KR20200056523A - Polypropylene resin composition with excellent stress-whitening resistance, process for preparing the same, and article molded therefrom - Google Patents
Polypropylene resin composition with excellent stress-whitening resistance, process for preparing the same, and article molded therefrom Download PDFInfo
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Abstract
Description
본 발명은 폴리프로필렌 수지 조성물, 그 제조방법 및 그로부터 제조된 성형품에 관한 것이다. 상세하게는, 본 발명은 에틸렌-프로필렌 블록 공중합체 수지를 포함하며, 내백화성, 투명성 및 내충격성이 우수한 폴리프로필렌 수지 조성물에 관한 것이다. 본 발명에 따른 폴리프로필렌 수지 조성물은 접혔을 때 외관이 불량해 보일 수 있는 식품 포장용 파우치의 열접착층 필름 또는 후가공 시 변형에 따른 백화가 발생할 수 있는 전지의 포장용 필름 등에 효과적으로 사용될 수 있다.The present invention relates to a polypropylene resin composition, a method for manufacturing the same, and a molded article manufactured therefrom. In detail, the present invention relates to a polypropylene resin composition comprising an ethylene-propylene block copolymer resin and having excellent whitening resistance, transparency and impact resistance. The polypropylene resin composition according to the present invention can be effectively used for a heat-adhesive layer film of a pouch for food packaging, which may have a poor appearance when folded, or a film for packaging a battery that may undergo whitening due to deformation during post-processing.
폴리프로필렌 수지는 가전 제품, 자동차용 복합 소재, 일반 포장 재료로 폭 넓게 사용되고 있는 고분자 재료이다. 폴리프로필렌 수지는 고분자의 구조에 따라서 강성, 투명성, 내충격성 등에 차이가 있다.Polypropylene resin is a polymer material that is widely used in home appliances, automobile composite materials, and general packaging materials. Polypropylene resins have different stiffness, transparency, and impact resistance depending on the structure of the polymer.
이중에서, 에틸렌-프로필렌 블록 공중합체 수지는 에틸렌-프로필렌 고무 공중합체를 포함하기 때문에, 호모 폴리프로필렌이나 폴리프로필렌 랜덤 공중합체에 비해 내충격 특성이 우수하다. 따라서, 에틸렌-프로필렌 블록 공중합체 수지는 내충격성이 요구되는 자동차용 복합 소재나 일반 잡화에 주로 사용되고 있다.Among them, since the ethylene-propylene block copolymer resin includes an ethylene-propylene rubber copolymer, impact resistance is superior to that of a homo polypropylene or polypropylene random copolymer. Therefore, the ethylene-propylene block copolymer resin is mainly used for automobile composite materials or general goods requiring impact resistance.
반면에, 에틸렌-프로필렌 블록 공중합체 수지는 이러한 고무 성분으로 인해 투명성이 낮아서 투명성이 요구되는 필름 등의 용도에는 사용되기 어렵다. 따라서, 알루미늄과 합지되는 레토르트 식품 포장 필름과 같이 투명성이 특별히 요구되지 않는 용도에만 제한적으로 사용되고 있는 실정이다.On the other hand, the ethylene-propylene block copolymer resin has low transparency due to the rubber component, and thus it is difficult to be used in applications such as films requiring transparency. Therefore, it is a situation that is limitedly used only in applications in which transparency is not particularly required, such as a retort food packaging film laminated with aluminum.
또한, 에틸렌-프로필렌 블록 공중합체 수지는 폴리프로필렌 매트릭스(matrix)와 고무상 사이에 계면이 존재하기 때문에, 이로부터 제조된 필름이 접혔을 때 접힌 부위가 하얗게 변하는 백화(stress-whitening) 현상으로 인해 외관이 수려하지 않다는 단점이 있다.In addition, since the ethylene-propylene block copolymer resin has an interface between the polypropylene matrix and the rubber phase, due to the stress-whitening phenomenon in which the folded portion turns white when the film produced therefrom is folded. The disadvantage is that the appearance is not beautiful.
이러한 에틸렌-프로필렌 블록 공중합체의 단점을 보완하기 위해 다양한 연구가 진행되어 왔다. 예를 들어, 대한민국 특허 제1298417호는 에틸렌-프로필렌 랜덤 공중합체와 에틸렌-프로필렌 고무 공중합체가 단계적으로 중합된 에틸렌-프로필렌 블록 공중합체 수지를 개시하고 있다. 이 수지는 투명성과 내충격성이 향상되었지만, 용융 온도가 낮아 후가공에서 내열성을 요구하는 경우에는 적용에 한계가 있다.Various studies have been conducted to compensate for the disadvantages of the ethylene-propylene block copolymer. For example, Korean Patent No. 1298417 discloses an ethylene-propylene block copolymer resin in which ethylene-propylene random copolymer and ethylene-propylene rubber copolymer are polymerized in stages. Although this resin has improved transparency and impact resistance, its application is limited when its low melting temperature requires heat resistance in post-processing.
또한, 대한민국 특허 제1598715호는 호모 폴리프로필렌을 매트릭스로 사용한 에틸렌-프로필렌 블록 공중합체 수지를 개시하고 있다. 이 수지는 내충격성이 우수하며 내열성이 높아 고온 살균 이후에도 외관이 우수하지만, 투명성과 내백화성은 고려되지 않았다.In addition, Korean Patent No. 1598715 discloses an ethylene-propylene block copolymer resin using homo polypropylene as a matrix. Although this resin has excellent impact resistance and high heat resistance, it has excellent appearance even after high-temperature sterilization, but transparency and whitening resistance are not considered.
위와 같은 문제점을 해결하기 위해, 본 발명의 목적은 내백화성, 투명성 및 내충격성이 우수한 폴리프로필렌 수지 조성물을 제공하는 것이다.In order to solve the above problems, an object of the present invention is to provide a polypropylene resin composition excellent in whitening resistance, transparency and impact resistance.
본 발명의 다른 목적은 위 폴리프로필렌 수지 조성물의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for preparing the above polypropylene resin composition.
본 발명의 또 다른 목적은 위 폴리프로필렌 수지 조성물로부터 제조되는 성형품, 구체적으로는 식품 포장용 파우치의 열접착층 필름 또는 전지의 포장용 필름을 제공하는 것이다.Another object of the present invention is to provide a molded article manufactured from the above polypropylene resin composition, specifically, a heat-adhesive layer film of a pouch for food packaging or a film for packaging a battery.
위 목적을 달성하기 위한 본 발명의 일 구체예에 따라서, 반응기에서 단계적으로 중합된 에틸렌-프로필렌 블록 공중합체 수지를 포함하되, 에틸렌-프로필렌 블록 공중합체 수지가 프로필렌 단독 중합체 및 탄소 수 2~4개의 α-올레핀이 공중합된 프로필렌-α-올레핀 랜덤 공중합체로 구성되는 군으로부터 선택되는 폴리프로필렌계 매트릭스 70~88 중량%와 용제 추출물 함량으로 측정되는 에틸렌-프로필렌 고무 공중합체 12~30 중량%를 포함하고, 에틸렌-프로필렌 블록 공중합체 수지 중의 에틸렌 함량이 4~10 중량%이며, 에틸렌-프로필렌 블록 공중합체 수지의 결정화 온도가 110~130℃와 67~77℃ 온도 범위에서 2개 존재하는 폴리프로필렌 수지 조성물이 제공된다.According to an embodiment of the present invention for achieving the above object, the reactor comprises an ethylene-propylene block copolymer resin polymerized in stages, wherein the ethylene-propylene block copolymer resin is a propylene homopolymer and 2 to 4 carbon atoms. Contains 70-88% by weight of a polypropylene matrix selected from the group consisting of propylene-α-olefin random copolymers copolymerized with α-olefins and 12-30% by weight of ethylene-propylene rubber copolymers measured by solvent extract content. And, the ethylene content in the ethylene-propylene block copolymer resin is 4 to 10% by weight, the polypropylene resin having two crystallization temperatures of 110 to 130 ° C and 67 to 77 ° C temperature range of the ethylene-propylene block copolymer resin Compositions are provided.
바람직하게는, 에틸렌-프로필렌 블록 공중합체 수지 중의 에틸렌-프로필렌 고무 공중합체의 함량(중량%)과 에틸렌 함량(중량%)의 비가 2.5~3.5이다.Preferably, the ratio of ethylene-propylene rubber copolymer content (% by weight) to ethylene content (% by weight) in the ethylene-propylene block copolymer resin is 2.5 to 3.5.
에틸렌-프로필렌 블록 공중합체 수지는 ASTM D1238에 의거하여 2.16 kg의 하중으로 230℃에서 측정 시 용융지수가 1.0~10 g/10분일 수 있다.The ethylene-propylene block copolymer resin may have a melt index of 1.0 to 10 g / 10 min when measured at 230 ° C under a load of 2.16 kg according to ASTM D1238.
또한, 에틸렌-프로필렌 블록 공중합체 수지는 용융온도가 160~170℃일 수 있다.In addition, the ethylene-propylene block copolymer resin may have a melting temperature of 160 to 170 ° C.
본 발명의 구체예에 따른 폴리프로필렌 수지 조성물은 산화방지제, 중화제, 슬립제, 블로킹방지제, 보강재, 충진재, 내후안정제, 대전방지제, 활제, 핵제, 난연제, 안료 및 염료로 구성되는 군으로부터 선택되는 적어도 하나의 첨가제를 더 포함할 수 있다.The polypropylene resin composition according to an embodiment of the present invention is at least selected from the group consisting of antioxidants, neutralizing agents, slip agents, anti-blocking agents, reinforcing materials, fillers, weathering stabilizers, antistatic agents, lubricants, nucleating agents, flame retardants, pigments and dyes It may further include one additive.
구체적으로, 본 발명의 구체예에 따른 폴리프로필렌 수지 조성물은 이 조성물 총 중량을 기준으로 산화방지제 0.01~0.2 중량%를 포함할 수 있다.Specifically, the polypropylene resin composition according to an embodiment of the present invention may contain 0.01 to 0.2% by weight of antioxidant based on the total weight of the composition.
바람직하게는, 산화방지제가 테트라키스(메틸렌(3,5-디-t-부틸-4-히드록시)히드로실릴네이트), 펜타에리스리톨 테트라키스(3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트), 1,3,5-트리메틸-트리스(3,5-디-t-부틸-4-히드록시벤젠) 및 트리스(2,4-디-t-부틸페닐)포스파이트로 구성되는 군으로부터 선택되는 적어도 하나이다.Preferably, the antioxidant is tetrakis (methylene (3,5-di-t-butyl-4-hydroxy) hydrosilylnate), pentaerythritol tetrakis (3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate), 1,3,5-trimethyl-tris (3,5-di-t-butyl-4-hydroxybenzene) and tris (2,4-di-t-butylphenyl) ) It is at least one selected from the group consisting of phosphite.
본 발명의 구체예에 따른 폴리프로필렌 수지 조성물은 이 조성물 총 중량을 기준으로 중화제 0.01~0.2 중량%를 포함할 수 있다.The polypropylene resin composition according to an embodiment of the present invention may include 0.01 to 0.2% by weight of a neutralizing agent based on the total weight of the composition.
바람직하게는, 중화제가 하이드로탈사이트 및 칼슘 스테아레이트로 구성되는 군으로부터 선택되는 적어도 하나이다.Preferably, the neutralizing agent is at least one selected from the group consisting of hydrotalcite and calcium stearate.
본 발명의 다른 구체예에 따라서, 2개 이상의 연속되는 반응기에서 프로필렌 단독 중합체 및 탄소 수 2~4개의 α-올레핀이 공중합된 프로필렌-α-올레핀 랜덤 공중합체로 구성되는 군으로부터 선택되는 폴리프로필렌계 매트릭스를 중합하는 제1 중합단계 및 중합된 폴리프로필렌계 매트릭스의 존재 하에 에틸렌과 프로필렌을 투입하여 에틸렌-프로필렌 고무 공중합체 성분을 공중합함으로써 에틸렌-프로필렌 블록 공중합체 수지를 얻는 제2 중합단계를 포함하는, 폴리프로필렌 수지 조성물의 제조방법이 제공된다.According to another embodiment of the present invention, a polypropylene system selected from the group consisting of a propylene homopolymer and a propylene-α-olefin random copolymer in which 2 to 4 carbon atoms are copolymerized in two or more consecutive reactors. A first polymerization step of polymerizing the matrix and a second polymerization step of obtaining an ethylene-propylene block copolymer resin by copolymerizing ethylene-propylene rubber copolymer components by introducing ethylene and propylene in the presence of a polymerized polypropylene matrix. , A method for producing a polypropylene resin composition is provided.
위 제조방법에 있어서, 각각의 중합단계는 지글러-나타(Ziegler-Natta) 촉매의 존재 하에 수행될 수 있다. 여기서, 지글러-나타 촉매는 염화 마그네슘(MgCl2) 담체에 TiCl3와 TiCl4로부터 선택되는 적어도 하나의 염화 티타늄을 담지시켜 합성될 수 있다.In the above manufacturing method, each polymerization step can be carried out in the presence of a Ziegler-Natta catalyst. Here, the Ziegler-Natta catalyst may be synthesized by supporting at least one titanium chloride selected from TiCl 3 and TiCl 4 on a magnesium chloride (MgCl 2 ) carrier.
또한, 지글러-나타 촉매의 공촉매로서 트리에틸 알루미늄, 디에틸클로로 알루미늄, 트리부틸 알루미늄, 트리스이소부틸 알루미늄 및 트리옥틸 알루미늄으로 구성되는 군으로부터 선택되는 적어도 하나의 알킬 알루미늄 화합물이 사용되고; 외부 전자공여체로서 디페닐디메톡시실란, 페닐트리메톡시실란, 페닐에틸디메톡시실란, 페닐메틸디메톡시실란, 메톡시트리메틸실란, 이소부틸트리메톡시실란, 디이소부틸디메톡시실란, 디이소프로필디메톡시실란, 디-t-부틸디메톡시실란, 디시클로펜틸디메톡시실란, 시클로헥실메틸디메톡시실란 및 디시클로헥실디메톡시실란으로 구성되는 군으로부터 선택되는 적어도 하나의 유기 실란 화합물이 사용될 수 있다.In addition, at least one alkyl aluminum compound selected from the group consisting of triethyl aluminum, diethylchloro aluminum, tributyl aluminum, trisisobutyl aluminum and trioctyl aluminum is used as a co-catalyst of the Ziegler-Natta catalyst; Diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane, phenylmethyldimethoxysilane, methoxytrimethylsilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, diisopropyl as external electron donor At least one organosilane compound selected from the group consisting of dimethoxysilane, di-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane and dicyclohexyldimethoxysilane can be used. .
바람직하게는, 제1 중합단계가 2개 이상의 벌크 중합 반응기에서 지글러-나타 촉매의 존재 하에 폴리프로필렌계 매트릭스를 중합하는 단계이고, 제2 중합단계가 기상 중합 반응기에서 제1 중합단계에서 중합된 폴리프로필렌계 매트릭스와 지글러-나타 촉매의 존재 하에 에틸렌과 프로필렌을 공급하여 고무 성분의 에틸렌-프로필렌 공중합체를 공중합함으로써 에틸렌-프로필렌 블록 공중합체를 얻는 단계이다.Preferably, the first polymerization step is a step of polymerizing the polypropylene-based matrix in the presence of a Ziegler-Natta catalyst in two or more bulk polymerization reactors, and the second polymerization step is a poly polymerization in the first polymerization step in a gas phase polymerization reactor. This is a step of obtaining an ethylene-propylene block copolymer by copolymerizing a rubber component ethylene-propylene copolymer by supplying ethylene and propylene in the presence of a propylene matrix and a Ziegler-Natta catalyst.
본 발명의 또 다른 구체예에 따라서, 위 폴리프로필렌 수지 조성물을 성형하여 제조되는 폴리프로필렌 수지 성형품이 제공된다.According to another embodiment of the present invention, a polypropylene resin molded article produced by molding the above polypropylene resin composition is provided.
본 발명의 구체예에 따른 폴리프로필렌 수지 성형품은 식품 포장용 파우치의 열접착층 필름 또는 전지의 포장용 필름일 수 있다.The polypropylene resin molded article according to an embodiment of the present invention may be a heat-adhesive layer film of a pouch for food packaging or a film for packaging a battery.
본 발명의 구체예에 따른 폴리프로필렌 수지 조성물은 내백화성, 투명성 및 내충격성이 우수하여, 접혔을 때 외관이 불량해 보일 수 있는 식품 포장용 파우치의 열접착층 필름 또는 후가공 시 변형에 따른 백화가 발생할 수 있는 전지의 포장용 필름 등에 효과적으로 사용될 수 있다.The polypropylene resin composition according to an embodiment of the present invention has excellent whitening resistance, transparency, and impact resistance, and may cause whitening due to deformation during post-processing or a heat-adhesive layer film of a food packaging pouch that may look poor when folded. It can be effectively used for packaging films of batteries.
도 1a와 도 1b는 각각 실시예 1과 비교예 2에서 제조된 에틸렌-프로필렌 블록 공중합체 수지의 시차 주사 열량계(DSC) 결정화 곡선이다.
도 2a와 도 2b는 각각 실시예 1과 비교예 2에서 제조된 필름의 백화 현상을 평가한 사진이다.1A and 1B are differential scanning calorimeter (DSC) crystallization curves of the ethylene-propylene block copolymer resins prepared in Example 1 and Comparative Example 2, respectively.
2A and 2B are photographs evaluating the whitening phenomenon of the films prepared in Example 1 and Comparative Example 2, respectively.
이하, 본 발명에 관하여 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 구체예에 따른 폴리프로필렌 수지 조성물은 반응기에서 단계적으로 중합된 에틸렌-프로필렌 블록 공중합체 수지를 포함하되, 에틸렌-프로필렌 블록 공중합체 수지가 프로필렌 단독 중합체 및 탄소 수 2~4개의 α-올레핀이 공중합된 프로필렌-α-올레핀 랜덤 공중합체로 구성되는 군으로부터 선택되는 폴리프로필렌계 매트릭스 70~88 중량%와 용제 추출물 함량으로 측정되는 에틸렌-프로필렌 고무 공중합체 12~30 중량%를 포함하고, 에틸렌-프로필렌 블록 공중합체 수지 중의 에틸렌 함량이 4~10 중량%이며, 에틸렌-프로필렌 블록 공중합체 수지의 결정화 온도가 110~130℃와 67~77℃ 온도 범위에서 2개 존재한다.The polypropylene resin composition according to an embodiment of the present invention comprises an ethylene-propylene block copolymer resin polymerized in stages in a reactor, wherein the ethylene-propylene block copolymer resin is a propylene homopolymer and an α-olefin having 2 to 4 carbon atoms. 70 to 88% by weight of a polypropylene matrix selected from the group consisting of this copolymerized propylene-α-olefin random copolymer and 12 to 30% by weight of an ethylene-propylene rubber copolymer measured by a solvent extract content, ethylene -The content of ethylene in the propylene block copolymer resin is 4 to 10% by weight, and the crystallization temperature of the ethylene-propylene block copolymer resin is 110 to 130 ° C and 2 to 67 to 77 ° C.
구체적으로, 본 발명의 구체예에 따른 폴리프로필렌 수지 조성물은 에틸렌-프로필렌 블록 공중합체 수지를 포함한다. 여기서, 에틸렌-프로필렌 블록 공중합체 수지는 반응기에서 단계적으로 중합된 것이다.Specifically, the polypropylene resin composition according to an embodiment of the present invention includes an ethylene-propylene block copolymer resin. Here, the ethylene-propylene block copolymer resin is polymerized stepwise in a reactor.
예를 들어, 먼저 폴리프로필렌계 매트릭스(matrix)가 중합되고, 이어서 이 폴리프로필렌계 매트릭스에 에틸렌-프로필렌 고무가 블록 공중합되어 에틸렌-프로필렌 블록 공중합체 수지가 제조될 수 있다.For example, a polypropylene matrix is first polymerized, and then ethylene-propylene rubber is block copolymerized to the polypropylene matrix to produce an ethylene-propylene block copolymer resin.
여기서, 폴리프로필렌계 매트릭스는 프로필렌 단독 중합체 또는 탄소 수 2~4개의 α-올레핀이 공중합된 프로필렌-α-올레핀 랜덤 공중합체일 수 있다. 바람직하게는, 폴리프로필렌계 매트릭스가 프로필렌 단독 중합체일 수 있다.Here, the polypropylene matrix may be a propylene homopolymer or a propylene-α-olefin random copolymer copolymerized with 2 to 4 carbon atoms. Preferably, the polypropylene matrix can be a propylene homopolymer.
에틸렌-프로필렌 블록 공중합체 수지 중의 폴리프로필렌계 매트릭스의 함량은 70~88 중량%이다. 폴리프로필렌계 매트릭스의 함량이 70 중량% 미만이면, 에틸렌-프로필렌 블록 공중합체 수지의 중합 시에 생산성이 저하되어 바람직하지 않다. 반면, 폴리프로필렌계 매트릭스의 함량이 88 중량%를 초과하면, 수지 조성물의 내충격성이 저하될 수 있다.The content of the polypropylene matrix in the ethylene-propylene block copolymer resin is 70 to 88% by weight. When the content of the polypropylene matrix is less than 70% by weight, productivity is lowered during polymerization of the ethylene-propylene block copolymer resin, which is undesirable. On the other hand, when the content of the polypropylene matrix exceeds 88% by weight, the impact resistance of the resin composition may be lowered.
에틸렌-프로필렌 블록 공중합체 수지 중의 에틸렌-프로필렌 고무 공중합체의 함량은 12~30 중량%이다. 에틸렌-프로필렌 고무 공중합체의 함량이 12 중량% 미만이면, 수지 조성물의 내충격성이 저하될 수 있다. 반면, 에틸렌-프로필렌 고무 공중합체의 함량이 30 중량%를 초과할 경우, 에틸렌-프로필렌 블록 공중합체 수지의 중합 시에 생산성이 저하되어 바람직하지 않다. 여기서, 에틸렌-프로필렌 고무 공중합체의 함량은 용제 추출물의 함량으로 측정될 수 있으며, 용제로는 자일렌(xylene)이 바람직하다.The content of the ethylene-propylene rubber copolymer in the ethylene-propylene block copolymer resin is 12 to 30% by weight. When the content of the ethylene-propylene rubber copolymer is less than 12% by weight, impact resistance of the resin composition may be deteriorated. On the other hand, when the content of the ethylene-propylene rubber copolymer exceeds 30% by weight, productivity is lowered during polymerization of the ethylene-propylene block copolymer resin, which is undesirable. Here, the content of the ethylene-propylene rubber copolymer may be measured by the content of the solvent extract, and xylene is preferred as the solvent.
한편, 에틸렌-프로필렌 블록 공중합체 수지 중의 에틸렌 함량은 4~10 중량%이다. 에틸렌 함량이 4 중량% 미만이면, 수지 조성물의 내충격성이 충분하지 않을 수 있다. 반면, 에틸렌 함량이 10 중량%를 초과하면, 수지 조성물의 투명성이 낮아지고 내백화 특성이 저하될 수 있다.On the other hand, the ethylene content in the ethylene-propylene block copolymer resin is 4 to 10% by weight. If the ethylene content is less than 4% by weight, the impact resistance of the resin composition may not be sufficient. On the other hand, when the ethylene content exceeds 10% by weight, the transparency of the resin composition is lowered and the whitening property may be deteriorated.
본 발명의 구체예에 따른 에틸렌-프로필렌 블록 공중합체 수지에 있어서, 에틸렌-프로필렌 고무 공중합체의 함량(중량%)과 에틸렌 함량(중량%)의 비가 2.5~3.5일 수 있다. 이 비율이 2.5 미만인 경우, 수지 조성물의 투명성과 내백화성이 저하될 수 있다. 반면, 이 비율이 3.5를 초과할 경우, 반응기에서 에틸렌과 프로필렌의 공중합 제어가 어렵다. 그 결과, 고무 공중합체가 아닌 랜덤 공중합체가 중합되어 에틸렌-프로필렌 블록 공중합체의 중합이 용이하지 않을 수 있다.In the ethylene-propylene block copolymer resin according to an embodiment of the present invention, the ratio of the content (% by weight) and the ethylene content (% by weight) of the ethylene-propylene rubber copolymer may be 2.5 to 3.5. When the ratio is less than 2.5, transparency and whitening resistance of the resin composition may be deteriorated. On the other hand, when this ratio exceeds 3.5, it is difficult to control the copolymerization of ethylene and propylene in the reactor. As a result, a random copolymer rather than a rubber copolymer is polymerized, so that polymerization of the ethylene-propylene block copolymer may not be easy.
본 발명의 구체예에 따른 에틸렌-프로필렌 블록 공중합체 수지는 시차 주사 열량계(differential scanning calorimetry; DSC)로 측정되는 결정화 온도(crystallization temperature; Tc)가 110~130℃와 67~77℃ 온도 범위에서 2개 존재한다. 110~130℃의 온도 범위에 존재하는 강한 피크는 폴리프로필렌계 매트릭스의 결정화에 의한 것이다. 이 결정화 피크가 110℃ 미만의 온도에서 나타나면, 수지 조성물의 내열성이 부족하다. 반면, 이 결정화 피크가 130℃ 초과의 온도에서 나타나면, 수지의 결정화 속도가 너무 빨라서 무연신 필름 제막 시 냉각 롤과의 접촉이 균일하지 못하여 필름 품질이 저하될 수 있어 바람직하지 않다.The ethylene-propylene block copolymer resin according to an embodiment of the present invention has a crystallization temperature (Tc) measured by differential scanning calorimetry (DSC) of 110 to 130 ° C and 67 to 77 ° C in a temperature range of 2 Dogs exist. The strong peak present in the temperature range of 110 to 130 ° C is due to crystallization of the polypropylene matrix. When this crystallization peak appears at a temperature of less than 110 ° C, the heat resistance of the resin composition is insufficient. On the other hand, when this crystallization peak appears at a temperature exceeding 130 ° C., the crystallization rate of the resin is too fast, and thus the film quality may deteriorate due to the non-uniform contact with the cooling roll when forming a non-stretched film.
한편, 67~77℃의 온도 범위에 존재하는 약한 피크는 폴리프로필렌계 매트릭스에 분산된 에틸렌-프로필렌 고무상 내에 존재하는 나노-한정된 공간(nano-confined geometry)상에서의 폴리프로필렌의 균질(homogenous) 핵 형성에 의한 것으로 이해된다. 이 결정화 피크가 67℃ 미만의 온도에서 나타나면, 폴리프로필렌이 수 나노(nanometer) 크기로 분산되어야 하기 때문에, 상업적으로 중합이 불가능하다. 반면, 이 결정화 피크가 77℃ 초과의 온도에서 나타나면, 폴리프로필렌이 아닌 폴리에틸렌의 불균질(heterogenous) 결정화 피크이어서, 에틸렌-프로필렌 고무상의 형태에 영향을 주어 수지 조성물의 투명성 및 내백화성이 저하될 수 있다.On the other hand, the weak peaks present in the temperature range of 67-77 ° C. are homogenous nuclei of polypropylene in the nano-confined geometry present in the ethylene-propylene rubber phase dispersed in the polypropylene matrix. It is understood to be due to formation. When this crystallization peak appears at a temperature of less than 67 ° C., polymerization is not commercially possible because polypropylene must be dispersed in several nanometer sizes. On the other hand, if this crystallization peak appears at a temperature above 77 ° C., it is a heterogeneous crystallization peak of polyethylene rather than polypropylene, which affects the morphology of the ethylene-propylene rubber phase, thereby deteriorating the transparency and whitening resistance of the resin composition. have.
바람직하게는, 에틸렌-프로필렌 블록 공중합체 수지는 ASTM D1238에 의거하여 2.16 kg의 하중으로 230℃에서 측정 시 용융지수가 1.0~10 g/10분일 수 있다. 용융지수가 1.0 g/10분 미만이면, 압출 시 부하가 상승하여 생산성이 저하된다. 반면, 용융지수가 10 g/10분을 초과하면, 압출 시 처짐이 발생하여 두께 균일도가 저하되어 바람직하지 않다.Preferably, the ethylene-propylene block copolymer resin may have a melt index of 1.0 to 10 g / 10 min when measured at 230 ° C under a load of 2.16 kg according to ASTM D1238. If the melt index is less than 1.0 g / 10 minutes, the load increases during extrusion, and productivity decreases. On the other hand, if the melt index exceeds 10 g / 10 minutes, sagging occurs during extrusion, and the thickness uniformity decreases, which is not preferable.
또한, 에틸렌-프로필렌 블록 공중합체 수지는 용융온도가 160~170℃일 수 있다. 용융온도가 160℃보다 낮으면, 내열성이 충분하지 않아 고온의 후가공 시 변형이 발생할 수 있다. 한편, 용융온도가 170℃를 초과하는 폴리프로필렌은 상업적으로 중합이 불가능하다.In addition, the ethylene-propylene block copolymer resin may have a melting temperature of 160 to 170 ° C. When the melting temperature is lower than 160 ° C, heat resistance is insufficient, and deformation may occur during high temperature post-processing. On the other hand, polypropylene having a melting temperature exceeding 170 ° C is not commercially polymerizable.
본 발명의 구체예에 따른 폴리프로필렌 수지 조성물은 본 발명의 목적을 벗어나지 않는 범위 내에서 통상적인 첨가제를 더 포함할 수 있다. 예를 들어, 폴리프로필렌 수지 조성물은 산화방지제, 중화제, 슬립제, 블로킹방지제, 보강재, 충진재, 내후안정제, 대전방지제, 활제, 핵제, 난연제, 안료 및 염료 등을 포함할 수 있으나, 이들로 제한되는 것은 아니다.The polypropylene resin composition according to the embodiment of the present invention may further include a conventional additive within a range not departing from the object of the present invention. For example, the polypropylene resin composition may include antioxidants, neutralizing agents, slip agents, anti-blocking agents, reinforcing materials, fillers, weathering stabilizers, antistatic agents, lubricants, nucleating agents, flame retardants, pigments and dyes, but is not limited thereto. It is not.
바람직하게는, 본 발명의 구체예에 따른 폴리프로필렌 수지 조성물은 그 내열안정성을 증가시키기 위해 산화방지제를 포함할 수 있다. 이때, 산화방지제는 폴리프로필렌 수지 조성물 총 중량을 기준으로 0.01~0.2 중량%, 바람직하게는 0.05~0.15 중량%의 함량으로 추가될 수 있다. 산화방지제의 함량이 0.01 중량% 미만이면, 장기 내열안정성을 확보하기 어렵다. 한편, 산화방지제의 함량이 0.2 중량%를 초과하면, 산화방지제가 용출되거나 제품의 경제성이 저하될 수 있어 바람직하지 않다.Preferably, the polypropylene resin composition according to an embodiment of the present invention may include an antioxidant to increase its heat stability. At this time, the antioxidant may be added in an amount of 0.01 to 0.2% by weight, preferably 0.05 to 0.15% by weight based on the total weight of the polypropylene resin composition. If the content of the antioxidant is less than 0.01% by weight, it is difficult to secure long-term heat stability. On the other hand, if the content of the antioxidant exceeds 0.2% by weight, it is not preferable because the antioxidant may elute or the economics of the product may deteriorate.
산화방지제로는 페놀계 산화방지제, 포스파이트계 산화방지제 등이 이용될 수 있고, 구체적으로 테트라키스(메틸렌(3,5-디-t-부틸-4-히드록시)히드로실릴네이트), 펜타에리쓰리톨 테트라키스(3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트), 1,3,5-트리메틸-트리스(3,5-디-t-부틸-4-히드록시벤젠) 및 트리스(2,4-디-t-부틸페닐)포스파이트로 구성되는 군으로부터 선택되는 적어도 하나일 수 있으나, 이들로 제한되는 것은 아니다.As the antioxidant, a phenolic antioxidant, a phosphite-based antioxidant, or the like can be used, and specifically, tetrakis (methylene (3,5-di-t-butyl-4-hydroxy) hydrosilylnate), pentae Rithitol tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), 1,3,5-trimethyl-tris (3,5-di-t-butyl-4 -Hydroxybenzene) and tris (2,4-di-t-butylphenyl) phosphite, but may be at least one selected from the group consisting of, but is not limited to.
바람직하게는, 본 발명의 구체예에 따른 폴리프로필렌 수지 조성물은 촉매 잔사를 제거하기 위한 중화제로서 하이드로탈사이트, 칼슘 스테아레이트 등을 포함할 수 있다. 이때, 중화제는 폴리프로필렌 수지 조성물 총 중량을 기준으로 0.01~0.2 중량%, 바람직하게는 0.02~0.10 중량%의 함량으로 추가될 수 있다. 중화제의 함량이 0.01 중량% 미만이면, 수지의 촉매 잔사를 제거하는 효과를 확보하기 어렵고, 0.2 중량%를 초과하면, 촉매 잔사 제거 효과의 증가가 미미하며 수지 조성물의 가격 경제성이 저하될 수 있어 바람직하지 않다.Preferably, the polypropylene resin composition according to an embodiment of the present invention may include hydrotalcite, calcium stearate, and the like as neutralizing agents for removing catalyst residues. At this time, the neutralizing agent may be added in an amount of 0.01 to 0.2% by weight, preferably 0.02 to 0.10% by weight based on the total weight of the polypropylene resin composition. If the content of the neutralizing agent is less than 0.01% by weight, it is difficult to secure the effect of removing the catalyst residues of the resin, and when it exceeds 0.2% by weight, the increase in the effect of removing the catalyst residues is minimal and the economical cost of the resin composition may be lowered. Does not.
본 발명의 다른 구체예에 따른 폴리프로필렌 수지 조성물의 제조방법은 2개 이상의 연속되는 반응기에서 프로필렌 단독 중합체 및 탄소 수 2~4개의 α-올레핀이 공중합된 프로필렌-α-올레핀 랜덤 공중합체로 구성되는 군으로부터 선택되는 폴리프로필렌계 매트릭스를 중합하는 제1 중합단계 및 중합된 폴리프로필렌계 매트릭스의 존재 하에 에틸렌과 프로필렌을 투입하여 에틸렌-프로필렌 고무 공중합체 성분을 공중합함으로써 에틸렌-프로필렌 블록 공중합체 수지를 얻는 제2 중합단계를 포함한다.The method for preparing a polypropylene resin composition according to another embodiment of the present invention is composed of a propylene homopolymer and a propylene-α-olefin random copolymer in which 2 to 4 carbon atoms are copolymerized with a propylene homopolymer in two or more consecutive reactors. An ethylene-propylene block copolymer resin is obtained by copolymerizing ethylene-propylene rubber copolymer components by introducing ethylene and propylene in the presence of a polymerized polypropylene matrix and a first polymerization step of polymerizing a polypropylene matrix selected from the group And a second polymerization step.
이때, 각각의 중합은 슬러리법, 벌크법, 기상법 등과 같이 본 발명의 기술분야에서 통상적으로 알려진 방법 및 반응 조건을 이용할 수 있다.At this time, each polymerization may use methods and reaction conditions commonly known in the technical field of the present invention, such as a slurry method, a bulk method, and a gas phase method.
한편, 위 각각의 중합은 지글러-나타(Ziegler-Natta) 촉매의 존재 하에 수행될 수 있다. 지글러-나타 촉매는 당업계에 공지된 촉매를 제한 없이 사용할 수 있으나, 구체적으로 염화 마그네슘(MgCl2) 담체에 염화 티타늄(TiCl3 또는 TiCl4)와 같은 티타늄 화합물을 담지시켜 얻을 수 있다. 여기에 공촉매와 외부 전자공여체를 함께 사용하는 것이 바람직하다.On the other hand, each of the above polymerization can be carried out in the presence of a Ziegler-Natta (Ziegler-Natta) catalyst. The Ziegler-Natta catalyst may be used without limitation, a catalyst known in the art, but may be specifically obtained by supporting a titanium compound such as titanium chloride (TiCl 3 or TiCl 4 ) on a magnesium chloride (MgCl 2 ) carrier. It is preferable to use a co-catalyst and an external electron donor together.
공촉매로는 알킬 알루미늄 화합물이 사용될 수 있다. 알킬 알루미늄 화합물의 예로는 트리에틸 알루미늄, 디에틸클로로 알루미늄, 트리부틸 알루미늄, 트리스이소부틸 알루미늄, 트리옥틸 알루미늄 등을 들 수 있으나, 이들로 제한되지는 않는다.As the cocatalyst, an alkyl aluminum compound can be used. Examples of the alkyl aluminum compound include, but are not limited to, triethyl aluminum, diethylchloro aluminum, tributyl aluminum, trisisobutyl aluminum, trioctyl aluminum, and the like.
또한, 외부 전자공여체로는 유기 실란 화합물이 바람직하다. 유기 실란 화합물의 예로는 디페닐디메톡시실란, 페닐트리메톡시실란, 페닐에틸디메톡시실란, 페닐메틸디메톡시실란, 메톡시트리메틸실란, 이소부틸트리메톡시실란, 디이소부틸디메톡시실란, 디이소프로필디메톡시실란, 디-t-부틸디메톡시실란, 디시클로펜틸디메톡시실란, 시클로헥실메틸디메톡시실란, 디시클로헥실디메톡시실란 등을 들 수 있으나, 이들로 제한되지는 않는다.In addition, an organic silane compound is preferable as the external electron donor. Examples of the organic silane compound include diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane, phenylmethyldimethoxysilane, methoxytrimethylsilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, di Isopropyldimethoxysilane, di-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclohexyldimethoxysilane, and the like, but are not limited thereto.
본 발명의 구체예에 따른 폴리프로필렌 수지 조성물의 제조방법에 있어서, 위 제1 중합단계와 제2 중합단계가 동일한 중합 반응기 또는 상이한 중합 반응기에서 이루어질 수 있다.In the method for producing a polypropylene resin composition according to an embodiment of the present invention, the first polymerization step and the second polymerization step may be made in the same polymerization reactor or different polymerization reactors.
바람직하게는, 제1 중합단계가 2개 이상의 벌크 중합 반응기에서 지글러-나타 촉매의 존재 하에 폴리프로필렌계 매트릭스를 중합하는 단계이고, 제2 중합단계가 기상 중합 반응기에서 제1 중합단계에서 중합된 폴리프로필렌계 매트릭스와 지글러-나타 촉매의 존재 하에 에틸렌과 프로필렌을 공급하여 고무 성분의 에틸렌-프로필렌 공중합체를 공중합함으로써 에틸렌-프로필렌 블록 공중합체를 얻는 단계이다. 각각의 중합 반응기에서 생성되는 중합체의 용융지수는 각 중합 반응기에 투입되는 수소의 함량으로 조절될 수 있다.Preferably, the first polymerization step is a step of polymerizing the polypropylene-based matrix in the presence of a Ziegler-Natta catalyst in two or more bulk polymerization reactors, and the second polymerization step is a poly polymerization in the first polymerization step in a gas phase polymerization reactor. This is a step of obtaining an ethylene-propylene block copolymer by copolymerizing a rubber component ethylene-propylene copolymer by supplying ethylene and propylene in the presence of a propylene matrix and a Ziegler-Natta catalyst. The melt index of the polymer produced in each polymerization reactor can be controlled by the content of hydrogen input to each polymerization reactor.
이어서, 제1 중합단계에서 얻어진 폴리프로필렌계 매트릭스를 에틸렌-프로필렌 공중합이 실시되는 기상 반응기로 이송시키고, 에틸렌과 프로필렌을 동시에 투입함으로써 고체 상태의 폴리프로필렌계 매트릭스와 새로 투입된 에틸렌 및 프로필렌이 에틸렌-프로필렌 고무 공중합체 성분으로서 계속적으로 공중합되어 에틸렌-프로필렌 블록 공중합체를 제조할 수 있다.Subsequently, the polypropylene matrix obtained in the first polymerization step is transferred to a gas phase reactor in which ethylene-propylene copolymerization is performed, and ethylene and propylene are simultaneously added to solid-state polypropylene matrix and newly introduced ethylene and propylene are ethylene-propylene. It can be continuously copolymerized as a rubber copolymer component to produce an ethylene-propylene block copolymer.
이와 같이 얻어진 에틸렌-프로필렌 블록 공중합체는 본 발명의 목적을 벗어나지 않는 범위 내에서 통상적인 첨가제와 혼합될 수 있다. 구체적인 첨가제의 종류 및 함량은 위 폴리프로필렌 수지 조성물에 대한 내용과 실질적으로 동일하다.The ethylene-propylene block copolymer thus obtained can be mixed with conventional additives without departing from the object of the present invention. The types and contents of specific additives are substantially the same as those for the above polypropylene resin composition.
이때, 에틸렌-프로필렌 블록 공중합체와 첨가제를 혼합하는 방법에 특별한 제한은 없으며, 본 발명이 속하는 기술분야에 공지된 폴리프로필렌 수지 조성물의 제조방법을 그대로 또는 적절히 변형하여 사용할 수 있다.At this time, there is no particular limitation on the method of mixing the ethylene-propylene block copolymer and the additive, and the method of manufacturing the polypropylene resin composition known in the art to which the present invention pertains may be used as it is or by appropriately modifying it.
구체적으로 예를 들면, 에틸렌-프로필렌 블록 공중합체와 첨가제를 소정의 양만큼 니더(kneader), 롤(roll), 밴버리 믹서(Banbury mixer) 등의 혼련기 또는 1축/2축 압출기 등에 투입한 후 이들 기기들을 사용하여 투입된 원료들을 블렌딩하는 방법에 의해 본 발명의 폴리프로필렌 수지 조성물을 제조할 수 있다.Specifically, for example, after the ethylene-propylene block copolymer and additives are added to a kneader such as a kneader, roll, Banbury mixer or a single-screw / two-screw extruder by a predetermined amount The polypropylene resin composition of the present invention can be produced by a method of blending the input raw materials using these devices.
본 발명의 또 다른 구체예에 따라서, 본 발명의 폴리프로필렌 수지 조성물을 성형하여 제조되는 폴리프로필렌 수지 성형품이 제공된다.According to another embodiment of the present invention, a polypropylene resin molded article produced by molding the polypropylene resin composition of the present invention is provided.
본 발명의 구체예에 따른 폴리프로필렌 수지 조성물로부터 성형품을 제조하는 방법에 특별한 제한은 없으며, 본 발명이 속하는 기술분야에 공지된 방법을 사용할 수 있다. 예를 들어, 본 발명의 구체예에 따른 폴리프로필렌 수지 조성물을 사출성형, 압출성형, 캐스팅성형 등의 통상적인 방법으로 성형하여 폴리프로필렌 수지 성형품을 제조할 수 있다.There is no particular limitation on a method for manufacturing a molded article from a polypropylene resin composition according to an embodiment of the present invention, and methods known in the art to which the present invention pertains can be used. For example, a polypropylene resin molded article may be manufactured by molding the polypropylene resin composition according to an embodiment of the present invention by a conventional method such as injection molding, extrusion molding, and casting molding.
본 발명의 구체예에 따른 폴리프로필렌 수지 성형품은 내백화성, 투명성 및 내충격성이 우수하다. 따라서, 위 성형품은 식품 포장용 파우치의 열접착층 필름 또는 전지의 포장용 필름일 수 있다.The polypropylene resin molded article according to the embodiment of the present invention is excellent in whitening resistance, transparency and impact resistance. Accordingly, the molded article may be a heat-adhesive layer film of a food packaging pouch or a film for packaging a battery.
실시예Example
이하, 실시예와 비교예를 통하여 본 발명을 보다 구체적으로 설명한다. 단, 아래의 실시예는 본 발명을 예시하기 위한 것일 뿐이며, 본 발명의 범위가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited to them.
실시예Example 1~3 및 1 to 3 and 비교예Comparative example 1~4 1-4
에틸렌-프로필렌 블록 공중합체의 중합Polymerization of ethylene-propylene block copolymer
2기의 벌크 반응기와 2기의 기상 반응기가 직렬로 연결되어 연속으로 중합할 수 있는 미츠이(Mitsui)사 하이폴 공정(Hypol process)를 이용하였다. 이때, 지글러-나타(Ziegler-Natta) 촉매를 사용하였는데, 염화 마그네슘(MgCl2) 담체에 염화 티타늄(TiCl4)를 담지시키고, 프탈레이트 계열의 내부 전자공여체(internal donor)를 사용하였다. 공촉매로는 트리에틸알루미늄을 사용하였고, 외부 전자공여체(external donor)로 디시클로펜틸디메톡시실란을 사용하였다.A two-phase bulk reactor and two gas-phase reactors were connected in series, and a Mitsui Hypol process, which can continuously polymerize, was used. At this time, a Ziegler-Natta catalyst was used, and titanium chloride (TiCl 4 ) was supported on a magnesium chloride (MgCl 2 ) carrier, and a phthalate-based internal donor was used. Triethyl aluminum was used as the cocatalyst, and dicyclopentyl dimethoxysilane was used as an external donor.
1, 2단의 벌크 반응기에서 운전 온도와 압력은 각각 68~75℃, 30~40 kg/㎠과 68~75℃, 25~35 kg/㎠이었다. 3, 4단의 기상 반응기에서 운전 온도와 압력은 각각 75~82℃, 15~20 kg/㎠과 68~75℃, 10~17 kg/㎠이었다. 1 내지 3단 반응기에서는 프로필렌을 단독 주입하여 프로필렌 단독 중합체를 생성하였다. 생성된 프로필렌 단독 중합체를 이어지는 4단의 반응기로 이송하고, 위 지글러-나타 촉매의 존재 하에 에틸렌과 프로필렌을 투입하여 에틸렌-프로필렌 고무를 공중합함으로써 에틸렌-프로필렌 블록 공중합체를 얻었다. 이때, 각각의 반응기에서 생성되는 중합체의 용융지수는 각 반응기에 투입되는 수소의 함량으로 조절하였다. 이러한 방법으로 아래 표 1과 같이 에틸렌 함량, 용제추출물 함량을 조절하여 에틸렌-프로필렌 블록 공중합체를 얻었다.In the first and second stage bulk reactors, the operating temperature and pressure were 68 to 75 ° C, 30 to 40 kg / cm2, and 68 to 75 ° C and 25 to 35 kg / cm2, respectively. The operating temperature and pressure in the gas phase reactors of 3 and 4 stages were 75 to 82 ° C, 15 to 20 kg / cm 2 and 68 to 75 ° C, and 10 to 17 kg / cm 2, respectively. In the 1 to 3 stage reactor, propylene was injected alone to produce a propylene homopolymer. The resulting propylene homopolymer was transferred to a subsequent four-stage reactor, and ethylene-propylene rubber was copolymerized by adding ethylene and propylene in the presence of the above Ziegler-Natta catalyst to obtain an ethylene-propylene block copolymer. At this time, the melt index of the polymer produced in each reactor was adjusted to the content of hydrogen input to each reactor. In this way, as shown in Table 1 below, the ethylene content and the solvent extract content were adjusted to obtain an ethylene-propylene block copolymer.
얻어진 에틸렌-프로필렌 블록 공중합체 수지의 조성 및 물성을 아래와 같은 방법으로 측정하고, 그 결과를 아래 표 1에 기재하였다.The composition and physical properties of the obtained ethylene-propylene block copolymer resin were measured by the following method, and the results are shown in Table 1 below.
(1) 용융지수(melt index; g/10분)(1) Melt index (g / 10 min)
ASTM D1238에 의거하여 2.16 kg 하중으로 230℃에서 에틸렌-프로필렌 블록 공중합체 수지의 용융지수를 측정하였다.The melt index of the ethylene-propylene block copolymer resin was measured at 230 ° C. under a load of 2.16 kg according to ASTM D1238.
(2) 에틸렌 함량(중량%)(2) Ethylene content (% by weight)
적외선 흡수 스펙트럼을 사용하여 720 ㎝- 1와 730 ㎝-1의 특성 피크를 이용하여 에틸렌-프로필렌 블록 공중합체 중의 에틸렌의 함량을 측정하였다.Using the characteristic peak of 1 and 730 ㎝ -1 ethylene-using the infrared absorption spectrum was measured for 720 ㎝ ethylene content of the propylene block copolymer.
(3) 에틸렌-프로필렌 고무 공중합체(용제 추출물)의 함량(중량%)(3) Content of ethylene-propylene rubber copolymer (solvent extract) (% by weight)
에틸렌-프로필렌 블록 공중합체 수지를 자일렌(xylene)에 1 중량%의 농도로 140℃에서 1시간 녹인 후, 상온에서 2시간 경과 후 추출된 중량을 측정하였다. 얻어진 중량을 에틸렌-프로필렌 블록 공중합체 수지의 중량에 대한 백분율로 표시하였다.The ethylene-propylene block copolymer resin was dissolved in xylene at a concentration of 1% by weight at 140 ° C for 1 hour, and the extracted weight was measured after 2 hours at room temperature. The weight obtained was expressed as a percentage of the weight of the ethylene-propylene block copolymer resin.
(4) 용융온도 및 결정화 온도(Tm, Tc)(4) Melting temperature and crystallization temperature (Tm, Tc)
시차 주사 열량계(DSC)를 이용하여 시료를 200℃에서 10분간 등온으로 유지하여 열이력을 제거한 후, 200℃로부터 30℃까지 분당 10℃씩 냉각하며 결정화시켜 결정화 온도(crystallization temperature; Tc)를 구하였다. 이와 같은 냉각으로 동일한 열이력을 갖도록 한 후, 30℃에서 10분간 등온으로 유지하였다. 이어서, 다시 분당 10℃씩 재승온시키며 피크 용융 온도로부터 용융 온도(melting temperature; Tm)를 구하였다. 실시예 1과 비교예 2의 결정화 곡선을 도 1에 나타내었다.Using a differential scanning calorimeter (DSC), the sample is kept at 200 ° C. for 10 minutes to remove the thermal history, and then cooled from 200 ° C. to 30 ° C. at 10 ° C. per minute and crystallized to obtain the crystallization temperature (Tc). Did. After having the same heat history by such cooling, it was maintained at isotherm at 30 ° C. for 10 minutes. Subsequently, the temperature was again raised at 10 ° C per minute to obtain a melting temperature (Tm) from the peak melting temperature. The crystallization curves of Example 1 and Comparative Example 2 are shown in FIG. 1.
시편의 제조Preparation of specimen
위 실시예 및 비교예에서 제조된 각각의 에틸렌-프로필렌 블록 공중합체 수지에 0.1 중량% 함량의 산화방지제(펜타에리쓰리톨 테트라키스(3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트))와 0.04 중량% 함량의 중화제(하이드로탈사이트)를 추가하여 혼련하고, 이축 압출기에서 압출 가공하여 펠렛으로 제조하였다. 얻어진 수지 조성물을 통상의 캐스트 필름 압출 설비를 사용하여 두께 0.4 mm의 필름으로 성형하였다. 필름 성형 시 압출기 온도는 230℃이었으며, 필름 성형을 위한 냉각 롤의 온도는 30℃이었다. 또한, 사출 성형품의 물성 평가를 위해, 통상의 사출 설비를 사용하여 ASTM 규격의 시편을 제조하였다. 사출기 온도는 220℃이었고, 금형 온도는 60℃이었다. 필름과 사출 시편의 물성을 아래와 같은 방법으로 측정하고, 평가 결과는 표 1에 나타내었다.0.1% by weight of antioxidant (pentaerythritol tetrakis (3- (3,5-di-t-butyl-4-hydro) in each ethylene-propylene block copolymer resin prepared in Examples and Comparative Examples above Roxyphenyl) propionate)) and 0.04% by weight of a neutralizing agent (hydrotalcite) were added and kneaded, and extruded in a twin-screw extruder to prepare pellets. The obtained resin composition was molded into a film having a thickness of 0.4 mm using a conventional cast film extrusion equipment. The extruder temperature during film forming was 230 ° C, and the temperature of the cooling roll for film forming was 30 ° C. In addition, for the evaluation of the properties of the injection molded article, specimens of ASTM standards were prepared using a conventional injection equipment. The injection machine temperature was 220 ° C and the mold temperature was 60 ° C. The properties of the film and the injection specimen were measured in the following manner, and the evaluation results are shown in Table 1.
(5) 흐림도(haze)(5) Haze
ASTM D1003에 의거하여 측정하였다.It was measured according to ASTM D1003.
(6) 낙구 충격 강도(falling dart impact; FDI)(6) Falling dart impact (FDI)
ASTM D4226에 의거하여 측정하였다.It was measured according to ASTM D4226.
(7) 내백화성(stress-whitening resistance)(7) stress-whitening resistance
필름에 흠집을 준 다음 양쪽으로 잡아당겨서 도 2와 같이 찢어진 부위의 백화 발생 정도를 육안으로 확인하였다.The film was scratched and then pulled on both sides to visually confirm the degree of whitening of the torn portion as shown in FIG. 2.
(8) 굴곡탄성율(flexural modulus, FM)(8) Flexural modulus (FM)
ASTM D790에 의거하여 측정하였다.It was measured according to ASTM D790.
(9) 아이조드(Izod) 충격강도(9) Izod impact strength
ASTM D256에 의거하여 상온에서 측정하였다.It was measured at room temperature according to ASTM D256.
(10) 열변형 온도(heat distortion temperature; HDT)(10) heat distortion temperature (HDT)
ASTM D648에 의거하여 측정하였다.It was measured according to ASTM D648.
특성Suzy
characteristic
Tc(저온; ℃)Tc (high temperature; ℃)
Tc (low temperature; ℃)
71121
71
72116
72
73116
73
-120
-
99122
99
95120
95
94119
94
용제 추출물 함량(중량%)
에틸렌 함량(중량%)
용제 추출물/에틸렌Matrix content (% by weight)
Solvent extract content (% by weight)
Ethylene content (% by weight)
Solvent extract / ethylene
17.0
5.3
3.283.0
17.0
5.3
3.2
20.0
6.5
3.180.0
20.0
6.5
3.1
23.0
8.5
2.777.0
23.0
8.5
2.7
11.0
5.0
2.289.0
11.0
5.0
2.2
11.5
8.0
1.488.5
11.5
8.0
1.4
11.6
9.0
1.388.4
11.6
9.0
1.3
20.0
9.5
2.180.0
20.0
9.5
2.1
물성film
Properties
낙구충격강도(g)
내백화성Cloudiness (%)
Falling impact strength (g)
Whitening resistance
1400
○16
1400
○
1500
○18
1500
○
1700
○19
1700
○
600
×38
600
×
1000
×63
1000
×
1200
×55
1200
×
1500
△10
1500
△
Izod(상온; kg cm/cm)
열변형 온도(℃)Flexural modulus (kg / ㎠)
Izod (room temperature; kg cm / cm)
Heat deflection temperature (℃)
25
10610500
25
106
35
1059500
35
105
65
1049000
65
104
9
10914500
9
109
10
10814000
10
108
10
10814000
10
108
30
1059500
30
105
표 1로부터 확인되는 바와 같이, 본 발명의 범위에 속하는 실시예 1~3의 경우, 필름의 흐림도가 낮고 낙구충격강도가 높아서, 투명성과 내충격성이 우수하였다.As can be seen from Table 1, in Examples 1 to 3, which fall within the scope of the present invention, the film had a low degree of cloudiness and a high drop impact strength, and thus excellent transparency and impact resistance.
반면, 본 발명의 범위에 속하지 않는 비교예 1~3의 경우, 용제 추출물 함량이 낮아 내충격성이 좋지 않았고, Tc가 120~121℃, 95~99℃이었고, 용제 추출물과 에틸렌의 비가 낮아서 필름의 투명성과 내백화성이 좋지 않았다. 비교예 4는 투명성과 내충격강도는 양호하였지만, Tc가 119℃, 94℃이었고, 용제 추출물과 에틸렌의 비율이 낮아서, 필름의 내백화성이 충분하지 않았다.On the other hand, in Comparative Examples 1 to 3, which do not belong to the scope of the present invention, the solvent extract content was low and the impact resistance was poor, and the Tc was 120 to 121 ° C, 95 to 99 ° C, and the ratio of the solvent extract to ethylene was low. Transparency and whitening resistance were not good. In Comparative Example 4, although transparency and impact resistance were good, Tc was 119 ° C and 94 ° C, and the ratio of the solvent extract and ethylene was low, so the whitening resistance of the film was insufficient.
본 발명의 범위에 속하는 실시예에 따른 폴리프로필렌 수지 조성물은 내백화성, 투명성 및 내충격성이 우수한 성형품, 구체적으로 필름을 제공할 수 있다. 따라서, 본 발명의 구체예에 따른 폴리프로필렌 수지 조성물은 식품 포장용 파우치의 열접착층 필름 또는 전지의 포장용 필름의 제조에 효과적으로 사용될 수 있다.The polypropylene resin composition according to an embodiment falling within the scope of the present invention can provide a molded article having excellent whitening resistance, transparency, and impact resistance, and specifically a film. Therefore, the polypropylene resin composition according to an embodiment of the present invention can be effectively used in the production of a heat-adhesive layer film of a pouch for food packaging or a film for packaging of a battery.
Claims (15)
The polypropylene resin molded article according to claim 14, which is a heat-adhesive layer film of a food packaging pouch or a film for packaging a battery.
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| KR1020180139836A KR102124702B1 (en) | 2018-11-14 | 2018-11-14 | Polypropylene resin composition with excellent stress-whitening resistance, process for preparing the same, and article molded therefrom |
| JP2019191630A JP6910407B6 (en) | 2018-11-14 | 2019-10-21 | Polypropylene resin composition with excellent whitening resistance, its preparation method, and molded products produced by it. |
| CN201911103017.9A CN111187482B (en) | 2018-11-14 | 2019-11-12 | Polypropylene resin composition having excellent whitening resistance, process for producing the same, and molded article molded from the same |
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| KR1020180139836A KR102124702B1 (en) | 2018-11-14 | 2018-11-14 | Polypropylene resin composition with excellent stress-whitening resistance, process for preparing the same, and article molded therefrom |
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| KR20220078043A (en) * | 2020-12-03 | 2022-06-10 | 에쓰대시오일 주식회사 | Polypropylene resin composition, manufacturing method of the same, and measuring method of rheological properties of the polypropylene resin composition |
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| Publication number | Publication date |
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| JP6910407B6 (en) | 2021-08-25 |
| JP6910407B2 (en) | 2021-07-28 |
| KR102124702B1 (en) | 2020-06-19 |
| JP2020084176A (en) | 2020-06-04 |
| CN111187482A (en) | 2020-05-22 |
| CN111187482B (en) | 2022-12-20 |
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