ∼ 40 중량%로 이루어져 있으며, 상기 결정성 에틸렌-프로필렌 공중합체 내에 함유된 에틸렌-프로필렌 고무의 함량이 25 ∼ 35 중량%인 고무의 조성은 에틸렌 45 ∼ 55 중량%로 이루어져 있다. 만일 에틸렌-프로필렌 고무의 함량을 7 ∼ 12 중량%로 제조한 에틸렌-프로필렌 공중합체의 함량이 20 중량% 미만이면 치수안정성이 떨어지는 문제점이 있으며, 40 중량%를 초과하면 성형성에 문제가 있다. 또한, 에틸렌-프로필렌 고무의 함량을 25 ∼ 35 중량%로 제조한 에틸렌-프로필렌 공중합체의 함량이 40 중량% 미만이면 저온충격강도에 문제점이 있으며, 50 중량%를 초과하면 유동성이 저하되는 문제가 있다.The crystalline ethylene-propylene copolymer used in the present invention is 20 to 40% by weight of the ethylene-propylene copolymer prepared from 7 to 12% by weight of ethylene-propylene rubber and 25 to 35% by weight of ethylene in the reactor at the time of manufacture. Preference is given to 40 to 50% of the ethylene-propylene copolymer directly prepared with -propylene rubber. Due to the direct manufacture of a large amount of ethylene-propylene rubber in the reactor, ethylene-propylene rubber is dispersed in the crystalline propylene matrix as uniform particles, so it has excellent impact strength. Significantly reduced, it is easy to manufacture a uniform product by reducing the deviation of each lot of the product. The composition of the rubber having a content of 7 to 12% by weight of ethylene-propylene rubber contained in the crystalline ethylene-propylene copolymer is 20 to 40% by weight of ethylene, and the ethylene contained in the crystalline ethylene-propylene copolymer. The composition of the rubber having a content of 25 to 35% by weight of propylene rubber is 45 to 55% by weight of ethylene. If the content of the ethylene-propylene copolymer prepared in an amount of 7 to 12% by weight of ethylene-propylene rubber is less than 20% by weight, there is a problem in inferior dimensional stability, and in excess of 40% by weight, there is a problem in moldability. In addition, when the content of the ethylene-propylene copolymer prepared in 25 to 35% by weight of the content of ethylene-propylene rubber is less than 40% by weight, there is a problem in low temperature impact strength. have.
본 발명에서는 충격강도를 보강하기 위해 부가로 에틸렌-α-올레핀 공중합고무를 사용하고 있다. α-올레핀으로는 1-프로필렌, 1-부텐, 1-헥센, 1-옥텐을 사용할 수 있고 용도에 따라 선택적으로 사용하게 된다. 본 발명에서 사용한 에틸렌-α-올레핀 공중합 고무는 에틸렌-프로필렌 고무와 에틸렌-옥텐 고무이다. 상기 에틸렌-프로필렌 고무의 함량은 5 ∼ 10 중량%이며, 고무의 조성은 프로필렌의 함량 25 ∼ 45 중량%이고 용융지수는 8 ∼ 12 g/10분(230 ℃)의 고무를 주로 사용한다. 상기 에틸렌-옥텐 고무의 함량은 5 ∼ 10 중량% 사용되며, 고무의 조성은 옥텐의 함량이 20 ∼ 30 중량%이고 용융지수가 1 ∼ 5 g/10분(230 ℃)의 고무를 주로 사용한다. 에틸렌-α-올레핀 공중합 고무의 함량이 증가할수록 점도가 감소할수록 입자가 작게 분산될수록 에틸렌-α-올레핀 공중합 고무 중에 α-올레핀의 함량이 증가할수록 일반적으로 수축율과 열팽창계수가 작아지게 되어 치수안정성을 개선시킬 수 있다.In the present invention, ethylene-α-olefin copolymer rubber is additionally used to reinforce the impact strength. As the α-olefin, 1-propylene, 1-butene, 1-hexene, 1-octene may be used and may be selectively used depending on the use. The ethylene-α-olefin copolymer rubbers used in the present invention are ethylene-propylene rubbers and ethylene-octene rubbers. The content of the ethylene-propylene rubber is 5 to 10% by weight, the composition of the rubber is 25 to 45% by weight of propylene and the melt index is mainly used rubber of 8 to 12 g / 10 minutes (230 ℃). The content of the ethylene-octene rubber is 5 to 10% by weight, the composition of the rubber is 20 to 30% by weight of the octene and the rubber of the melt index of 1 to 5 g / 10 minutes (230 ℃) is mainly used . As the content of ethylene-α-olefin copolymer rubber increases, the viscosity decreases, the particles are dispersed smaller, the amount of α-olefin in the ethylene-α-olefin copolymer rubber generally decreases in shrinkage rate and coefficient of thermal expansion. Can be improved.
강성을 높이기 위해 미세 탈크를 사용하게 되는데 탈크의 함량은 5 ∼ 20 중량% 사용하는 것이 바람직하며, 평균 입자크기가 2 ∼ 4 ㎛인 탈크를 주로 사용하고 있다. 조성물에 탈크를 사용시 조성물의 성형수축율과 열팽창계수를 작게하여 치수안정성을 개선시킬 수 있다.In order to increase the rigidity, fine talc is used, but the content of talc is preferably used in an amount of 5 to 20 wt%, and a talc having an average particle size of 2 to 4 μm is mainly used. When talc is used in the composition, the dimensional stability can be improved by reducing the molding shrinkage and the coefficient of thermal expansion of the composition.
또한, 본 발명에서는 도장성을 개선시키기 위해 에틸렌-α-올레핀 공중합 고무의 점도를 조절하여 조성물의 사출시 고무를 표면으로 돌출시키는 방법과 변성수지를 사용하는 방법을 사용하고 있다. 변성수지로는 에틸렌-2-하이드록시에틸메타아크릴레이트 공중합체를 1 ∼ 2 중량% 사용한다. 이때 변성수지를 1 중량% 미만으로 사용하면 도장성에 문제점이 있으며, 2 중량% 초과하여 사용하면과도하게 표면도출 되는 문제가 있다.In addition, in the present invention, in order to improve paintability, a method of controlling the viscosity of the ethylene-α-olefin copolymer rubber to protrude the rubber to the surface during injection of the composition and a method of using modified resin are used. As a modified resin, 1-2 weight% of ethylene-2-hydroxyethyl methacrylate copolymer is used. In this case, when the modified resin is used in less than 1% by weight, there is a problem in paintability, and when used in excess of 2% by weight, there is a problem of excessive surface derivation.
한편, 본 발명에 사용한 첨가제로는 금속염 및 유기 활제, 1차 산화방지제, 2차 산화방지제, 대전방지제, UV 안정제, 핵제이다. 첨가제의 종류에 따라 조성물의 도장성에 영향을 끼치므로 적절한 첨가제의 선정이 중요하다. 첨가제의 조성물은 다음과 같다.On the other hand, the additives used in the present invention include metal salts and organic lubricants, primary antioxidants, secondary antioxidants, antistatic agents, UV stabilizers, and nucleating agents. Since the type of additive affects the paintability of the composition, selection of an appropriate additive is important. The composition of the additive is as follows.
금속염 및 유기 활제 : 500 ∼ 1000 ppmMetal salts and organic lubricants: 500 to 1000 ppm
1차 산화방지제 : 2000 ∼ 3000 ppmPrimary antioxidant: 2000-3000 ppm
2차 산화방지제 : 1000 ∼ 1500 ppmSecondary antioxidant: 1000 to 1500 ppm
UV 안정제 : 2000 ∼ 4000 ppmUV stabilizer: 2000 ~ 4000 ppm
대전방지제 : 4000 ∼ 5000 ppmAntistatic Agent: 4000 ~ 5000 ppm
핵제 : 2000 ∼ 3000 ppmNucleating agent: 2000-3000 ppm
상기 첨가제에서 금속염 및 유기활제로는 칼슘-스테아레이트, 1차 산화방지제로는 테트라키스[메틸렌(3,5-디-테트라-부틸-4-하이드록시-하이드록시나메이트)]메탄을 사용하며, 2차 산화방지제로는 트리스(2,4-디-테트라-부틸페닐)포스페이트를 사용한다. UV 안정제로는 힌더드 아민계의 폴리-{[6-[(1,1,3,3-테트라메틸부틸)-이미노]-1,3,5-트리아진-2,4-디일][2-(2,2,6,6-테트라메틸피페리딜)-이미노]-헥사메틸렌-[4-(2,2,6,6-테트라메틸-피페리딜)-이미노]}를 사용한다. 그리고, 대전방지제는 알킬아민계를 사용하였고, 핵제는 비스-(파라-테트라-부틸벤조익에시드)하이드록시 알루미늄을 사용한다. 상기 첨가제의 함량 범위에 벗어나면 도장성이 떨어지는 문제점이 있다.In the above additives, metal salts and organic lubricants are used as calcium stearate, and primary antioxidants are tetrakis [methylene (3,5-di-tetra-butyl-4-hydroxy-hydroxynamate)] methane. As the secondary antioxidant, tris (2,4-di-tetra-butylphenyl) phosphate is used. UV stabilizers include hindered amine poly-{[6-[(1,1,3,3-tetramethylbutyl) -imino] -1,3,5-triazine-2,4-diyl] [ 2- (2,2,6,6-tetramethylpiperidyl) -imino] -hexamethylene- [4- (2,2,6,6-tetramethyl-piperidyl) -imino]} use. In addition, the antistatic agent is an alkylamine type, and the nucleus agent is bis- (para-tetra-butylbenzoic acid) hydroxy aluminum. If outside the content range of the additive, there is a problem in paintability.
이하, 본 발명을 실시예에 의거하여 상세히 설명하겠는바, 본 발명이 다음 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.
실시예 1 ∼ 3 및 비교예 1 ∼ 2Examples 1-3 and Comparative Examples 1-2
다음 표 1과 같은 조성으로 수지 조성물을 제조하였다.Next, a resin composition was prepared in the same composition as in Table 1.
시험예Test Example
(1) 용융 지수: ASTM D1238(230 ℃, 2.16 kg)에 규정된 방법으로 측정하고, 자동 측정 장치와 수동 측정 장치를 병행하여 사용하였다.(1) Melt index: Measured by the method specified in ASTM D1238 (230 ° C., 2.16 kg), and an automatic measuring device and a manual measuring device were used in parallel.
(2) 인장 강도 및 신율 : ASTM D683(Type I, cross-head speed = 50 mm/분)에 규정된 방법으로 측정하였다.(2) Tensile strength and elongation: It measured by the method of ASTM D683 (Type I, cross-head speed = 50 mm / min).
(3) 굴곡 탄성율 : ASTM D790(cross-head speed = 10 mm/분)에 규정된 방법으로 측정하였다.(3) Flexural modulus: measured by the method specified in ASTM D790 (cross-head speed = 10 mm / min).
(4) 충격 강도 : ASTM D256에 규정된 방법으로 23 ℃ 및 -30 ℃에서 측정하였다. 이때 회전추의 무게는 5파운드였다.(4) Impact strength: measured at 23 ° C and -30 ° C by the method specified in ASTM D256. The weight of the rotary weight was 5 pounds.
(5) 성형 수축율 : ASTM D 696-79에 규정된 방법으로 측정하였다(5) Mold shrinkage: measured by the method specified in ASTM D 696-79.
(6) 열팽창계수: ASTM D 696-79에 규정된 방법으로 측정하였다..(6) Coefficient of thermal expansion: measured by the method specified in ASTM D 696-79.
(7) 도장 접착성 : 50(L) ×100(W) ×2(H) mm의 복합수지 시편에 클로로네이크폴리프로필렌 프라이머를 두께 5 내지 7 ㎛로 도장한 후, 온도 85 ℃의 오븐에 약 30 분 동안 경화시키고 상온에서 약 24 시간 동안 방치시키고 2 mm 격자를 100개 제조하여 테이프로 도장 접착성을 테스트하였다.(7) Coating adhesiveness: After coating the chloro-nake polypropylene primer with a thickness of 5 to 7 ㎛ on a composite resin specimen of 50 (L) × 100 (W) × 2 (H) mm, and in an oven at a temperature of 85 ℃ It was cured for about 30 minutes, left at room temperature for about 24 hours, and 100 2 mm grids were prepared to test paint adhesion with tape.
상기 측정 결과를 다음 표 2에 나타내었다.The measurement results are shown in Table 2 below.
이상에서 설명한 바와 같이, 본 발명은 수지 조성물 총량에 대하여 결정성 에틸렌-프로필렌 공중합체로는 에틸렌-프로필렌 공중합체(에틸렌-프로필렌 고무 7 ∼ 12 중량%) 20 ∼ 40 중량%과 에틸렌-프로필렌 공중합체(에틸렌-프로필렌 고무 25 ∼ 35 중량%) 40 ∼ 50 중량%, 에틸렌-α-올레핀 공중합 고무로는 에틸렌-프로필렌 고무 5 ∼ 10 중량%과 에틸렌-옥텐 고무 5 ∼ 10 중량%, 미세 탈크 5 ∼ 20 중량%, 변성수지 1 ∼ 2 중량% 및 첨가제를 포함하는 올레핀계 수지 조성물에 관한 것으로서, 강성, 성형성, 내충격성, 내열성, 도장성 등이 우수하고, 이와 같은 제반 특성을 유지하면서 특히 성형수축율과 열팽창계수가 작아서 치수안정성이 우수하고 유동성이 크게 향상되어 자동차 외장용으로 사용할 수 있다.As described above, the present invention relates to a crystalline ethylene-propylene copolymer based on the total amount of the resin composition, 20 to 40% by weight of an ethylene-propylene copolymer (7 to 12% by weight of ethylene-propylene rubber) and an ethylene-propylene copolymer ( 25 to 35% by weight of ethylene-propylene rubber) 40 to 50% by weight, 5 to 10% by weight of ethylene-propylene rubber, 5 to 10% by weight of ethylene-octene rubber, and fine talc 5 to 20 as the ethylene-α-olefin copolymer rubber The present invention relates to an olefin resin composition comprising a weight%, a modified resin 1 to 2 weight%, and an additive. The olefin resin composition is excellent in rigidity, moldability, impact resistance, heat resistance, paintability, and the like. Due to the small coefficient of thermal expansion, it has excellent dimensional stability and greatly improves fluidity, so it can be used for automobile exterior.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2002-0008690A KR100439798B1 (en) | 2002-02-19 | 2002-02-19 | Olefin-based resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2002-0008690A KR100439798B1 (en) | 2002-02-19 | 2002-02-19 | Olefin-based resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20030068939A KR20030068939A (en) | 2003-08-25 |
| KR100439798B1 true KR100439798B1 (en) | 2004-07-12 |
Family
ID=32221775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR10-2002-0008690A KR100439798B1 (en) | 2002-02-19 | 2002-02-19 | Olefin-based resin composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100439798B1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100809092B1 (en) * | 2004-06-28 | 2008-03-03 | (주)코스탯아이앤씨 | Polymer resin composition having color |
| KR101470127B1 (en) * | 2013-02-27 | 2014-12-05 | 현대자동차주식회사 | A polyolefin resin composition having high impact strength and method for preparing thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0841369A1 (en) * | 1996-11-06 | 1998-05-13 | Tonen Chemical Corporation | Polyolefin composition for exterior trims |
| JPH10139978A (en) * | 1996-09-11 | 1998-05-26 | Nippon Porikemu Kk | Thermoplastic resin composition |
| JPH10139960A (en) * | 1996-11-06 | 1998-05-26 | Tonen Chem Corp | Polyolefin composition for automotive exterior parts |
| KR19990039954A (en) * | 1997-11-15 | 1999-06-05 | 정몽규 | Polyolefin Composite Resin Composition for Automotive Parts |
| KR19990039953A (en) * | 1997-11-15 | 1999-06-05 | 정몽규 | Polyolefin Composite Resin Composition for Automotive Parts |
| US20020123572A1 (en) * | 2000-12-28 | 2002-09-05 | Bong-Hyun Park | Polyolefin-based composite resin composition having high strength and low linear expansion |
-
2002
- 2002-02-19 KR KR10-2002-0008690A patent/KR100439798B1/en not_active IP Right Cessation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10139978A (en) * | 1996-09-11 | 1998-05-26 | Nippon Porikemu Kk | Thermoplastic resin composition |
| EP0841369A1 (en) * | 1996-11-06 | 1998-05-13 | Tonen Chemical Corporation | Polyolefin composition for exterior trims |
| JPH10139960A (en) * | 1996-11-06 | 1998-05-26 | Tonen Chem Corp | Polyolefin composition for automotive exterior parts |
| KR19990039954A (en) * | 1997-11-15 | 1999-06-05 | 정몽규 | Polyolefin Composite Resin Composition for Automotive Parts |
| KR19990039953A (en) * | 1997-11-15 | 1999-06-05 | 정몽규 | Polyolefin Composite Resin Composition for Automotive Parts |
| US20020123572A1 (en) * | 2000-12-28 | 2002-09-05 | Bong-Hyun Park | Polyolefin-based composite resin composition having high strength and low linear expansion |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030068939A (en) | 2003-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3039071B1 (en) | Soft touch compositions and articles thereof | |
| CN102391583A (en) | Low-temperature-resistance polypropylene composition and preparation method thereof | |
| KR20010059003A (en) | A polyolefin-based composite resin composition having low linear expansion | |
| EP0069479A1 (en) | Thermoplastic resin composition | |
| KR20020055282A (en) | A polyolefin-based composite resin composition having high strength and low linear expansion | |
| KR100918290B1 (en) | Polypropylene resin compositions having excellent flow and impact properties and polypropylene molding manufactured therefrom | |
| KR100439798B1 (en) | Olefin-based resin composition | |
| KR100387648B1 (en) | Composition of polypropylene resin | |
| KR101783084B1 (en) | Polypropylene composition having low density and low linear thermal expansion, and molded product | |
| KR100204658B1 (en) | An elastic resin complex used for outside material of a car | |
| KR19990033557A (en) | Polyolefin composite resin composition for automobile interior | |
| KR100187185B1 (en) | Olefin resin compositions | |
| KR20040008806A (en) | Polypropylene resin composition for automobil thinwall bumper cover | |
| KR100225672B1 (en) | A polyolefin resin complex used for inside material of a car | |
| JPH0671829A (en) | Polypropylene resin molding | |
| KR100578167B1 (en) | A composition of polyolefin-based complex resin | |
| KR100339278B1 (en) | A polyolefin resin complex using for exterior material of car | |
| KR100262887B1 (en) | Composition of polyolefins polymer blend | |
| KR20070048992A (en) | Polypropylene resin composition for automobile trim | |
| KR100187192B1 (en) | Resin compositions of semi-regidity based on olefin | |
| KR100187188B1 (en) | Resin composition based on olefin | |
| KR100448121B1 (en) | Polypropylene resin composition | |
| KR100187191B1 (en) | Olefin resin composition | |
| KR19990039953A (en) | Polyolefin Composite Resin Composition for Automotive Parts | |
| KR100187190B1 (en) | Olefin resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20080630 Year of fee payment: 5 |
|
| LAPS | Lapse due to unpaid annual fee |