KR100538713B1 - Polyolefin resin composition having exellent transparency and thermoformability - Google Patents

Polyolefin resin composition having exellent transparency and thermoformability Download PDF

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KR100538713B1
KR100538713B1 KR10-2003-0098656A KR20030098656A KR100538713B1 KR 100538713 B1 KR100538713 B1 KR 100538713B1 KR 20030098656 A KR20030098656 A KR 20030098656A KR 100538713 B1 KR100538713 B1 KR 100538713B1
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ethylene
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propylene
resin composition
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KR20050067658A (en
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차승엽
최연범
김창희
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삼성토탈 주식회사
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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

본 발명은 내백화성, 저온충격성, 인열강도가 우수하고, 투명성 및 진공성형특성이 우수한 진공성형 시트용 수지 조성물에 관한 것으로, 좀 더 상세하게는 하기 성분 (a) 50~95중량부, 성분 (b) 5~50중량부 및 성분 (c) 0.05~0.5중량부를 포함하는 것을 특징으로 하는 폴리올레핀 수지 조성물에 관한 것이다:The present invention relates to a resin composition for vacuum forming sheet having excellent whitening resistance, low temperature impact resistance, tear strength, and excellent transparency and vacuum forming characteristics, and more specifically, the following component (a) 50 to 95 parts by weight, component (b) 5 to 50 parts by weight and component (c) 0.05 to 0.5 parts by weight, the present invention relates to a polyolefin resin composition comprising:

(a) 용융지수(230℃, 2.16kg 하중 조건하, ASTM D1238 규격)가 0.6~10g/10min, 바람직하게는 0.6~5g/10min이고, 0.5~10중량%의 에틸렌을 함유하는 결정성 에틸렌-프로필렌 랜덤 공중합체 65~95중량%와, 절대점도가 0.5~1.5dl/g이고, 20~70중량%의 에틸렌을 함유하는 에틸렌-프로필렌 탄성 공중합체 5~35중량%로 구성된 에틸렌-프로필렌 공중합체 조성물;(a) crystalline ethylene-containing melt index (230 DEG C, 2.16 kg load condition, ASTM D1238 standard) of 0.6 to 10 g / 10 min, preferably 0.6 to 5 g / 10 min, and containing 0.5 to 10% by weight of ethylene; Ethylene-propylene copolymer composed of 65 to 95% by weight of propylene random copolymer, and 5 to 35% by weight of ethylene-propylene elastic copolymer containing 20 to 70% by weight of absolute viscosity of 0.5 to 1.5 dl / g. Composition;

(b) 저밀도 폴리에틸렌; 및(b) low density polyethylene; And

(c) 유기 솔비톨계 핵제.(c) an organic sorbitol-based nucleating agent.

Description

투명성 및 진공성형성이 우수한 폴리올레핀 수지 조성물{POLYOLEFIN RESIN COMPOSITION HAVING EXELLENT TRANSPARENCY AND THERMOFORMABILITY}POLYOLEFIN RESIN COMPOSITION HAVING EXELLENT TRANSPARENCY AND THERMOFORMABILITY}

본 발명은 내백화성, 저온충격성, 인열강도가 우수하고, 투명성 및 진공성형특성이 우수한 폴리올레핀 수지 조성물에 관한 것으로, 좀 더 상세하게는 에틸렌-프로필렌 공중합체 조성물, 저밀도 폴리에틸렌 및 유기 솔비톨계 핵제를 포함하는 것을 특징으로 하는 폴리올레핀 수지 조성물에 관한 것이다.The present invention relates to a polyolefin resin composition having excellent whitening resistance, low temperature impact resistance, tear strength, and excellent transparency and vacuum forming characteristics. More specifically, the present invention relates to an ethylene-propylene copolymer composition, a low density polyethylene and an organic sorbitol-based nucleating agent. It relates to a polyolefin resin composition comprising.

일반적으로, 폴리프로필렌 시트는 프로필렌-α-올레핀 랜덤 공중합체를 함유하는 공중합체 조성물을 사용하는 경우, 투명성은 우수하나 저온충격특성이 약한 문제점이 있다. 또한, 프로필렌 단독 중합체와 프로필렌-α-올레핀 공중합체로 이루어진 공중합체 조성물을 사용하는 경우, 저온 충격성은 우수하나 투명성이 떨어지고, 낙하충격시 백화현상이 발생하는 문제점이 있다. 또한, 프로필렌-α-올레핀 랜덤 공중합체에 에틸렌-α-올레핀 공중합체를 혼합한 수지 조성물을 적용하여 투명성을 유지하면서 저온충격성이 개선된 수지 조성물을 사용하는 경우, 프로필렌 단독 중합체와 프로필렌-α-올레핀 공중합체보다 투명성은 우수하나, 프로필렌-α-올레핀 랜덤 공중합체를 함유하는 공중합체 조성물보다는 투명성이 저하되는 단점이 있다. 또한, 상기한 3가지 조성물의 경우, MD 방향에서 인열강도가 낮은 단점이 있다. In general, when using a copolymer composition containing a propylene-α-olefin random copolymer, a polypropylene sheet has a problem of excellent transparency but low temperature impact characteristics. In addition, in the case of using a copolymer composition composed of a propylene homopolymer and a propylene-α-olefin copolymer, there is a problem in that impact resistance is low but transparency is low, and bleaching occurs during drop impact. In addition, when using the resin composition which mixed the ethylene-alpha-olefin copolymer with the propylene-alpha-olefin random copolymer, and improved transparency while maintaining low transparency, the propylene homopolymer and propylene-alpha- Transparency is superior to olefin copolymers, but has a disadvantage in that transparency is lowered than copolymer compositions containing propylene-α-olefin random copolymers. In addition, in the case of the three compositions described above, there is a disadvantage that the tear strength in the MD direction is low.

또한, 진공성형용 폴리프로필렌 시트는, 선형 사슬구조에 기인하는 약한 용융장력으로 인하여 다른 플라스틱 재료에 비해 진공성형이나 중공성형의 경우에, 가열도중 시트(Sheet)나 프리폼(free form)의 처짐현상(sagging)이 심하여 만족할 만한 성형성을 확보하지 못하였다. In addition, the polypropylene sheet for vacuum molding has a sagging phenomenon of sheet or free form during heating in the case of vacuum molding or blow molding compared to other plastic materials due to the weak melt tension due to the linear chain structure. Sagging was so severe that satisfactory formability was not obtained.

따라서, 상기한 문제점을 극복하기 위한 여러가지 방법이 제시되고 있는 바, 대한민국공개특허 제98-042450호에서는 0.5~90몰%의 1-부텐이 포함된 프로필렌-1-부텐 랜덤 공중합체로 이루어진 수지 조성물이 개시되어 있으며, 상기 수지 조성물은 경도가 낮아 유연성이 뛰어나고, 이를 폴리프로필렌 수지와 혼합한 경우 유연성, 인장신율특성, 내상부성 및 투명성 등이 우수한 열가소성 수지 조성물을 얻을 수 있다. 그러나, 상기 수지 조성물을 폴리프로필렌 수지와 혼합할 경우, 2㎛ 이하의 미세 분산에 의해 투명성에 한계가 있으며, 내백화특성의 향상이 미흡한 문제점이 있다.      Therefore, various methods for overcoming the above problems have been proposed. In Korean Patent Laid-Open Publication No. 98-042450, a resin composition composed of propylene-1-butene random copolymer containing 0.5-90 mol% of 1-butene It is disclosed, the resin composition is low in hardness and excellent in flexibility, when mixed with a polypropylene resin it can be obtained a thermoplastic resin composition excellent in flexibility, tensile elongation characteristics, scratch resistance and transparency. However, when the resin composition is mixed with a polypropylene resin, transparency is limited by fine dispersion of 2 μm or less, and there is a problem in that improvement of the whitening resistance is insufficient.

또한, 작용기로 변형된 폴리프로필렌(Functionalized Polypropylen)을 이용하여 시트 및 코팅의 특성을 개선하려는 시도가 있어 왔으며, 유럽특허 제574801호, 제678527호 및 제688817호 등에서는 기존의 폴리프로필렌에 이온화 방사선(ionizing radiation)이나 유리라디칼제(free radical agent)를 이용하여 작용기(functional group)나 불포화 모노머(unsaturated monomer)를 반응시킨 변형된 폴리프로필렌이 개시되어 있다. 또한, 이러한 수지 조성물을 기존의 폴리프로필렌에 혼합하여 폴리프로필렌의 시트 및 코팅 특성을 향상시키려는 시도가 있어 왔으나, 대부분 열안정성, 치수 안정성 및 진공성형성 등은 개선될 수 있는 반면, 투명성, 내백화성 및 인열특성을 향상시키지는 못하였다.In addition, attempts have been made to improve the properties of sheets and coatings using functionalized polypropylenes (Functionalized Polypropylen), and EP 574801, 678527, and 688817 have ionized radiation to existing polypropylenes. A modified polypropylene is disclosed in which functional groups or unsaturated monomers are reacted using ionizing radiation or free radical agents. In addition, attempts have been made to improve the sheet and coating properties of polypropylene by mixing such a resin composition with existing polypropylene, but in most cases, thermal stability, dimensional stability, and vacuum forming can be improved, while transparency and whitening resistance And did not improve the tear characteristics.

또한, 진공성형성을 향상시키기 위하여 용융지수가 매우 낮은 폴리프로필렌에 폴리에틸렌을 물리적으로 블렌드하는 방법이 있으나, 용융지수가 너무 낮아 가공성이 저하되고, 폴리프로필렌내에 폴리에틸렌의 미분산 효과에 의하여 투명성이 현격히 저하된다는 문제점이 있다. In addition, there is a method of physically blending polyethylene to polypropylene having a very low melt index in order to improve vacuum forming, but the melt index is too low to reduce workability, and the transparency is markedly due to the fine dispersion effect of polyethylene in the polypropylene. There is a problem of deterioration.

따라서, 종래의 폴리프로필렌을 이용한 투명시트 제품은 투명성과 저온내충격성, 내백화성, 인열특성 및 진공성형성 등 모두를 만족시키지는 못하였다. Therefore, the conventional transparent sheet product using polypropylene did not satisfy all of transparency and low temperature impact resistance, whitening resistance, tearing property and vacuum forming.

본 발명은 상기와 같은 종래 기술의 문제점들을 해결하기 위한 것으로, 투명성과 저온내충격성이 우수하면서, 내백화성, 인열특성 및 진공성형성이 모두 우수한 폴리올레핀 수지 조성물을 제공하는 것을 목적으로 한다.The present invention is to solve the problems of the prior art as described above, it is an object of the present invention to provide a polyolefin resin composition excellent in transparency and low temperature impact resistance, excellent in all the whitening resistance, tear properties and vacuum forming.

본 발명에 따른 수지 조성물은, 하기 성분 (a) 50~95중량부, 성분 (b) 5~50중량부 및 성분 (c) 0.05~0.5중량부를 포함하는 것을 특징으로 하는 폴리올레핀 수지 조성물이다:The resin composition according to the present invention is a polyolefin resin composition comprising 50 to 95 parts by weight of the component (a), 5 to 50 parts by weight of the component (b) and 0.05 to 0.5 parts by weight of the component (c):

(a) 용융지수(230℃, 2.16kg 하중 조건하, ASTM D1238 규격)가 0.6~10g/10min, 바람직하게는 0.6~5g/10min이고, 0.5~10중량%의 에틸렌을 함유하는 결정성 에틸렌-프로필렌 랜덤 공중합체 65~95중량%와, 절대점도가 0.5~1.5dl/g이고, 20~70중량%의 에틸렌을 함유하는 에틸렌-프로필렌 탄성 공중합체 5~35중량%로 구성된 에틸렌-프로필렌 공중합체 조성물;(a) crystalline ethylene-containing melt index (230 DEG C, 2.16 kg load condition, ASTM D1238 standard) of 0.6 to 10 g / 10 min, preferably 0.6 to 5 g / 10 min, and containing 0.5 to 10% by weight of ethylene; Ethylene-propylene copolymer composed of 65 to 95% by weight of propylene random copolymer, and 5 to 35% by weight of ethylene-propylene elastic copolymer containing 20 to 70% by weight of absolute viscosity of 0.5 to 1.5 dl / g. Composition;

(b) 저밀도 폴리에틸렌; 및(b) low density polyethylene; And

(c) 유기 솔비톨계 핵제.(c) an organic sorbitol-based nucleating agent.

본 발명에 사용되는 공중합체 조성물(a)중 에틸렌-프로필렌 랜덤 공중합체는 중합 반응장치에서 에틸렌과 프로필렌을 동시에 투입하여 제조한 랜덤 공중합체로서, 본 발명에서 에틸렌-프로필렌 랜덤 공중합체 성분의 역할은 제조물의 기계적 강성을 유지하는 동시에 적절한 정도의 내열성을 부여하고, 성분 (b)와의 적절한 광학적, 열역학적 상용성을 가지고 있어 투명성을 유지시키는 것이다. The ethylene-propylene random copolymer in the copolymer composition (a) used in the present invention is a random copolymer prepared by simultaneously adding ethylene and propylene in a polymerization reactor, and the role of the ethylene-propylene random copolymer component in the present invention is It maintains the mechanical rigidity of the product and at the same time gives heat resistance to an appropriate degree, and has an appropriate optical and thermodynamic compatibility with the component (b) to maintain transparency.

상기 에틸렌-프로필렌 랜덤 공중합체중의 에틸렌 성분의 함량은 0.5~10중량%인 것이 바람직하다. 에틸렌성분의 함량이 0.5중량% 미만인 경우 공중합체의 결정화도가 필요 이상으로 높아져서 생성된 조성물의 투명성을 저하시키게 되고, 10중량%를 초과하는 경우에는 결정화도가 급격히 저하되므로 강성이 저하되고, 내열성이 떨어져서 일상 생활에서 사용하는 시트의 재질로는 부적합하게 된다. The content of the ethylene component in the ethylene-propylene random copolymer is preferably 0.5 to 10% by weight. If the content of the ethylene component is less than 0.5% by weight, the degree of crystallinity of the copolymer is higher than necessary to decrease the transparency of the resulting composition. If the content of the ethylene content is more than 10% by weight, the crystallinity is sharply lowered, so the rigidity is lowered and the heat resistance is poor. The material of the sheet used in everyday life is not suitable.

상기 에틸렌-프로필렌 랜덤 공중합체의 용융지수는 0.6~10g/10min인 것이 바람직한데, 0.6g/10min 미만이면 처짐특성 및 내충격성은 향상되나 가공시 수지의 용융특성이 나쁘고, 10g/10min을 초과하면 처짐특성 및 내충격성 모두 나빠지는 단점이 있기 때문이다.It is preferable that the melt index of the ethylene-propylene random copolymer is 0.6 to 10 g / 10 min. If the melt index is less than 0.6 g / 10 min, the deflection characteristics and the impact resistance are improved, but the melt characteristics of the resin during processing are poor and the deflection exceeds 10 g / 10 min. This is because both characteristics and impact resistance deteriorate.

또한, 상기 공중합체 조성물(a)중에서의 에틸렌-프로필렌 랜덤 공중합체의 함량은 65~95중량%인 것이 바람직한데, 65중량% 미만인 경우 강성 및 내열성이 현격히 저하되고, 95중량%를 초과하는 경우 내충격특성의 향상에 효과가 없기 때문이다.In addition, the content of the ethylene-propylene random copolymer in the copolymer composition (a) is preferably 65 to 95% by weight, when less than 65% by weight stiffness and heat resistance is significantly lowered, when more than 95% by weight This is because it is not effective in improving the impact resistance.

본 발명에 사용되는 공중합체 조성물(a)중 에틸렌-프로필렌 탄성 공중합체는 에틸렌-프로필렌 랜덤 공중합체를 제조한 후에 이어지는 일련의 반응장치에서 제조되는데, 본 발명에서의 에틸렌-프로필렌 탄성 공중합체의 역할은 공중합체 조성물에 내충격특성을 부여하고, 처짐특성을 향상시키는 것이다. 또한, 에틸렌-프로필렌 랜덤 공중합체와 적절한 정도의 광학적, 열역학적 상용성을 가지고 있어, 조성물 제조시 ㎛ 이하의 미세 분산이 가능하여 투명성과 내백화특성을 동시에 부여하는 특징을 가지고 있다. In the copolymer composition (a) used in the present invention, the ethylene-propylene elastomer is prepared in a series of reaction apparatuses following the preparation of the ethylene-propylene random copolymer, and the role of the ethylene-propylene elastomer in the present invention. Silver imparts impact resistance to the copolymer composition and improves sag characteristics. In addition, it has an optical and thermodynamic compatibility with an appropriate degree of ethylene-propylene random copolymer, it is possible to finely disperse the micron or less at the time of manufacturing the composition, and has the characteristic of simultaneously providing transparency and whitening resistance.

상기 에틸렌-프로필렌 탄성 공중합체중의 에틸렌 함량은 20~70중량%인 것이 바람직하다. 에틸렌 함량이 20중량% 미만이거나 70중량%를 초과하는 경우에는 중합체의 탄성이 감소하여 내충격성이 저하된다. 에틸렌-프로필렌 탄성 공중합체의 절대점도는 0.5~1.5dl/g이 바람직하다. 절대점도가 0.5dl/g 미만인 경우에는 공중합체 조성물의 가공시, 성형직후에는 분산성이 양호하여 투명성이 향상되나, 낮은 절대점도로 인하여 저분자 물질의 표면전이현상이 나타나 투명을 오히려 악화시키는 단점이 있고, 절대점도가 1.5dl/g를 초과하는 경우에는 조성물의 성형시 탄성 공중합체 성분의 분산성이 저하되어 투명성이 감소하는 단점이 있다. The ethylene content in the ethylene-propylene elastic copolymer is preferably 20 to 70% by weight. If the ethylene content is less than 20% by weight or more than 70% by weight, the elasticity of the polymer is reduced, thereby lowering the impact resistance. As for the absolute viscosity of an ethylene-propylene elastic copolymer, 0.5-1.5 dl / g is preferable. When the absolute viscosity is less than 0.5 dl / g, during the processing of the copolymer composition, the dispersibility is good immediately after molding to improve the transparency, but the low absolute viscosity causes the surface transition phenomenon of the low molecular material, which worsens the transparency. And, if the absolute viscosity exceeds 1.5dl / g, there is a disadvantage in that the dispersibility of the elastic copolymer component during molding of the composition is lowered to decrease the transparency.

본 발명에 사용되는 저밀도 폴리에틸렌(b)은, 용융지수(190℃, 2.16kg 하중 조건하, ASTM D1238 규격)가 0.1~10g/10min인 것이 바람직하다. 용융지수가 0.1g/10min 미만이면 용융강도는 증가하나 혼련시 겔이 발생할 수 있으며, 10g/10min을 초과하면 과다한 양을 혼합하여야만 용융강도가 증가하는 단점이 있기 때문이다.As for the low density polyethylene (b) used for this invention, it is preferable that melt index (190 degreeC, ASTM D1238 standard under 2.16 kg load conditions) is 0.1-10 g / 10min. If the melt index is less than 0.1g / 10min, the melt strength may increase, but gel may occur during kneading. If the melt index exceeds 10g / 10min, the melt strength may increase only when an excessive amount is mixed.

저밀도 폴리에틸렌(b)은 폴리프로필렌에 블렌드시 용융강도를 증가시키는 역할을 한다. 다만, 일반적으로 LDPE와 폴리프로필렌의 블렌드시 용융강도는 증가하나 투명성이 나빠지는 문제가 있으므로, 용융강도와 투명성을 모두 증가시키기 위한 매개체가 필요한데, 이러한 역할을 에틸렌-프로필렌 탄성 공중합체가 수행한다. Low density polyethylene (b) serves to increase the melt strength when blended into polypropylene. However, in general, when the LDPE and polypropylene are blended, the melt strength is increased but the transparency is deteriorated. Therefore, a medium for increasing both the melt strength and the transparency is required, and the ethylene-propylene elastic copolymer plays such a role.

저밀도 폴리에틸렌(b)이 5중량부 미만일 경우에는 용융강도의 증가가 크지 않고, 50중량부를 초과하는 경우에는 용융강도 및 투명성이 나빠지는 단점이 있으므로, 5~50중량부 첨가하는 것이 바람직하다.When the low-density polyethylene (b) is less than 5 parts by weight, the increase in melt strength is not large, and when it exceeds 50 parts by weight, the melt strength and transparency are deteriorated. Therefore, 5 to 50 parts by weight is preferably added.

폴리프로필렌 시트의 투명용 핵제로는 통상 무기계 핵제와 유기 솔비톨계 핵제를 사용하나, 무기계 핵제는 투명성 향상 효과가 떨어지고, 분산성이 떨어지는 단점이 있다. 따라서, 본 발명에서는 시트의 투명성 향상을 위하여 유기 솔비톨계 핵제(c)를 사용하고, 바람직하게는 우수한 투명성을 발현하며, 냄새 문제가 가장 적은 3,4-디메틸벤질리덴 솔비톨을 사용한다. 상기 유기 솔비톨계 핵제의 함량이 0.05중량부 미만인 경우에는 투명성이 발현되지 않으며, 0.5중량부를 초과하는 경우에는 초과된 양에 비하여 시트의 투명성 향상 효과가 거의 없으므로, 본 발명의 수지 조성물에는 유기 솔비톨계 핵제를 0.05~0.5중량부 첨가하는 것이 바람직하다.As the transparent nucleating agent of the polypropylene sheet, an inorganic nucleating agent and an organic sorbitol nucleating agent are generally used, but the inorganic nucleating agent has a disadvantage of poor transparency and dispersibility. Therefore, in the present invention, the organic sorbitol-based nucleating agent (c) is used to improve the transparency of the sheet, and preferably 3,4-dimethylbenzylidene sorbitol is used which expresses excellent transparency and has the least odor problem. When the content of the organic sorbitol-based nucleating agent is less than 0.05 parts by weight, transparency is not expressed. When the content of the organic sorbitol-based nucleating agent is greater than 0.5 parts by weight, the transparency of the sheet is not substantially improved compared to the amount exceeded. It is preferable to add 0.05-0.5 weight part of nucleating agents.

본 발명의 수지 조성물에는, 그 특성을 크게 해치지 않는 범위내에서, 통상적으로 사용되는 산화방지제, 중화제, 분산제, 내후제, 대전방지제, UV 안정제, 슬립제, 안티블럭킹제, 안료, 탈크 및 무기핵제 등의 첨가제를 첨가하여 사용할 수 있다. In the resin composition of the present invention, antioxidants, neutralizing agents, dispersants, weathering agents, antistatic agents, UV stabilizers, slip agents, antiblocking agents, pigments, talc and inorganic nucleating agents which are usually used within a range that does not significantly impair the characteristics thereof Additives, such as these, can be used.

이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다. 그러나, 이들 실시예는 단지 예시적인 목적일 뿐 본 발명이 이에 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are merely for illustrative purposes and the present invention is not limited thereto.

[실시예]EXAMPLE

실시예 1Example 1

1단계 : 에틸렌-프로필렌 랜덤 공중합체의 제조 Step 1: Preparation of Ethylene-Propylene Random Copolymer

반응장치에 온도 70℃, 압력 38kg/cm2의 조건하에서 에틸렌과 프로필렌을 동시에 주입하여 통상의 방법으로 중합반응을 시키되, 생성되는 랜덤 공중합체내의 에틸렌과 프로필렌의 함량 비율이 에틸렌 3중량%, 프로필렌 97중량%가 되도록 공중합을 하여 에틸렌-프로필렌 랜덤 공중합체(1)를 제조하였다.Ethylene and propylene were simultaneously injected into the reactor under the conditions of 70 ° C. and a pressure of 38 kg / cm 2. The polymerization reaction was carried out in a conventional manner, but the content ratio of ethylene and propylene in the resulting random copolymer was 3% by weight of ethylene and propylene. Copolymerization was carried out to 97% by weight to prepare an ethylene-propylene random copolymer (1).

2단계 : 에틸렌-프로필렌 탄성 공중합체의 제조 및 공중합체 조성물의 제조Step 2: Preparation of Ethylene-Propylene Elastic Copolymer and Preparation of Copolymer Composition

1단계 중합이 이루어진 후, 이어지는 일련의 반응장치에 온도 80℃, 압력 17kg/cm2의 조건하에서 반응을 시키되, 생성되는 탄성 공중합체내의 에틸렌과 프로필렌의 함량 비율이 에틸렌 30중량%, 프로필렌 70중량%가 되도록 하고, 동시에 절대점도가 0.88dl/g이 되도록 에틸렌-프로필렌 탄성 공중합체(2)를 제조하되, 상기 성분 (1)과 성분 (2)의 함량 비율이, 성분 (1)이 90중량%, 성분 (2)가 10중량%가 되도록 각 단계의 중합량을 조절하여, 용융지수가 2g/10min인 공중합체 조성물(a)를 얻었다.After the one-stage polymerization was carried out, the subsequent series of reactors were reacted under the conditions of a temperature of 80 ° C. and a pressure of 17 kg / cm 2 , wherein the content ratio of ethylene and propylene in the resulting elastomeric copolymer was 30% by weight of ethylene and 70% by weight of propylene. Ethylene-propylene elastic copolymer (2) was prepared so as to be% and the absolute viscosity was 0.88 dl / g, wherein the content ratio of component (1) to component (2) was 90 weight component (1). The polymerization amount of each step was adjusted so that% and component (2) would be 10 weight%, and the copolymer composition (a) whose melt index is 2 g / 10min was obtained.

다음, 상기 공중합체 조성물(a) 95중량부와, 용융지수(190℃, 2.16kg 하중 조건하, ASTM D1238 규격)가 8g/10min인 저밀도 폴리에틸렌(b) 5중량부를 혼합한 조성물(성분 (a)+(b))을 제조하였다. Next, a composition (component (a) containing 95 parts by weight of the copolymer composition (a) and 5 parts by weight of a low density polyethylene (b) having a melt index (190 ° C., 2.16 kg load condition, ASTM D1238 standard) of 8 g / 10 min. ) + (b)) was prepared.

3단계 : 펠렛 및 시험 시편 제조Step 3: prepare pellets and test specimens

상기 단계에서 얻어진 조성물(성분 (a)+(b))에, 산화방지제 0.2중량부와 3,4-디메틸벤질리덴 솔비톨 0.2중량부를 혼련 및 2축 압출기에서 압출가공하여 펠렛으로 제조한 후, T-다이(die) 및 연마롤(polishing roll)을 구비한 시트성형기를 이용하여, T-다이법으로 압출온도 220℃, 냉각롤 온도 40℃ 및 성형속도 2m/분의 조건에서 성형시켜 두께 0.3mm의 시트를 얻었다. 또한, 내백화특성을 평가하기 위해, 상기 수지 조성물을 삼성클뢰크너 FCM-110(형체력=110톤) 성형사출기로 사출하여 100mm×100mm×2mm의 시편을 제조하였다.0.2 parts by weight of the antioxidant and 0.2 parts by weight of 3,4-dimethylbenzylidene sorbitol were kneaded and extruded into a composition (component (a) + (b)) obtained in the above step to produce pellets, followed by T -Using a sheet molding machine equipped with a die and a polishing roll, a thickness of 0.3 mm is formed by a T-die method at an extrusion temperature of 220 ° C., a cooling roll temperature of 40 ° C., and a molding rate of 2 m / min. Sheet was obtained. In addition, in order to evaluate the anti-whitening characteristics, the resin composition was injected into a Samsung Klukner FCM-110 (molding force = 110 tons) molding injection molding machine to prepare a specimen of 100 mm x 100 mm x 2 mm.

실시예 2 내지 3 및 비교예 1 내지 5Examples 2 to 3 and Comparative Examples 1 to 5

표 1에 나타낸 바와 같이, 성분 (1), (2), (a), (b), (c)의 조성 및 함량비를 대체하는 이외에는, 실시예 1에 준하여 폴리올레핀 수지 조성물을 제조하고, 실시예 1과 동일한 방법으로 시편을 제조하였다.As shown in Table 1, except for replacing the composition and the content ratio of components (1), (2), (a), (b) and (c), a polyolefin resin composition was prepared and carried out according to Example 1 A specimen was prepared in the same manner as in Example 1.

물성측정Property measurement

상기 실시예 1 내지 3 및 비교예 1 내지 5의 시편의 물성을 하기의 방법으로 측정하였다.The physical properties of the specimens of Examples 1 to 3 and Comparative Examples 1 to 5 were measured by the following method.

1) 절대점도1) absolute viscosity

고유점도를 135℃ 데칼린 용매에서 측정하였다.Intrinsic viscosity was measured in 135 ° C. decalin solvent.

2) 용융지수2) Melt Index

ASTM D1238 규격에 따라 230℃/190℃에서 2.16Kg 하중으로 측정하였다.According to ASTM D1238 standard was measured at 2.16Kg load at 230 ℃ / 190 ℃.

3) 펀칭시 내충격성3) Impact resistance when punching

삼성아토피나 자체 방법으로 측정하였다. 즉, 수지 조성물을 삼성클뢰크너 FCM-110(형체력=110톤) 성형사출기를 이용하여 100mm×100mm×2mm 시편으로 제작한 후, 1~5kg의 추(치구 지름 25 mm)를 한정된 높이에서 떨어뜨려 충격을 준 후에, 시편수의 절반이 파괴되는 힘을 측정하였다.It was measured by Samsung Atopina's own method. In other words, the resin composition was made into a 100mm × 100mm × 2mm specimen using the Samsung Klockner FCM-110 (mold force = 110 tons) molding injection machine, and then the 1-5 kg weight (25 mm diameter) was dropped from the limited height. After the impact, the force at which half the number of specimens was measured was measured.

4) 투명성4) transparency

ASTM D1004 규격에 따라 흐림도(haze) 값을 측정하였다. Haze values were measured according to ASTM D1004 specifications.

5) 백화 발생 정도(충격 백화)5) Whitening outbreak degree (impact whitening)

삼성아토피나 자체 방법으로 측정하였다. 즉, 수지 조성물을 삼성클뢰크너 FCM-110(형체력=110톤) 성형사출기를 이용하여 100mm×100mm×2mm 시편으로 제작한 후, 500g의 추(치구 지름 25 mm)를 10cm 높이에서 떨어뜨려 충격을 준 후에, 낙하 지점의 백화 발생 부위의 지름을 측정하였다.It was measured by Samsung Atopina's own method. That is, after the resin composition was manufactured into a 100mm × 100mm × 2mm specimen by using a Samsung Klukner FCM-110 (mold force = 110 ton) molding injection machine, 500 g of weight (25 mm diameter) was dropped from the height of 10 cm to give an impact. After giving, the diameter of the whitening site | part of the fall point was measured.

6) 인열강도6) tear strength

ASTM D1922 규격에 따라 엘리멘도르프(Elemendorf) 인열강도를 MD 및 TD 방향에서 측정하였다.Elemendorf tear strength was measured in the MD and TD directions according to ASTM D1922 specifications.

7) 열처짐특성(처짐시간)7) Thermal Deflection Characteristics (Sag Time)

펠렛 형태의 수지 조성물을 T-다이 형태의 캐스팅 장비를 활용하여 두께가 0.3mm인 시트로 성형한 후, 10cm 직경의 두 원판 사이에 시트를 장착하여 200℃의 오븐 속에서 10mm 처졌을 때의 시간을 측정하였다.The time when the resin composition in the form of pellets was formed into a sheet having a thickness of 0.3 mm by using a casting apparatus in the form of a T-die, and then the sheet was placed between two disks of 10 cm diameter and sag 10 mm in an oven at 200 ° C. Was measured.

물성 평가 결과Property evaluation result

본 발명의 물성평가 결과를 하기 표 1에 나타내었다.Physical property evaluation results of the present invention are shown in Table 1 below.

실시예 1 내지 3과 비교예 1을 비교해 보면, 성분 (1)에 에틸렌이 포함되지 않은 비교예 1에 비하여 실시예 1 내지 3이 투명성, 백화, 인열강도 및 처짐특성이 개선되었음을 알 수 있다.Comparing Examples 1 to 3 and Comparative Example 1, it can be seen that Examples 1 to 3 have improved transparency, whitening, tear strength and deflection characteristics compared to Comparative Example 1 in which component (1) does not contain ethylene. .

실시예 1 내지 3과 비교예 2를 비교해 보면, 성분 (2)와 성분 (b)가 포함되지 않은 비교예 2에 비해서 실시예 1 내지 3이 충격강도, 인열강도 및 처짐특성이 월등히 개선되었음을 알 수 있다. Comparing Examples 1 to 3 and Comparative Example 2, the impact strength, tear strength and deflection characteristics of Examples 1 to 3 were significantly improved compared to Comparative Example 2, which did not include component (2) and component (b). Able to know.

실시예 1 내지 3과 비교예 3을 비교해 보면, 절대점도가 1.5dl/g보다 큰 비교예 3에 비해서 절대점도가 0.5~1.5dl/g인 실시예 1 내지 3이 투명성이 우수하고 백화도 덜 발생한다는 것을 알 수 있다.Comparing Examples 1 to 3 and Comparative Example 3, Examples 1 to 3 having an absolute viscosity of 0.5 to 1.5 dl / g compared to Comparative Example 3 having an absolute viscosity greater than 1.5 dl / g had excellent transparency and less whitening. It can be seen that it occurs.

실시예 1 내지 3과 비교예 4를 비교해 보면, 성분 (c)가 포함되지 않은 비교예 4에 비해서 성분 (c)가 포함된 실시예 1 내지 3이 투명성이 개선되었음을 알 수 있다.Comparing Examples 1 to 3 and Comparative Example 4, it can be seen that Examples 1 to 3 containing component (c) improved transparency compared to Comparative Example 4, which did not contain component (c).

실시예 1 내지 3과 비교예 5를 비교해 보면, 성분 (b)가 50중량부를 초과하는 비교예 5에 비해서, 성분 (b)가 5~50중량부의 범위내인 실시예 1 내지 3이 투명성이 개선되었음을 알 수 있다.Comparing Examples 1 to 3 and Comparative Example 5, Examples 1 to 3 in which the component (b) is in the range of 5 to 50 parts by weight compared to Comparative Example 5 in which the component (b) exceeds 50 parts by weight It can be seen that the improvement.

[표 1]TABLE 1

구분division 측정항목 (단위)Measurement Item (Unit) 실시예Example 비교예Comparative example 1One 22 33 1One 22 33 44 55 성분(1)의 조성Composition of Component (1) 프로필렌 함량(중량%)Propylene Content (wt%) 9797 9797 96.596.5 100100 96.596.5 97.297.2 9797 9797 에틸렌 함량(중량%)Ethylene Content (wt%) 33 33 3.53.5 -- 3.53.5 2.82.8 33 33 성분(2)의 조성Composition of Component (2) 프로필렌 함량(중량%)Propylene Content (wt%) 7070 6161 6666 6060 -- 6363 7070 7070 에틸렌 함량(중량%)Ethylene Content (wt%) 3030 3939 3434 4040 -- 3737 3030 3030 절대점도 (dl/g)Absolute viscosity (dl / g) 0.880.88 0.910.91 1.301.30 2.502.50 -- 1.801.80 0.880.88 0.880.88 성분 (a)의 조성Composition of component (a) 성분 (a)내성분(1)의함량 (중량%)Component (a) Content of Component (1) (wt%) 9090 8888 7979 8585 100100 8383 9090 9090 성분 (a)내성분(2)의함량 (중량%)Component (a) Content of Component (2) (wt%) 1010 1212 2121 1515 -- 1717 1010 1010 성분 (a)+(b)의 조성The composition of component (a) + (b) 성분 (a)+(b)내 성분 (a)의함량 (중량부)Content of component (a) in components (a) + (b) (parts by weight) 9090 8080 7070 100100 100100 9090 9797 4040 성분 (a)+(b)내 성분 (b)의함량 (중량부)Content of component (b) in components (a) + (b) (parts by weight) 1010 2020 3030 00 00 1010 33 6060 성분 (a)+(b)+(c)내 성분 (c)의 함량(중량부)Content of component (c) in components (a) + (b) + (c) (parts by weight) 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 -- 0.20.2 물성 Properties 성분 (a)의 용융지수 (g/10min)Melt Index of Component (a) (g / 10min) 22 33 0.60.6 0.60.6 55 3.53.5 22 22 성분 (b)의 용융지수Melt index of component (b) 77 77 77 -- -- 77 77 77 성분 (a)+(b)의용융지수Melt Index of Components (a) + (b) 2.22.2 33 1.51.5 0.60.6 55 3.63.6 22 33 펀칭시 내충격성(J)Impact resistance when punching (J) 99 1010 1212 77 22 88 88 1515 투명성(haze)(%)% Haze 22 44 44 1010 22 55 1010 1515 백화 발생(충격백화)(mm)Whitening occurrence (shock whitening) (mm) 2.22.2 2.42.4 2.52.5 19.119.1 2.22.2 1010 2.22.2 55 인열강도 MDTear strength MD 252252 242242 200200 5050 5050 241241 262262 205205 인열강도 TDTear strength TD 303303 296296 282282 250250 260260 300300 340340 263263 처짐시간(sec)Deflection time (sec) 212212 201201 200200 8080 5050 210210 193193 202202

* 성분(1) : 에틸렌-프로필렌 랜덤 공중합체Component (1): ethylene-propylene random copolymer

* 성분(2) : 에틸렌-프로필렌 탄성 공중합체Component (2): ethylene-propylene elastic copolymer

* 성분 (a) : 에틸렌-프로필렌 공중합체 조성물(성분(1)+성분(2))Component (a): ethylene-propylene copolymer composition (component (1) + component (2))

* 성분 (b) : 저밀도 폴리에틸렌Component (b): low density polyethylene

* 성분 (c) : 3,4-디메틸벤질리덴 솔비톨Component (c): 3,4-dimethylbenzylidene sorbitol

본 발명에 의하면, 투명성이 우수하면서 내충격성, 내백화특성, 인열특성 및 처짐특성이 우수한 폴리올레핀 수지 조성물이 제공되며, 이는 이러한 특성이 특별히 요구되는 투명 시트 및 진공성형용 시트 용도에 특히 적합하다. According to the present invention, a polyolefin resin composition having excellent transparency and excellent impact resistance, whitening resistance, tearing property, and sagging property is provided, which is particularly suitable for transparent sheet and vacuum forming sheet applications in which such characteristics are particularly required.

Claims (3)

하기 성분 (a) 50~95중량부, 성분 (b) 5~50중량부 및 성분 (c) 0.05~0.5중량부를 포함하는 것을 특징으로 하는 폴리올레핀 수지 조성물:A polyolefin resin composition comprising the following components (a) 50 to 95 parts by weight, component (b) 5 to 50 parts by weight and component (c) 0.05 to 0.5 parts by weight: (a) 용융지수(230℃, 2.16kg 하중 조건하, ASTM D1238 규격)가 0.6~10g/10min, 바람직하게는 0.6~5g/10min이고, 0.5~10중량%의 에틸렌을 함유하는 결정성 에틸렌-프로필렌 랜덤 공중합체 65~95중량%와, 절대점도가 0.5~1.5dl/g이고, 20~70중량%의 에틸렌을 함유하는 에틸렌-프로필렌 탄성 공중합체 5~35중량%로 구성된 에틸렌-프로필렌 공중합체 조성물;(a) crystalline ethylene-containing melt index (230 DEG C, 2.16 kg load condition, ASTM D1238 standard) of 0.6 to 10 g / 10 min, preferably 0.6 to 5 g / 10 min, and containing 0.5 to 10% by weight of ethylene; Ethylene-propylene copolymer composed of 65 to 95% by weight of propylene random copolymer, and 5 to 35% by weight of ethylene-propylene elastic copolymer containing 20 to 70% by weight of absolute viscosity of 0.5 to 1.5 dl / g. Composition; (b) 저밀도 폴리에틸렌; 및(b) low density polyethylene; And (c) 유기 솔비톨계 핵제.(c) an organic sorbitol-based nucleating agent. 제 1항에 있어서, 상기 저밀도 폴리에틸렌은 용융지수(190℃, 2.16kg 하중 조건하, ASTM D1238 규격)가 0.1~10g/10min인 것을 특징으로 하는 폴리올레핀 수지 조성물.The polyolefin resin composition according to claim 1, wherein the low density polyethylene has a melt index (190 DEG C, 2.16 kg load condition, ASTM D1238 standard) of 0.1 to 10 g / 10 min. 제 1항에 있어서, 상기 유기 솔비톨계 핵제가 3,4-디메틸벤질리덴 솔비톨인 것을 특징으로 하는 폴리올레핀 수지 조성물.The polyolefin resin composition according to claim 1, wherein the organic sorbitol-based nucleating agent is 3,4-dimethylbenzylidene sorbitol.
KR10-2003-0098656A 2003-12-29 2003-12-29 Polyolefin resin composition having exellent transparency and thermoformability KR100538713B1 (en)

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