KR100571034B1 - Polyolefin resin composition having high transparency, rigidity and impact strength - Google Patents
Polyolefin resin composition having high transparency, rigidity and impact strength Download PDFInfo
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- KR100571034B1 KR100571034B1 KR1020030082823A KR20030082823A KR100571034B1 KR 100571034 B1 KR100571034 B1 KR 100571034B1 KR 1020030082823 A KR1020030082823 A KR 1020030082823A KR 20030082823 A KR20030082823 A KR 20030082823A KR 100571034 B1 KR100571034 B1 KR 100571034B1
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- 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
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Abstract
본 발명은 고투명성, 고강성 및 고충격특성 폴리올레핀 수지 조성물에 관한 것으로서, 보다 상세하게는, 고입체규칙성 호모폴리프로필렌(homo-polypropylene)과 단일 활성점 촉매를 사용하여 제조된 에틸렌/α-올레핀 공중합체 및 핵제를 포함하여 이루어지는 고투명성, 고강성 및 고충격특성 폴리올레핀 수지 조성물에 관한 것이다. 본 발명의 수지 조성물을 사용하여 제조된 성형품은 기존의 폴리프로필렌 수지 대비 투명성, 표면경도, 내충격성이 우수하므로, 이러한 특성들이 요구되는 전기전자, 자동차용 대형제품, 산업용 사출품, 사무용 사출품 등의 분야에 있어서 외관용 성형품으로서 사용될 수 있다.The present invention relates to a high transparency, high rigidity and high impact polyolefin resin composition, more specifically, ethylene / α- prepared using a high-stereoregular homo-polypropylene and a single active site catalyst It relates to a high transparency, high rigidity and high impact polyolefin resin composition comprising an olefin copolymer and a nucleating agent. Since the molded article manufactured using the resin composition of the present invention has excellent transparency, surface hardness, and impact resistance compared to the conventional polypropylene resin, electrical and electronic products, large products for automobiles, industrial injection parts, office injection parts, etc., which require these characteristics, etc. It can be used as a cosmetic molded article in the field of.
고투명성, 고강성, 고충격특성, 폴리프로필렌, 에틸렌/α-올레핀 공중합체, 핵제High transparency, high rigidity, high impact property, polypropylene, ethylene / α-olefin copolymer, nucleating agent
Description
본 발명은 고투명성, 고강성 및 고충격특성 폴리올레핀 수지 조성물에 관한 것으로서, 보다 상세하게는, 고입체규칙성 호모폴리프로필렌(homo-polypropylene)과 단일 활성점 촉매를 사용하여 제조된 에틸렌/α-올레핀 공중합체 및 핵제를 포함하여 이루어지는 고투명성, 고강성 및 고충격특성 폴리올레핀 수지 조성물에 관한 것이다.The present invention relates to a high transparency, high rigidity and high impact polyolefin resin composition, more specifically, ethylene / α- prepared using a high-stereoregular homo-polypropylene and a single active site catalyst It relates to a high transparency, high rigidity and high impact polyolefin resin composition comprising an olefin copolymer and a nucleating agent.
폴리프로필렌 수지는 여타 폴리올레핀 소재에 비하여 강성, 내약품성 및 성형성이 뛰어나 자동차 내장부품, 가전부품 등 공업적 이용분야의 범위가 매우 넓은 소재이다.Polypropylene resin is excellent in rigidity, chemical resistance and moldability compared to other polyolefin materials, and thus has a wide range of industrial applications such as automobile interior parts and home appliances parts.
그러나, 일반적으로, 프로필렌이 단독 중합된 호모폴리프로필렌의 경우, 강성, 경도, 인장강도 및 내열성은 뛰어나지만, 낮은 충격강도, 특히 저온에서의 낮은 충격 강도 때문에 자동차 부품, 일반 가전용 및 사무용 사출품 등의 재질로 사용될 때에는 많은 제한이 있어 왔다. 이러한 낮은 내충격성을 개질하기 위하여 폴리프로필렌을 중합시킬 때에 에틸렌을 부가적으로 첨가하여 공중합시킨 프로필렌- 에틸렌 블록 공중합체(propylene-ethylene block copolymer)가 개발된 바 있다. 그러나, 이러한 프로필렌-에틸렌 블록 공중합체는 충격특성 개질에는 효과가 있으나, 공중합체의 특성상 기존 폴리프로필렌에 비해 강성 및 내열성 등이 저하되고, 고무특성성분의 함량 증가에 따라 표면경도 저하, 투명성, 내스크래치특성 등의 외관물성이 열세해지는 문제를 지니게 된다.Generally, however, homopolypropylene homopolymerized with propylene has excellent stiffness, hardness, tensile strength and heat resistance, but due to its low impact strength, especially low impact strength at low temperatures, automotive parts, general home appliances and office injections When used as a material such as has been a lot of limitations. In order to modify the low impact resistance, a propylene-ethylene block copolymer has been developed in which ethylene is added and copolymerized when the polypropylene is polymerized. However, the propylene-ethylene block copolymer is effective in modifying the impact characteristics, but the stiffness and heat resistance of the copolymer is lower than that of the existing polypropylene, and the surface hardness decreases, transparency, and resistance increase with increasing content of rubber components. It has a problem that the appearance physical properties such as scratch characteristics are inferior.
폴리프로필렌의 충격특성을 향상시키기 위한 몇가지 시도들이 있어 왔다. 그중 하나는 앞에서 언급된 바와 같이 프로필렌 중합시 α-올레핀, 예를 들면 에틸렌을 블록 공중합시키는 것인데, 이 경우, 에틸렌 함량이 높아짐에 따라 충격특성은 올라가지만, 강성, 내열성, 경도 등이 저하되는 문제가 발생함은 상기한 바와 같으며, 또한 블록 공중합체 자체가 불투명해진다. 다른 시도로는, 에틸렌-프로필렌 공중합체 혹은 에틸렌-프로필렌-다이엔 공중합체와 같은 고무성분의 물질을 폴리프로필렌에 용융혼합시키는 방법이 폭넓게 이용되어져 왔으나, 이 방법 역시 충격특성은 향상되지만 투명성의 개선 효과는 보지 못하였다.Several attempts have been made to improve the impact properties of polypropylene. One of them is the block copolymerization of α-olefins such as ethylene during the propylene polymerization as mentioned above. In this case, the impact properties increase as the ethylene content increases, but the rigidity, heat resistance, hardness, etc. are deteriorated. Is generated as described above, and the block copolymer itself becomes opaque. In another attempt, melt mixing of rubber-based materials, such as ethylene-propylene copolymers or ethylene-propylene-diene copolymers, with polypropylene has been widely used, but this method also improves impact properties but improves transparency. No effect was seen.
상기한 방법들 이외에, 충격특성을 저하시키지 않으면서 강성 및 경도 등을 향상시키는 방법으로는 핵제를 첨가제로 사용하는 방법이 있다. 이러한 핵제처방기술로는 유기조핵제를 첨가하는 방법, 무기 충전재를 첨가하는 방법 등이 있다. 또한, 중합시 고강성의 폴리프로필렌을 제조하기 위하여 아이소탁틱성(isotacticity)을 높이는 방법도 알려져 있다(일본공개특허공보 소55-81125호).In addition to the above-described methods, there is a method of using a nucleating agent as an additive as a method of improving rigidity and hardness without deteriorating impact characteristics. Such nucleation prescription techniques include a method of adding an organic nucleating agent, a method of adding an inorganic filler, and the like. In addition, a method of increasing isotacticity is also known in order to produce high rigid polypropylene during polymerization (Japanese Patent Laid-Open No. 55-81125).
한편, 폴리프로필렌 수지는 결정성 수지이기 때문에 용융성형후 냉각과정에서 수축이 발생한다. 충분한 흐름성을 갖지 못하는 폴리프로필렌 수지를 사용하여 얇은 판 형상의 제품이나 가는 빗살(rib)이 많은 형상의 제품을 사출성형할 경우, 사출성형시의 과도한 사출압으로 인한 성형후 휨 발생, 높은 수지온도로 인한 가스자국 발생, 흐름성 불량으로 인한 성형품 말단의 미성형 등의 문제가 발생하게 된다.On the other hand, since the polypropylene resin is a crystalline resin, shrinkage occurs in the cooling process after melt molding. When injection molding a thin plate-shaped product or a product having a large number of ribs by using a polypropylene resin that does not have sufficient flowability, warpage occurs after molding due to excessive injection pressure during injection molding, and high resin Problems such as gas traces caused by temperature and unmolding of the ends of molded parts due to poor flowability occur.
이를 해결하기 위해서는 용융지수가 높은 수지를 사용하여 수지의 흐름성을 향상시키거나 또는 보강재를 첨가하는 방법이 검토될 수 있으나, 단순히 용융지수가 높은 수지를 사용할 경우, 수지의 흐름성은 개선되지만 충격강도가 떨어지는 문제점이 있다. 또한, 보강재로서 무기충전재를 첨가하는 경우, 성형후 휨 및 수축은 개선되지만, 충전재로 인한 외관불량, 재료의 비중상승에 따른 비용발생 등의 문제점이 있으며, 또한 충전재에 의해 수지의 흐름성이 나빠지는 단점도 있다.In order to solve this problem, a method of improving resin flowability or adding a reinforcing material by using a resin having a high melt index may be considered, but when simply using a resin having a high melt index, the flowability of the resin may be improved but the impact strength may be improved. There is a problem falling. In addition, when the inorganic filler is added as a reinforcing material, the warpage and shrinkage after molding are improved, but there are problems such as appearance defects due to the filler and cost incurred due to the increase in specific gravity of the material, and also the flowability of the resin is deteriorated by the filler. There are also disadvantages.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 투명성, 내스크래치특성 등과 같은 외관물성과 강성, 충격강도, 경도 등의 성능특성이 우수하고, 또한 용융흐름성이 적절하기 때문에, 전기전자, 자동차용 대형제품, 산업용 사출품, 사무용 사출품 등의 분야에 있어서 투명성이 요구되는 외관용 성형품의 제조를 가능하게 하는 고투명성, 고강성 및 고충격특성 폴리올레핀 수지 조성물을 제공하는 것이다.The present invention has been made to solve the above problems, and an object of the present invention is to provide excellent performance properties such as stiffness, impact strength, hardness, etc., such as transparency and scratch resistance, and proper melt flow. It is to provide a high transparency, high rigidity and high impact polyolefin resin composition which enables the manufacture of molded articles for external appearance that requires transparency in the fields of electrical, electronic, automotive large products, industrial injection products, office injection products, etc. .
본 발명에 따르면, 아이소택틱 펜타드(isotactic pentad) 분율이 95중량% 이상이고 분자량 분포(중량평균분자량(Mw)/수평균 분자량(Mn))가 7~12인 호모폴리프 로필렌, 밀도가 0.85∼0.90g/㎤이고 190℃에서의 용융지수가 1∼10g/10분이며 단일 활성점 촉매를 사용하여 제조된 에틸렌/α-올레핀 공중합체 및 핵제를 포함하여 이루어지고, 상기 에틸렌/α-올레핀 공중합체는 상기 호모폴리프로필렌과 상기 에틸렌/α-올레핀 공중합체로 이루어지는 기본수지 100중량부 내에 1~20중량부가 포함되고, 상기 핵제는 상기 기본수지 100중량부에 대하여 0.05~0.5중량부가 포함되는 것을 특징으로 하는 고투명성, 고강성 및 고충격특성 폴리올레핀 수지 조성물이 제공된다.According to the present invention, homopolypropylene has a isotactic pentad fraction of at least 95% by weight and a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 7 to 12, density Is 0.85 to 0.90 g / cm 3, the melt index at 190 ° C. is 1 to 10 g / 10 minutes, and includes an ethylene / α-olefin copolymer and a nucleating agent prepared using a single active site catalyst, and the ethylene / α The -olefin copolymer contains 1 to 20 parts by weight in 100 parts by weight of the base resin consisting of the homopolypropylene and the ethylene / α-olefin copolymer, and the nucleating agent is 0.05 to 0.5 parts by weight based on 100 parts by weight of the base resin. A high transparency, high rigidity and high impact polyolefin resin composition is provided.
본 발명의 수지 조성물은, 230℃에서의 용융지수가 6∼30g/10분인 것이 바람직하다. 230℃에서의 수지 조성물의 용융지수가 6g/10분 미만이면, 사출성형시 사출압이 높아져야 하므로 사출성형품의 품질이 나빠지는 문제점이 있고, 30g/10분을 초과하면 충격강도가 떨어지는 단점이 있다.It is preferable that the resin composition of this invention is 6-30 g / 10min in melt index in 230 degreeC. If the melt index of the resin composition at 230 ° C is less than 6g / 10 minutes, the injection pressure should be increased during injection molding, there is a problem that the quality of the injection molded product deteriorates, and if it exceeds 30g / 10 minutes, the impact strength is lowered .
본 발명의 수지 조성물에 포함되는 상기 호모폴리프로필렌은, 고입체규칙성 호모폴리프로필렌으로서, 핵자기공명법(Nuclear Magnetic Resonance) 상의 입체 규칙도 지수인 아이소택틱 펜타드 분율이 95중량% 이상이고, 겔투과크로마토그래피(gel permeation chromatography, GPC)법에 의한 분자량 분포(중량평균분자량(Mw)/수평균 분자량(Mn))가 7~12인 것이 바람직하다. 상기 호모폴리프로필렌의 아이소택틱 펜타드 분율이 95중량% 미만이면 내열성 및 강성이 낮아지기 때문에, 고온에서 사용하는 복잡한 형상의 제품의 경우 사용중에 휘거나 뒤틀리는 단점이 있다. 또한, 상기 호모폴리프로필렌의 분자량 분포가 7 미만이면 같은 용융지수의 다른 수지조성물에 비하여 용융흐름성이 나빠지고, 12를 초과하면 사출성형시 계량시간이 길어져 생산성이 저하된다.The homopolypropylene contained in the resin composition of the present invention is a high-stereoregular homopolypropylene, and the isotactic pentad fraction, which is a stereoregularity index on Nuclear Magnetic Resonance, is 95% by weight or more. It is preferable that the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) by the gel permeation chromatography (GPC) method is 7-12. When the isotactic pentad fraction of the homopolypropylene is less than 95% by weight, heat resistance and rigidity are lowered, and thus, a complicated shape product used at a high temperature has a disadvantage of being warped or twisted during use. In addition, when the molecular weight distribution of the homopolypropylene is less than 7, the melt flowability is worse than that of other resin compositions having the same melt index, and when it is more than 12, the metering time is increased during injection molding, thereby decreasing productivity.
본 발명의 수지 조성물에 포함되는 상기 에틸렌/α-올레핀 공중합체는, 밀도가 0.85∼0.90g/㎤이고 190℃에서의 용융지수가 1∼10g/10분이며 단일 활성점 촉매를 사용하여 제조된 것이 바람직하다. 상기 에틸렌/α-올레핀 공중합체의 밀도가 0.85g/㎤ 미만이면 제조된 사출물 중의 저결정성 물질이 증가하게 되고, 0.90g/㎤를 초과하면 투명성이 나빠진다. 또한, 상기 에틸렌/α-올레핀 공중합체의 190℃에서의 용융지수가 1g/10분 미만이면 상기 호모폴리프로필렌 수지와의 분산성이 저하되어 투명성이 떨어지고, 10g/10분을 초과하여도 마찬가지로 상기 호모폴리프로필렌 수지와의 분산성이 저하되어 투명성이 떨어진다. 또한, 상기 에틸렌/α-올레핀 공중합체가 단일 활성점 촉매로 제조된 것이 아니라, 예컨대 지글러-나타 촉매로 제조된 것일 경우에는, 사출물 중의 저결정성 물질이 증가하여 물성이 나빠지는 단점이 있다.The ethylene / α-olefin copolymer included in the resin composition of the present invention has a density of 0.85 to 0.90 g / cm 3, a melt index of 1 to 10 g / 10 min at 190 ° C., and is prepared using a single active site catalyst. It is preferable. When the density of the ethylene / α-olefin copolymer is less than 0.85 g / cm 3, the low crystalline material in the prepared injection molding increases, and when it exceeds 0.90 g / cm 3, transparency becomes poor. In addition, when the melt index at 190 ° C. of the ethylene / α-olefin copolymer is less than 1 g / 10 min, dispersibility with the homopolypropylene resin is lowered, resulting in poor transparency. Dispersibility with homopolypropylene resin falls and transparency is inferior. In addition, when the ethylene / α-olefin copolymer is not made of a single active site catalyst, but is made of, for example, a Ziegler-Natta catalyst, a low crystalline material in the injection molding increases, thereby deteriorating physical properties.
본 발명의 수지 조성물에 포함되는 상기 핵제로는, 수지 조성물의 투명성 개선을 위해 첨가되는 것으로서, 무기계 핵제 또는 솔비톨계 핵제가 있다. 무기계 핵제의 경우, 솔비톨계 핵제에 비해 투명성 향상 효과가 떨어지고 분산성이 떨어지는 단점이 있으므로, 사출물의 투명성 향상을 위해서는 솔비톨계 핵제를 사용하는 것이 바람직하며, 우수한 투명성을 부여하면서 냄새 문제가 가장 적은 3,4-디메틸벤질리덴 솔비톨을 사용하는 것이 특히 바람직하다.The nucleating agent included in the resin composition of the present invention is added to improve the transparency of the resin composition, and includes an inorganic nucleating agent or a sorbitol nucleating agent. In the case of inorganic nucleating agent, the transparency improving effect and inferior dispersibility are inferior to sorbitol nucleating agent. Therefore, it is preferable to use sorbitol nucleating agent to improve the transparency of the injection molding. Particular preference is given to using, 4-dimethylbenzylidene sorbitol.
본 발명의 수지 조성물에 있어서, 상기 에틸렌/α-올레핀 공중합체는 상기 호모폴리프로필렌과 상기 에틸렌/α-올레핀 공중합체로 이루어지는 기본수지 100중 량부 내에 1~20중량부가 포함되는 것이 바람직하며, 5∼15중량부가 포함되는 것이 보다 바람직하다. 상기 에틸렌/α-올레핀 공중합체의 함량이 1중량부 미만이면 충격특성의 개선 효과가 없으며, 20중량부를 초과하면 호모폴리프로필렌과 에틸렌/α-올레핀 공중합체의 상분리가 일어나기 때문에, 가공시 불균일 현상이 발생하여 사출물의 투명성이 나빠진다.In the resin composition of the present invention, it is preferable that the ethylene / α-olefin copolymer is contained in an amount of 1 to 20 parts by weight in 100 parts by weight of the basic resin comprising the homopolypropylene and the ethylene / α-olefin copolymer. It is more preferable that 15 weight part is included. If the content of the ethylene / α-olefin copolymer is less than 1 part by weight, there is no effect of improving the impact characteristics, and if it exceeds 20 parts by weight, the phase separation of the homopolypropylene and the ethylene / α-olefin copolymer occurs, it is a non-uniform phenomenon during processing This occurs, resulting in poor transparency of the injection molding.
본 발명의 수지 조성물에 있어서, 상기 핵제는 상기 기본수지 100중량부에 대하여 0.05~0.5중량부가 포함되는 것이 바람직하다. 상기 핵제의 함량이 0.05중량부 미만이면 투명성이 나타나지 않으며, 0.5중량부를 초과하면 더 이상의 투명성 향상 효과를 기대할 수 없다.In the resin composition of this invention, it is preferable that the said nucleating agent contains 0.05-0.5 weight part with respect to 100 weight part of said base resins. If the content of the nucleating agent is less than 0.05 parts by weight, the transparency does not appear, if more than 0.5 parts by weight can not be expected to further improve the transparency.
상기에서 설명한 것 이외에도, 본 발명의 목적의 범위 내에서, 본 발명의 수지조성물에는 산화방지제, 내열안정제, 내후안정제, 대전방지제, 활제, 슬립제, 난연제, 안료, 염료 등과 같은 각종 첨가제가 첨가될 수 있다.In addition to those described above, within the scope of the object of the present invention, various additives such as antioxidants, heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, flame retardants, pigments, dyes, etc. may be added to the resin compositions of the present invention. Can be.
본 발명의 수지조성물을 제조하는 방법에 있어서는 특별한 제한이 없고, 일반적으로 알려진 폴리올레핀 수지 조성물을 제조하는 방법을 이용할 수 있다. 즉, 본 발명의 조성비에 따른 상기 성분들 및 기타 첨가제를 니더(kneader), 롤, 반바리(banbury) 믹서 등의 혼련기를 사용하여 혼련한 다음, 1축 또는 2축 압출기 등을 사용하여 압출하므로써, 본 발명의 수지 조성물을 펠렛상으로 제조할 수 있다.There is no restriction | limiting in particular in the method of manufacturing the resin composition of this invention, The method of manufacturing generally known polyolefin resin composition can be used. That is, the above components and other additives according to the composition ratio of the present invention are kneaded using a kneader such as a kneader, a roll, a banbury mixer, and then extruded using a single screw or twin screw extruder. , The resin composition of the present invention can be produced in pellet form.
이하 실시예 및 비교예에 의해 본 발명을 상세히 설명하나, 이들 실시예는 예시적인 목적으로 사용될 뿐이며, 이에 의해 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by Examples and Comparative Examples, but these Examples are only used for illustrative purposes, and the present invention is not limited thereto.
실시예 및 비교예Examples and Comparative Examples
[수지 조성물의 제조][Production of Resin Composition]
실시예 1~2 및 비교예 1~5에 대하여, 표 1에 표시된 바에 해당되는 호모폴리프로필렌, 에틸렌/α-올레핀 공중합체, 3,4-디메틸벤질리덴 솔비톨을 표 1에 나타난 조성비로 하여 배합하고, 여기에 기타 첨가제로서 산화방지제 및 중화제를 적당량 첨가한 후 믹서로 혼합하였다. 다음으로 혼합된 수지 조성물을 압출기 온도 200℃의 압출기로 압출하여 실시예 1~2 및 비교예 1~5에 해당하는 펠렛상의 수지 조성물을 제조하였다.For Examples 1 to 2 and Comparative Examples 1 to 5, a homopolypropylene, an ethylene / α-olefin copolymer, and 3,4-dimethylbenzylidene sorbitol corresponding to those shown in Table 1 were used as the composition ratios shown in Table 1. And an appropriate amount of antioxidant and neutralizing agent was added thereto as other additives and then mixed by a mixer. Next, the resin composition mixed was extruded by the extruder of 200 degreeC of extruders, and the pellet-like resin composition corresponding to Examples 1-2 and Comparative Examples 1-5 was manufactured.
[시편의 제조]Preparation of Specimen
상기에서 제조된, 실시예 1~2 및 비교예 1~5에 해당하는 펠렛상의 수지 조성물을 사용하여 ASTM 규격에 따른 굴곡탄성률, 충격강도, 경도, 흐림도(haze) 등의 물성측정용 시편을 만들었다. 시편은 사출기(삼성 클뢰크너 FM140TON)를 이용하여 만들었으며, 사출은, 노즐의 온도분포를 호퍼로부터 170, 200, 220, 230, 230℃로 하고, 금형온도를 60℃로 고정하고, 사출압력을 50~120기압으로 한 사출조건 하에서 수행되었다.Specimens for measuring physical properties such as flexural modulus, impact strength, hardness, haze, etc. according to ASTM standards were prepared using the pelletized resin compositions corresponding to Examples 1 to 2 and Comparative Examples 1 to 5 prepared above. made. Specimens were made using an injection machine (Samsung Klikner FM140TON), and injection was carried out by setting the temperature distribution of the nozzle to 170, 200, 220, 230, 230 ℃ from the hopper, fixing the mold temperature at 60 ℃, and adjusting the injection pressure. It was carried out under injection conditions at 50-120 atmospheres.
[물성의 측정][Measurement of Physical Properties]
상기에서 제조된, 실시예 1~2 및 비교예 1~5에 해당하는 수지 조성물로 만든 시편을 23℃의 실내에서 72시간 동안 방치한 다음 물성을 측정하였으며, 그 측정결과를 표 1에 나타내었다.The specimens prepared from the resin compositions corresponding to Examples 1 and 2 and Comparative Examples 1 to 5 prepared above were left at 23 ° C. for 72 hours and then measured for physical properties. .
각 물성의 측정은 다음과 같이 하였다.The measurement of each physical property was carried out as follows.
① 아이소택틱 펜타드 분율① isotactic pentad fraction
핵자기 공명장치(C13-NMR)를 이용하여, 폴리프로필렌 분자쇄 중의 펜타드 단위로서의 아이소택틱 분율(중량%)을 측정하여 입체규칙성을 평가하였다.Stereoregularity was evaluated by using a nuclear magnetic resonance apparatus (C 13 -NMR) by measuring the isotactic fraction (% by weight) as pentad unit in the polypropylene molecular chain.
② 분자량 분포② molecular weight distribution
겔투과크로마토그래피(GPC)로 중량평균분자량(Mw)과 수평균분자량(Mn)을 측정하고, 그 비율(Mw/Mn)을 계산하여 분자량 분포로 하였다.The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC), and the ratio (Mw / Mn) was calculated and made into molecular weight distribution.
③ 용융흐름지수(Melt flow index, MI)③ Melt flow index (MI)
ASTM D1238의 방법에 따라, 190℃ 또는 230℃ 온도에서 2.16 kg 하중에 의해 10분간 흘러내리는 수지의 양(g/10분)을 측정하였다.According to the method of ASTM D1238, the amount of resin (g / 10 min) flowing down for 10 minutes by 2.16 kg load at 190 ° C or 230 ° C was measured.
④ 스파이럴 플로우(spiral flow)④ Spiral flow
110톤 사출기를 이용하여, 235℃에서 스파이럴 금형으로 사출하여 제조된 시편의 길이를 측정하였다.Using a 110 ton injection machine, the length of the specimen prepared by injection into a spiral mold at 235 ℃ was measured.
⑤ 굴곡탄성률⑤ Flexural modulus
ASTM D790의 방법에 따라 측정하였다.It measured according to the method of ASTM D790.
⑥ 흐림도(haze)⑥ haze
ASTM D1004의 방법에 따라 흐림도를 측정하여 투명성을 평가하였다.The transparency was measured by measuring the cloudiness according to the method of ASTM D1004.
⑦ 표면경도⑦ Surface Hardness
ASTM D785의 방법에 따라 측정하였다.It was measured according to the method of ASTM D785.
⑧ 열변형온도⑧ Heat deflection temperature
ASTM D648의 방법에 따라 측정하였다.It was measured according to the method of ASTM D648.
⑨ 저온충격강도⑨ Low temperature impact strength
수지 조성물을 2mm 두께의 시트로 사출성형한 후, -20℃의 온도하에 추를 일정 높이에서 시트로 떨어뜨려, 평균적으로 파괴되는 높이를 측정하였다.After injection molding the resin composition into a sheet having a thickness of 2 mm, the weight was dropped onto the sheet at a constant height under a temperature of -20 ° C, and the average breaking height was measured.
[물성 측정 결과][Property Measurement Results]
[표 1]TABLE 1
상기 표 1에 따르면, 실시예 2는, 실시예 1 대비 에틸렌/α-올레핀 공중합체의 함량이 감소된 것으로서, 실시예 1 대비 굴곡탄성율, 투명성(흐림도가 낮을수록 투명성은 좋다), 표면경도 등이 우수해지고 저온충격강도가 감소하는 경향을 나타 내었다.According to Table 1, Example 2, the content of the ethylene / α-olefin copolymer is reduced compared to Example 1, flexural modulus, transparency (the lower the transparency is better transparency), the surface hardness than Example 1 The back light was excellent and the low temperature impact strength was decreased.
한편 비교예 1은, 에틸렌/α-올레핀 공중합체를 20중량부 이상 포함하고, 핵제가 포함되지 않은 것으로서, 실시예 1 대비 굴곡탄성율, 투명성, 표면경도 등이 열세하였다.On the other hand, Comparative Example 1 contained 20 parts by weight or more of ethylene / α-olefin copolymer and contained no nucleating agent, and the flexural modulus, transparency, surface hardness, and the like of Example 1 were inferior.
또한 비교예 2는, 실시예 1 대비 호모폴리프로필렌의 아이소택틱 펜타드 분율이 낮고, 에틸렌/α-올레핀 공중합체를 20중량부 이상 포함한 것으로서, 실시예 1 대비 스파이럴 플로우, 굴곡탄성율, 투명성 등이 열세하였다.In addition, Comparative Example 2 has a lower isotactic pentad fraction of homopolypropylene than Example 1 and contains 20 parts by weight or more of an ethylene / α-olefin copolymer, and has a spiral flow, flexural modulus, transparency, and the like. This was inferior.
또한 비교예 3은, 에틸렌/α-올레핀 공중합체를 포함하지 않은 것으로서, 실시예 1 대비 투명성, 표면경도 등은 우수하나, 저온충격강도가 지나치게 낮아 저온환경에서의 사용이 불가하였다.In addition, Comparative Example 3, which does not include an ethylene / α-olefin copolymer, is excellent in transparency, surface hardness and the like compared to Example 1, but the low temperature impact strength is too low to use in a low temperature environment.
또한 비교예 4는, 에틸렌/α-올레핀 공중합체 및 핵제를 포함하지 않은 것으로서, 실시예 1 대비 스파이럴 플로우, 투명성, 열변형온도, 저온충격강도 등 거의 모든 물성이 열세하였다.In addition, Comparative Example 4, which does not contain an ethylene / α-olefin copolymer and a nucleating agent, was inferior to almost all physical properties, such as spiral flow, transparency, heat deformation temperature, low temperature impact strength.
또한 비교예 5는, 실시예 2 대비 호모폴리프로필렌의 아이소택틱 펜타드 분율이 낮은 것으로서, 실시예 2 대비 스파이럴 플로우가 열세하였다.In Comparative Example 5, the isotactic pentad fraction of homopolypropylene was lower than that of Example 2, and the spiral flow was inferior to that of Example 2.
본 발명에 따른 수지 조성물은, 흐름성이 적절하여 제품의 크기가 크고 복잡한 제품을 사출성형할 경우 휨, 미성형 등이 발생하지 않고, 강성, 충격강도, 경도 등의 기계적 강도가 우수하며, 특히 저온의 환경에서도 우수한 충격강도를 유지하며, 또한 투명성이 우수하다. 따라서, 이를 사용하여 제조된 성형품은 기존의 폴리 프로필렌 수지 대비 투명성, 표면경도, 내충격성이 우수하므로, 이러한 특성들이 요구되는 전기전자, 자동차용 대형제품, 산업용 사출품, 사무용 사출품 등의 분야에 있어서 외관용 성형품으로서 사용될 수 있다.The resin composition according to the present invention is suitable for flowability and does not cause warpage or unmolding when injection molding large and complicated products, and has excellent mechanical strength such as stiffness, impact strength, and hardness. It maintains excellent impact strength even in low temperature environment and also has excellent transparency. Therefore, the molded article manufactured using the same has excellent transparency, surface hardness, and impact resistance compared to the existing polypropylene resin, and therefore, it is suitable for fields such as electric and electronic products, large products for automobiles, industrial injection products, and office injection products requiring such characteristics. It can be used as a molded article for appearance.
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