KR20010009458A - Ethylene propylene block copolymers composition - Google Patents
Ethylene propylene block copolymers composition Download PDFInfo
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- KR20010009458A KR20010009458A KR1019990027823A KR19990027823A KR20010009458A KR 20010009458 A KR20010009458 A KR 20010009458A KR 1019990027823 A KR1019990027823 A KR 1019990027823A KR 19990027823 A KR19990027823 A KR 19990027823A KR 20010009458 A KR20010009458 A KR 20010009458A
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Abstract
Description
본 발명은 에틸렌 프로필렌 블록 공중합체 수지 조성물에 관한 것으로서, 특히 160℃ 이상에서 단시간 고온 살균할 수 있는 레토르트 식품 포장용 에틸렌 프로필렌 공중합체 수지 조성물에 관한 것이다.The present invention relates to an ethylene propylene block copolymer resin composition, and more particularly to a retort food packaging ethylene propylene copolymer resin composition capable of high temperature sterilization at 160 ° C. or higher for a short time.
일반적으로 프로필렌이 단독 중합된 호모 폴리프로필렌은 강성, 인장강도 및 내열성은 뛰어나나 저온 보관 식품 포장용이나 열접착층의 재질로 사용될 때 낮은 저온 충격 강도나 낮은 열접착 강도 때문에 사용에 많은 제한이 있어 왔다.In general, homo propylene homopolymerized with propylene has excellent rigidity, tensile strength and heat resistance, but has been limited in use due to low cold impact strength or low thermal adhesive strength when used as a material for low temperature food packaging or heat adhesive layer.
이러한 낮은 내충격성과 낮은 열접착 강도를 개질하기 위하여 폴리프로필렌을 중합시킬 때 α-올레핀 예컨대, 에틸렌을 부가적으로 첨가하여 공중합시킨 에틸렌 프로필렌 블록 공중합체가 개발되었다. 이러한 에틸렌 프로필렌 블록 공중합체는 충격과 열접착성의 개질에는 효과가 있으나 공중합체의 특성상 기존 호모폴리프로필렌에 비해 강성, 내열성 및 외관이 저하되는 문제가 발생하게 된다.In order to modify such low impact resistance and low thermal adhesive strength, an ethylene propylene block copolymer has been developed in which a polyolefin is polymerized to additionally copolymerize α-olefins such as ethylene. The ethylene propylene block copolymer is effective in modifying impact and heat adhesiveness, but the stiffness, heat resistance, and appearance are degraded compared to conventional homopolypropylene due to the characteristics of the copolymer.
폴리프로필렌의 충격 및 열접착 특성을 향상시키기 위한 다른 몇 가지 방법이 있다. 그 중 하나가 EPM(에틸렌 프로필렌 공중합체) 혹은 EPDM(에틸렌 프로필렌 다이엔 공중합체) 같은 고무 성분의 물질을 폴리프로필렌에 용융 혼합시키는 방법이 폭넓게 이용되어 왔다. 그러나 이 경우 EPM 혹은 EPDM의 분산이 문제가 될 수 있고, 가격이 상승하는 문제가 발생한다.There are several other ways to improve the impact and thermal adhesion properties of polypropylene. One of them has been widely used to melt-mix a rubber component such as EPM (ethylene propylene copolymer) or EPDM (ethylene propylene diene copolymer) to polypropylene. However, in this case, the dispersion of EPM or EPDM can be a problem, and the price rises.
따라서 본 발명의 목적은 종래의 제품과 비교할 때 외관 및 강성, 내열성, 내충격성이 우수한 에틸렌 프로필렌 블록 공중합체를 제공하려는 것이다.Accordingly, an object of the present invention is to provide an ethylene propylene block copolymer having excellent appearance and stiffness, heat resistance, and impact resistance as compared with conventional products.
이에 본 발명자는 특별히 전자공여체를 사용하여 호모폴리프로필렌의 아이소탁티시티 및 분자량 분포를 조절하여 강성 및 내열성을 향상시키고, 또한 공중합시키는 EPR(Ethylene-propylene rubber: 이하에서 "EPR"이라 함)의 함량을 적절히 조절하여 내충격성 및 열접착 특성을 향상시켰고 EPR의 절대점도(IV, intrinsic viscosity)를 적절히 조절하여 외관을 향상시켰다.Accordingly, the present inventors specifically control the isotacticity and molecular weight distribution of homopolypropylene using an electron donor to improve rigidity and heat resistance, and also to copolymerize EPR (Ethylene-propylene rubber: hereinafter referred to as "EPR"). By appropriately adjusting, the impact resistance and heat adhesive properties were improved, and the absolute viscosity (IV, intrinsic viscosity) of EPR was properly adjusted to improve appearance.
좀더 구체적으로는 본 발명자는 호모 폴리프로필렌의 아이소탁티시티를 95% 이상, 더욱 바람직하게는 95 ~ 97%로 조절하고, 절대 점도 1.5 ~ 3.0dl/g 인 EPR의 함량을 7 ~ 12중량%로 조절하여 외관, 내충격성, 열접착 특성 등의 물성을 향상시킨 에틸렌 프로필렌 블록 공중합체 수지 조성물을 제조하였다.More specifically, the present inventors adjust the isotacticity of homopolypropylene to 95% or more, more preferably 95 to 97%, and adjust the content of EPR having an absolute viscosity of 1.5 to 3.0 dl / g to 7 to 12% by weight. The ethylene propylene block copolymer resin composition was prepared by adjusting physical properties such as appearance, impact resistance, and heat adhesive properties by adjusting.
본 발명으로 제조된 에틸렌 프로필렌 블록 공중합체는 제1단계에서 고입체규칙성 폴리프로필렌 단독중합체가 70∼95% 중합되고, 이어서 제 2단계에서 에틸렌 또는 에틸렌 프로필렌 공중합체가 생성된다.The ethylene propylene block copolymers prepared according to the present invention are polymerized from 70 to 95% of the high-stereoregular polypropylene homopolymer in the first stage, followed by the production of ethylene or ethylene propylene copolymer in the second stage.
구체적으로 이러한 에틸렌 프로필렌 블록공중합체 시스템에서 사용되는 촉매성분은 특허출원 제97-17650호에 기재되어 있다. 상기 특허출원의 내용을 간략히 요약해 보면 마그네슘과 할로겐함유 티타늄화합물 및 내부 전자공여체를 필수 성분으로 하는 고체착물 티타늄 촉매와, 주기율표 제I족 및 제III족 금속의 유기금속 화합물 및 외부 전자공여체로서 동일 중합조건에서 각각의 유기규소 화합물을 사용하여 중합한 호모폴리머의 용융지수가 각각 5 이하, 5∼20, 20 이상인 유기규소 화합물 3종 이상을 혼합하여 중합하는 것을 특징으로 하는 α-올레핀의 중합 또는 공중합 방법에 관한 것이다. 이 발명에 의하면 고수율로 고입체규칙성인 올레핀 (공)중합체를 제조할 수 있다.Specifically, the catalyst components used in such ethylene propylene block copolymer systems are described in patent application 97-17650. Briefly summarized in the above patent application, the solid complex titanium catalyst containing magnesium, a halogen-containing titanium compound and an internal electron donor as an essential component, the organometallic compound of the Group I and Group III metals of the periodic table and the same as the external electron donor Polymerization of? -Olefins characterized in that the homopolymers polymerized using each organosilicon compound under polymerization conditions are polymerized by mixing three or more organosilicon compounds having a melt index of 5 or less, 5 to 20, and 20 or more, respectively. It relates to a copolymerization method. According to this invention, the olefin (co) polymer which is high stereoregular in high yield can be manufactured.
본 발명의 호모 폴리프로필렌은 아이소탁티시티 95% 이상, 더욱 바람직하게는 95∼97%가 되도록 제조한다. 아이소탁티시티가 95% 이하이면 내열성 및 강성이 낮아지는 단점이 있다.The homopolypropylene of this invention is manufactured so that it is 95% or more of isotacticity, More preferably, it is 95 to 97%. If isotacticity is 95% or less, there is a disadvantage in that heat resistance and rigidity are lowered.
또한, 에틸렌 프로필렌 블록 공중합체 수지 조성물 중의 EPR 함량은 7∼12중량%가 바람직하다. EPR 함량이 7중량% 미만이면 충격 강도와 열접착 강도가 저하되고, EPR 함량이 12중량%를 초과하면 강성 및 내열성이 저하된다.Moreover, as for EPR content in an ethylene propylene block copolymer resin composition, 7-12 weight% is preferable. If the EPR content is less than 7% by weight, the impact strength and the heat adhesive strength are lowered. If the EPR content is more than 12% by weight, the stiffness and heat resistance are lowered.
또한, 상기 EPR의 절대점도는 1.5∼3.0dl/g이 바람직하다. 절대점도가 1.5 미만이면 강성 및 내열성이 약해지고, 절대점도가 3.0 을 초과하면 외관 및 내충격성이 저하된다.In addition, the absolute viscosity of the EPR is preferably 1.5 to 3.0dl / g. If absolute viscosity is less than 1.5, rigidity and heat resistance will weaken, and if absolute viscosity exceeds 3.0, external appearance and impact resistance will fall.
본 발명의 수지 조성물의 용융지수(MI)는 2∼5g/10분(ASTM D1238, 230℃)이 바람직하다. 용융지수가 2g/10분 미만인 경우에는 가공이 양호하지 못하여 생산성이 저하되는 반면, 용융지수가 5g/10분을 초과하는 경우에는 충격 강도가 저하되는 단점이 있다.As for melt index (MI) of the resin composition of this invention, 2-5 g / 10min (ASTM D1238, 230 degreeC) is preferable. If the melt index is less than 2g / 10 minutes, the processing is not good, the productivity is lowered, while if the melt index is more than 5g / 10 minutes, the impact strength is lowered.
본 발명의 에틸렌 프로필렌 블록 공중합체는 물성에 큰 영향을 받지 않는 범위 내에서 산화 방지제, 중화제 등 통상의 첨가제를 부가하여 사용할 수 있다.The ethylene propylene block copolymer of the present invention can be used by adding conventional additives such as antioxidants and neutralizing agents within a range not significantly affected by physical properties.
아래에서는 실시예 및 비교예를 통하여 본 발명을 좀더 구체적으로 설명한다. 그러나, 아래의 실시예가 본 발명의 범위를 제한하고자 하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are not intended to limit the scope of the invention.
실시예 및 비교예에 있어서의 물성의 측정방법은 다음과 같다.The measuring method of the physical property in an Example and a comparative example is as follows.
물성 측정방법Property measurement method
1) 에틸렌 프로필렌 고무(EPR)의 함량 : n-데칸 추출법을 이용하여 측정하였다.1) Content of Ethylene Propylene Rubber (EPR): Measured by n-decane extraction.
2) 용융흐름지수(MI) : 용융흐름지수는 230℃에서 2.16kg의 하중 하에 10분 동안의 용융수지 용융 유동량을 ASTM D1238에 기준하여 측정하였다.2) Melt Flow Index (MI): The melt flow index was measured based on ASTM D1238 for a melt flow rate of 10 minutes under a load of 2.16 kg at 230 ° C.
3) 아이소탁티시티 : 13C-NMR을 이용하여 폴리프로필렌 분자쇄 중의 펜타드 단위로서의 아이소탁틱 분율을 측정하였다(단위:%).3) Isotacticity: The isotactic fraction as the pentad unit in the polypropylene molecular chain was measured using 13C-NMR (unit:%).
사출성형의 물성 측정방법Measurement method of injection molding properties
1) 굴곡탄성률 : ASTM D790에 따라 측정하였다.1) Flexural modulus: measured according to ASTM D790.
2) 인장강도 : ASTM D638에 따라 측정하였다.2) Tensile strength: measured according to ASTM D638.
3) 아이조드 충격강도 : ASTM D256에 따라 측정하였다.3) Izod impact strength was measured according to ASTM D256.
4) 열변형온도:ASTM D648에 따라 측정하였다.4) Heat deflection temperature: measured according to ASTM D648.
필름 성형물의 물성 측정방법Method of measuring physical property of film molding
1) 피쉬 아이: 가로 10cm, 세로 10cm 크기로 시편 5장을 취해 피쉬 아이 개수를 세고, 단위 중량당 피쉬 아이 개수로 환산하였다.1) Fish Eyes: Take 5 specimens with a size of 10 cm and 10 cm, and count the number of fish eyes and convert them to the number of fish eyes per unit weight.
2) 열수축율: 160℃ 오븐에 필름 시편을 5분간 방치한 후 기계 방향(MD)과 기계 수직 방향(TD)의 길이 변화로 열수축율을 측정하였다.2) Heat Shrinkage: After leaving the film specimen in the oven at 160 ° C. for 5 minutes, the heat shrinkage was measured by changing the length of the machine direction (MD) and the machine vertical direction (TD).
3) 열접착 강도: 40㎛ 두께의 폴리에스터 필름을 실시예 및 비교예에서 제조한 필름의 위, 아래에 대고 184℃, 1 기압의 압력으로 1초 동안 열접착시킨 후 인장 파단 강도를 측정하였다.3) Thermal Bond Strength: Tensile breaking strength of the polyester film having a thickness of 40 μm was heat-bonded for 1 second at a pressure of 184 ° C. and 1 atm above and below the films prepared in Examples and Comparative Examples. .
실시예Example
특허출원 제97-17650호에 기재된 촉매를 이용하여 표 1의 함량과 같이 호모 폴리프로필렌과 에틸렌 프로필렌 블록 공중합체로부터 파우더를 제조한 후 이축압출기를 이용하여 첨가제를 처방하여 압출 다이를 통해 빠져 나오는 수지의 스트랜드를 상온상태의 물속에서 냉각시킨 후 컷터를 이용하여 직경 2mm 정도의 팰렛으로 다시 제조하였다.Using the catalyst described in Patent Application No. 97-17650 to prepare a powder from homo polypropylene and ethylene propylene block copolymer as shown in Table 1 content, and then the resin exited through the extrusion die by prescribing an additive using a twin screw extruder After strands were cooled in water at room temperature, a cutter was used to produce pellets having a diameter of about 2 mm.
제조된 조성물의 굴곡탄성률, 충격강도와 열변형온도 등의 사출 물성을 측정하기 위하여 사출기를 이용하여 ASTM 패밀리 4호 시편을 만들었다. 이때 사용된 사출기는 삼성 클뢰크너 FM140톤이며 사출조건은 호퍼로부터의 온도분포가 30, 200, 220, 230, 230℃(노즐의 온도), 160℃(금형온도)로 고정하고 사출압력은 50 ~ 120 기압 범위에서 실시되었다. 사출된 시편을 상온 23℃의 실내에 72시간 방치 후 물성을 측정하였다.In order to measure the injection properties such as flexural modulus, impact strength and heat deflection temperature of the prepared composition, ASTM Family No. 4 specimens were made using an injection machine. The injection machine used was Samsung Klockner FM140 ton, and the injection condition is fixed at 30, 200, 220, 230, 230 ℃ (temperature of nozzle), 160 ℃ (molding temperature) from the hopper and the injection pressure is 50 ~. It was carried out in the range of 120 atm. The extruded specimens were placed in a room temperature of 23 ° C. for 72 hours, and then physical properties thereof were measured.
또한 제조된 조성물의 필름 물성을 측정하기 위하여 티다이 캐스터를 이용하여 30㎛ 두께의 필름을 제막하였다.In addition, in order to measure the film properties of the prepared composition, a film having a thickness of 30 μm was formed using a TiDy caster.
비교예 1∼3Comparative Examples 1 to 3
표 1과 같이 물성 또는 함량을 달리 하여 실시예와 동일한 방법으로 에틸렌 프로필렌 블록공중합체를 제조하고 물성을 측정하였다.As shown in Table 1, the ethylene propylene block copolymer was prepared in the same manner as in Example, and the physical properties or contents thereof were measured, and the physical properties thereof were measured.
각 실시예 및 비교예의 사출/필름 물성 결과를 표 1에 나타내었다.Table 1 shows the results of the injection / film properties of each Example and Comparative Example.
실시예 1과 비교예 1의 비교Comparison of Example 1 with Comparative Example 1
실시예 1, 비교예 1 모두 고입체규칙성 폴리프로필렌 중합체로서 강성 및 내열성이 모두 우수하나, 비교예 1의 경우 EPR 함량이 지나치게 낮아 저온충격 및 열접착 강도가 실시예 1 대비 매우 열세하다.Example 1, Comparative Example 1 is a high-stereoregular polypropylene polymer, both excellent in rigidity and heat resistance, but in the case of Comparative Example 1 EPR content is too low, low temperature impact and heat adhesive strength is very inferior to Example 1.
비교예 2Comparative Example 2
비교예 2는 EPR 절대점도가 높은 것을 제외하고는 실시예 1과 동일한 조건의 에틸렌 프로필렌 공중합체를 사용하였다. 실시예 1 보다 충격강도와 외관이 열세하다.In Comparative Example 2, an ethylene propylene copolymer was used under the same conditions as in Example 1 except that the EPR absolute viscosity was high. The impact strength and appearance are inferior to those of Example 1.
비교예 3Comparative Example 3
비교예 3은 고입체규칙성 폴리프로필렌 중합체 대신에 아이소탁티시티가 낮은 폴리프로필렌 중합체를 사용하였다. 저온충격이나 열접착 강도는 실시예 1과 유사하나 강성 및 내열성이 실시예 1보다 매우 열세하다.Comparative Example 3 used a low isotacticity polypropylene polymer instead of a high stereoregular polypropylene polymer. The low temperature impact and thermal bond strength are similar to those of Example 1, but the stiffness and heat resistance are much lower than those of Example 1.
상기 실시예 및 비교예에서 살펴 본 바와 같이 본 발명에 의하여 제조된 입체규칙도가 95% 이상인 호모 폴리프로필렌 88 ∼ 93중량%에 절대점도 1.5 ~ 3.0dl/g인 EPR 7 ~ 12중량%로 구성된 에틸렌 프로필렌 블록 공중합체 수지 조성물은 강성, 내열성, 열접착강도, 충격강도 및 외관 등 물성이 우수한 것으로 나타났다.As described in the Examples and Comparative Examples composed of 88 to 93% by weight of homopolypropylene having a 95% or more stereoregularity produced by the present invention in an EPR 7 to 12% by weight of absolute viscosity 1.5 ~ 3.0dl / g The ethylene propylene block copolymer resin composition was found to have excellent physical properties such as stiffness, heat resistance, thermal adhesive strength, impact strength and appearance.
따라서, 본 발명의 수지 조성물은 상기와 같은 우수한 물성으로 식품의 포장용이나 열접착층의 재질로 이용될 수 있다.Therefore, the resin composition of the present invention can be used as a material for packaging food or heat adhesive layer with excellent physical properties as described above.
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| JP3002119B2 (en) * | 1994-11-21 | 2000-01-24 | 昭和電工株式会社 | Propylene block copolymer and method for producing the same |
| EP0811639B1 (en) * | 1995-02-13 | 2001-08-01 | Toho Titanium Co., Ltd. | Solid catalytic component for olefin polymerization and catalyst |
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