KR20020046391A - Heat-adhesive polyolefine resine composition - Google Patents

Heat-adhesive polyolefine resine composition Download PDF

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KR20020046391A
KR20020046391A KR1020000076187A KR20000076187A KR20020046391A KR 20020046391 A KR20020046391 A KR 20020046391A KR 1020000076187 A KR1020000076187 A KR 1020000076187A KR 20000076187 A KR20000076187 A KR 20000076187A KR 20020046391 A KR20020046391 A KR 20020046391A
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resin
ethylene
heat
film
weight
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KR1020000076187A
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Korean (ko)
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정혁성
김창희
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유현식
삼성종합화학주식회사
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • 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

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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)

Abstract

PURPOSE: A heat-adhesive polyolefin resin composition is provided, to improve heat adhesive power and blocking resistance of a film by inhibiting the production of low crystalline materials and to reduce the roll mark generated in a film process. CONSTITUTION: The heat-adhesive polyolefin resin composition comprises 100 parts by weight of a crystalline ethylene-propylene-1-butene terpolymer which has a melting point of 125-135 deg.C; and 1-10 parts by weight of an ethylene-α-olefin copolymer which has a density of 0.85-0.90 and a melting index(230 deg.C) of 1-10 and is prepared by using a single active site catalyst.

Description

열접착성 폴리올레핀 수지 조성물 {Heat-adhesive polyolefine resine composition}Heat-adhesive polyolefine resine composition

본 발명의 조성물은 무연신 폴리프로필렌 필름용으로 사용되는 열접착성 폴리프로필렌 수지조성물에 관한 것으로, 보다 상세하게는 용융온도가 125~135℃인 결정성 에틸렌-프로필렌-1-부텐 삼원공중합체 100 중량부 및 밀도가 0.85∼0.90이고, 용융지수(230℃)가 1∼10이며, 단일 활성점 촉매를 사용하여 제조된 에틸렌-알파올레핀 공중합체 1∼10 중량부를 포함하는 열접착성 폴리프로필렌 수지 조성물에 관한 것이다.The composition of the present invention relates to a heat-adhesive polypropylene resin composition for use in an unstretched polypropylene film, and more particularly, crystalline ethylene-propylene-1-butene terpolymer 100 having a melting temperature of 125 to 135 ° C. Heat-adhesive polypropylene resin containing 1 to 10 parts by weight of ethylene-alpha olefin copolymer prepared using a single active site catalyst with a weight part and density of 0.85 to 0.90, a melt index (230 ° C.) of 1 to 10. It relates to a composition.

무연신 폴리프로필렌 필름은 가격이 저렴하고 열접착성이 우수하여 식품포장에 널리 사용되고 있다. 포장시 생산속도를 높이면 열접착에 소요되는 시간이 감소하므로 고온에서 접착하거나, 열접착층에 사용되는 수지의 열접착온도를 낮추어야 하는데, 고온에서 접착하면 열에 의해 필름이 손상될 수 있으므로 낮은 열접착온도를 갖는 수지를 사용하는 것이 바람직하다.Unstretched polypropylene films are widely used in food packaging because of their low cost and excellent thermal adhesiveness. Increasing the production speed during packaging reduces the time required for thermal bonding, so it is necessary to bond at high temperatures or to lower the thermal bonding temperature of the resin used in the thermal bonding layer.At high temperatures, the film may be damaged by heat. It is preferable to use resin having

수지의 열접착온도는 수지의 용융온도와 관계가 있어 용융온도가 낮을수록 열접착온도가 낮아진다. 그러나, 낮은 용융온도를 가지면 저결정성 물질이 많아져필름의 블로킹을 유발하는 것으로 알려져 있다. 국내특허공개 1998-065047호에서는 이를 해결하기 위해서 저결정성 물질이 적은 프로필렌-에틸렌-부텐-1 3원중합체를 사용하고 있다. 상기 3원 공중합체는 일반적으로 125~135℃ 사이에서 용융온도를 가지고 있다.The thermal bonding temperature of the resin is related to the melting temperature of the resin, so that the lower the melting temperature, the lower the thermal bonding temperature. However, it is known that having a low melting temperature increases the number of low crystalline materials, causing blocking of the film. In Korean Patent Laid-Open Publication No. 1998-065047, in order to solve this problem, propylene-ethylene-butene-1 terpolymer having low low crystalline material is used. The terpolymers generally have a melting temperature between 125 and 135 ° C.

그러나 이 경우, 용융온도가 낮아지면 저결정성 물질들이 증가하여 표면으로 전이되면서 블로킹을 유발하게 되는 문제점을 완전히 해결하지 못하였다. 또한 수지의 용융온도가 낮아질수록 결정화온도도 낮아져, 수지가 다이(Die)에서 나와 고화가 덜 된 상태에서 플레이트 아웃 롤(Plate-Out Roll)이 닿게 되면 롤자국이 발생하는 문제가 있다. 투명한 필름 적용시에는 이러한 자국들이 후가공업체에서 문제가 된다.However, in this case, when the melting temperature is lowered, the low crystalline materials increase and transfer to the surface, which does not completely solve the problem of causing blocking. In addition, the lower the melting temperature of the resin, the lower the crystallization temperature, there is a problem that roll marks occur when the plate out roll (Plate-Out Roll) is in contact with the resin is less solidified out of the die (Die). These marks are a problem for finishing companies when applying transparent film.

한편 필름의 내블로킹성을 높이기 위해 일반적으로 수지에 블록킹 방지제를 혼합하는 방법이 있다. 사용되는 블록킹 방지제로는 이산화실리콘이 가장 널리 사용되며 (EP-A-27 586, EP-A-189 242), 경화된 실리콘(EP-A-242 055), 폴리아미드-6, 폴리아미드-6,6, 폴리에틸렌 테레프탈레이트, 폴리에틸렌 벤조에이트 (DE-A-2 244)등이 사용되기도 한다. 그러나 상기 블록킹 방지제가 과도하게 사용되면 필름의 투명성이나 광택성이 저하되는 단점이 있다.On the other hand, in order to improve the blocking resistance of a film, there exists a method of mixing a blocking agent with resin generally. As the blocking agent used, silicon dioxide is the most widely used (EP-A-27 586, EP-A-189 242), cured silicone (EP-A-242 055), polyamide-6, polyamide-6 , 6, polyethylene terephthalate, polyethylene benzoate (DE-A-2 244) and the like may be used. However, when the blocking agent is excessively used, there is a disadvantage in that transparency or glossiness of the film is lowered.

열접착성을 높이는 다른 방법으로 유럽특허 제27586호는 에틸렌 코폴리머에 긴사슬의 알리패틱 아민(Aliphatic Amine)과 폴리다이알킬 실록산(Polydialkyl Siloxane)을 포함하는 열접착성 폴리프로필렌에 대해 개시하고 있다. 그러나 이러한 종류의 필름은 표면에 끈적한 물질이 발생하고, 필름의 투명성이 떨어지는 단점이 있다.As another method of increasing the thermal adhesion, EP 27586 discloses a thermally adhesive polypropylene comprising a long chain aliphatic amine and a polydialkyl siloxane in an ethylene copolymer. . However, this kind of film has a disadvantage that a sticky material is generated on the surface, the transparency of the film is poor.

본 발명의 목적은 상술한 바와같이 종래 기술의 문제점을 해결하는 것에 있어, 폴리프로필렌 수지에 단일 활성점 촉매로 제조된 에틸렌-알파올레핀 공중합체를 첨가하여 필름의 열접착성을 높이면서도 저결정성 물질 생성은 억제시켜 내블로킹성이 우수하며, 필름 가공시 롤자국 발생문제를 줄인 열접착성 폴리프로필렌 필름을 제공하는 것에 있다.An object of the present invention is to solve the problems of the prior art as described above, by adding an ethylene-alpha olefin copolymer made of a single active site catalyst to the polypropylene resin to increase the thermal adhesiveness of the film, while also having low crystallinity It is to provide a heat-adhesive polypropylene film that suppresses the formation of materials and has excellent blocking resistance and reduces the problem of roll marks during film processing.

즉, 본 발명은 용융온도가 125~135℃인 결정성 에틸렌-프로필렌-1-부텐 삼원공중합체 100 중량부 및 밀도가 0.85∼0.90이고, 용융지수(230℃)가 1∼10이며, 단일 활성점 촉매를 사용하여 제조된 에틸렌-알파올레핀 공중합체 1∼10 중량부를 포함하는 열접착용 폴리프로필렌 수지 조성물에 관한 것이다.That is, in the present invention, 100 parts by weight of crystalline ethylene-propylene-1-butene terpolymer having a melting temperature of 125 to 135 ° C, a density of 0.85 to 0.90, a melt index (230 ° C) of 1 to 10, and a single activity It relates to a heat-adhesive polypropylene resin composition comprising 1 to 10 parts by weight of an ethylene-alphaolefin copolymer prepared using a point catalyst.

하기에서 본 발명에 대해서 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명의 폴리올레핀계 수지조성물은 용융온도가 125~135℃인 결정성 에틸렌-프로필렌-1-부텐 삼원공중합체로 되어 있는 수지 100 중량부와 밀도가 0.85∼0.90이고, 용융지수(230℃)가 1∼10이며, 단일활성점 촉매로 제조된 에틸렌-알파올레핀 공중합체 1∼10 중량부를 포함한다.The polyolefin resin composition of the present invention is 100 parts by weight of a resin made of a crystalline ethylene-propylene-1-butene terpolymer having a melting temperature of 125 to 135 ° C, a density of 0.85 to 0.90, and a melt index (230 ° C) of 1-10, and 1-10 weight part of ethylene-alpha olefin copolymers prepared with a single site catalyst.

본 발명의 조성물 중에 포함되는 폴리프로필렌 수지는 프로필렌을 주성분으로 하는 결정성 에틸렌-프로필렌-1-부텐 삼원공중합체로서, 용융온도가 125~135도인 것으로 열접착성이 우수하다. 상기 용융온도가 125도 미만이면 폴리프로필렌 수지의 생산공정상 어려움이 있으며, 135도를 초과하면 열접착성이 열세하다. 수지의 용융지수(230℃)는 6.0∼8.0으로 일반적으로 무연신 폴리프로필렌 필름에 사용되는 폴리프로필렌 수지와 유사한 흐름성을 갖는다.The polypropylene resin contained in the composition of the present invention is a crystalline ethylene-propylene-1-butene terpolymer having propylene as a main component, and has a melting temperature of 125 to 135 degrees, and is excellent in heat adhesiveness. If the melting temperature is less than 125 degrees, there is a difficulty in the production process of the polypropylene resin, and if it exceeds 135 degrees, thermal adhesiveness is inferior. The melt index of the resin (230 ° C.) is 6.0-8.0, which has a flow similar to that of polypropylene resins generally used for unstretched polypropylene films.

본 발명의 조성물 중에 포함되는 에틸렌-알파올레핀 공중합체는 밀도가 0.85∼0.90인 것으로, 밀도가 0.85 미만이면 첨가한 필름의 저결정성 물질이 증가하게 되고, 0.90를 초과하면 필름의 열접착성이 낮아진다. 또한 상기 에틸렌-알파올레핀 공중합체의 용융지수(230도)는 1∼10으로, 용융지수가 1 미만이거나 10을 초과하면 상기의 폴리프로필렌 수지와의 분산성이 저하되어 열접착성과 투명성이 떨어진다. 이러한 에틸렌-알파올레핀 공중합체는 단일 활성점 촉매(SSC)로 제조된 것으로, 만일 지글러-나타 촉매로 제조된 것을 사용하는 경우 저결정성 물질의 증가로 필름의 블로킹이 열세해진다.The ethylene-alpha olefin copolymer included in the composition of the present invention has a density of 0.85 to 0.90. If the density is less than 0.85, the low crystalline material of the added film increases, and if it exceeds 0.90, the thermal adhesiveness of the film is increased. Lowers. In addition, the melt index of the ethylene-alpha olefin copolymer (230 degrees) is 1 to 10, when the melt index is less than 1 or more than 10, the dispersibility with the polypropylene resin is lowered, and heat adhesiveness and transparency are inferior. These ethylene-alphaolefin copolymers are made of a single site catalyst (SSC), and the blocking of the film is inferior due to the increase in low crystalline materials when using those made with Ziegler-Natta catalysts.

상기 에틸렌-알파올레핀 공중합체는 기본수지 100 중량부 대비 1~10 중량부가 첨가되며, 이 중 3∼7 중량부 첨가되는 것이 보다 우수한 물성을 나타낸다. 상기 에틸렌-알파올레핀 공중합체의 함량이 1 중량부 미만이면 열접착성의 증가가 없으며, 10 중량부를 초과하면 폴리프로필렌 수지와 에틸렌-알파올레핀 공중합체의 상분리가 일어나서 가공시 불균일현상이 일어나 필름의 두께편차가 발생한다.The ethylene-alpha olefin copolymer is added 1 to 10 parts by weight with respect to 100 parts by weight of the base resin, 3 to 7 parts by weight of the added is more excellent physical properties. If the content of the ethylene-alpha olefin copolymer is less than 1 part by weight, there is no increase in thermal adhesiveness, and if the content of the ethylene-alpha olefin copolymer is more than 10 parts by weight, phase separation of the polypropylene resin and the ethylene-alpha olefin copolymer may occur, resulting in nonuniformity in processing. Deviation occurs.

본 발명의 수지조성물에는 또한 산화방지제, 중화제, 안티블로킹제 등과 같은 각종 첨가제가 본 발명의 특징에 어긋나지 않는 범위 내에서 첨가될 수 있다.The resin composition of the present invention may also be added with various additives such as antioxidants, neutralizers, antiblocking agents, and the like within the scope of the present invention.

이하 실시예를 통하여 본 발명을 더욱 구체적으로 설명하고자 하나, 하기의 실시예는 설명의 목적을 위한 것으로 본 발명을 제한하기 위한 것이 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are for the purpose of explanation and are not intended to limit the present invention.

하기 실시예에 사용되는 수지의 종류는 다음과 같다.The kind of resin used for the following Example is as follows.

1) 수지 1 : 삼원공중합체(프로필렌-에틸렌-1-부텐), 용융온도 130도,1) Resin 1: terpolymer (propylene-ethylene-1-butene), melting temperature 130 degrees,

용융지수(230℃)=7.0g/10minMelt Index (230 ℃) = 7.0g / 10min

2) 수지 2: 삼원공중합체(프로필렌-에틸렌-1-부텐), 용융온도 120도,2) Resin 2: Terpolymer (propylene-ethylene-1-butene), melting temperature 120 degrees,

용융지수(230℃)=7.0g/10minMelt Index (230 ℃) = 7.0g / 10min

3) 수지 3 : 단일 활성점 촉매로 제조된 에틸렌-알파올레핀 공중합체,3) Resin 3: Ethylene-alphaolefin copolymer prepared with a single active site catalyst,

밀도=0.88, 용융지수(230℃)=6.0g/10minDensity = 0.88, Melt Index (230 ° C) = 6.0g / 10min

4) 수지 4 : 지글러-나타 촉매로 제조된 에틸렌-알파올레핀 공중합체,4) Resin 4: Ethylene-alpha olefin copolymer prepared by Ziegler-Natta catalyst,

밀도=0.88, 용융지수(190℃)=6.0g/10minDensity = 0.88, Melt Index (190 ℃) = 6.0g / 10min

5) 수지 5 : 단일 활성점 촉매로 제조된 에틸렌-알파올레핀 공중합체,5) Resin 5: Ethylene-alpha olefin copolymer made of a single active site catalyst,

밀도=0.91, 용융지수(230℃)=6.0g/10minDensity = 0.91, Melt Index (230 ° C) = 6.0g / 10min

6) 수지 6 : 저밀도 폴리에틸렌6) Resin 6: Low Density Polyethylene

밀도=0.92, 용융지수(190℃)=7.0g/10minDensity = 0.92, Melt Index (190 ℃) = 7.0g / 10min

실시예 1Example 1

수지 1 100중량부에 첨가제로 산화방지제, 중화제 및 안티블로킹제를 적당량 배합하고 수지 3을 4중량부를 첨가하여 믹서로 혼합한 후, 압출기를 이용하여 210℃에서 펠렛상 조성물을 얻었다. 이 조성물을 구경 45mm의 압출기 및 T-다이를 이용하여 용융온도 240℃에서 압출하여, 표면온도 20℃의 냉각롤로 급냉하여 필름을 성형하여 권취 두께 30μm, 폭 40cm의 롤상 필름을 얻었다. 이를 가지고 열접착온도, △헤이즈 및 플레이아웃 롤자국 발생 등을 측정하였다.An appropriate amount of an antioxidant, a neutralizing agent, and an antiblocking agent were blended as additives to 100 parts by weight of the resin 1, 4 parts by weight of the resin 3 were added and mixed by a mixer, and then a pellet-like composition was obtained at 210 ° C using an extruder. The composition was extruded at a melting temperature of 240 ° C. using an extruder having a diameter of 45 mm and a T-die, quenched with a cooling roll having a surface temperature of 20 ° C. to form a film, and a rolled film having a winding thickness of 30 μm and a width of 40 cm was obtained. The thermal bonding temperature, △ haze and playout roll marks were measured with this.

실시예 2 및 비교예 1∼6Example 2 and Comparative Examples 1-6

표 1에서와 같이 수지의 종류 및 함량을 변화시키는 것을 제외하고는 실시예 1과 동일하게 실시하였다. 그 결과를 표 2에 나타내었다.As in Table 1 it was carried out in the same manner as in Example 1 except for changing the type and content of the resin. The results are shown in Table 2.

구 분division 조성물Composition 기본 수지(100 중량부)Basic resin (100 parts by weight) 첨가 수지Additive resin 첨가수지의 량(중량부)Quantity of Additive Resin (part by weight) 실시예 1Example 1 수지 1Resin 1 수지 3Resin 3 44 실시예 2Example 2 수지 1Resin 1 수지 3Resin 3 88 비교예 1Comparative Example 1 수지 2Resin 2 -- 00 비교예 2Comparative Example 2 수지 1Resin 1 -- 00 비교예 3Comparative Example 3 수지 1Resin 1 수지 3Resin 3 1515 비교예 4Comparative Example 4 수지 1Resin 1 수지 4Resin 4 44 비교예 5Comparative Example 5 수지 1Resin 1 수지 5Resin 5 44 비교예 6Comparative Example 6 수지 1Resin 1 수지 6Resin 6 44

필름 특성Film properties 열접착온도(도)Thermal bonding temperature (degrees) △ 헤이즈△ haze 플레이트아웃롤자국Plate Out Roll Marks 실시예 1Example 1 120120 33 미발생Not Occurred 실시예 2Example 2 120120 33 미발생Not Occurred 비교예 1Comparative Example 1 120120 1515 발생Occur 비교예 2Comparative Example 2 126126 66 미발생Not Occurred 비교예 3Comparative Example 3 118118 1010 발생Occur 비교예 4Comparative Example 4 120120 1515 미발생Not Occurred 비교예 5Comparative Example 5 123123 33 미발생Not Occurred 비교예 6Comparative Example 6 123123 66 미발생Not Occurred

[물성측정방법][Measurement of physical properties]

(1) 열접착온도 : 필름을 일정 온도에서 열접착기를 이용하여 2kgf하중 하에서 1.5초 동안 접착시킨 후 폭 1.5cm로 샘플링한 후 인장시험기에서 300mm/min의 속도로 필름의 접착강도를 측정하여 열접착강도값이 0.6kg가 되는 온도로 측정하였다. 낮을수록 열접착성이 우수하다.(1) Thermal bonding temperature: After the film is bonded for 1.5 seconds at 2kgf load using a heat bonder at a certain temperature, it is sampled at 1.5cm in width, and then measured by the tensile tester at a speed of 300mm / min. The adhesive strength value was measured at a temperature of 0.6 kg. The lower the value, the better the thermal adhesiveness.

(2) △헤이즈(haze) : 100℃ 오븐에 방치하여 6 시간 후 탁도의 변화값을 측정하였다. 낮을수록 필름표면으로의 저결정 전이물질이 적다.(2) Haze (haze): The change in turbidity was measured after 6 hours in an oven at 100 ° C. The lower the less the low crystal transition material to the film surface.

(3) 플레이트아웃 롤(Plate-Out Roll) 자국 관찰 : 캐스티드 폴리프로필렌 (CPP) 필름 압출기에서 플레이트아웃 롤을 닿게 하여 가공시켜 롤자국 발생여부를 관찰하였다.(3) Plate-Out Roll Marking Observation: The plate-out roll was processed in a cast polypropylene (CPP) film extruder and processed to observe roll marks.

본 발명에 의해 필름의 열접착성을 높이면서도 저결정성 물질 생성은 억제시켜 내블로킹성이 우수하며 필름 가공시 롤자국 발생문제도 줄인 열접착성 폴리프로필렌 필름을 제공할 수 있다.According to the present invention, it is possible to provide a heat-adhesive polypropylene film which improves the heat adhesiveness of the film while suppressing the formation of low crystalline material and thus has excellent blocking resistance and reduces the problem of roll marks during film processing.

Claims (1)

용융온도가 125~135℃인 결정성 에틸렌-프로필렌-1-부텐 삼원공중합체 100 중량부 및 밀도가 0.85∼0.90이고 용융지수(230℃)가 1∼10이며, 단일 활성점 촉매를 사용하여 제조된 에틸렌-알파올레핀 공중합체 1∼10 중량부를 포함하는 열접착성 폴리프로필렌 수지 조성물.100 parts by weight of a crystalline ethylene-propylene-1-butene terpolymer having a melting temperature of 125 to 135 ° C, a density of 0.85 to 0.90, a melt index (230 ° C) of 1 to 10, and prepared using a single active site catalyst A heat-adhesive polypropylene resin composition comprising 1 to 10 parts by weight of ethylene-alpha olefin copolymer.
KR1020000076187A 2000-12-13 2000-12-13 Heat-adhesive polyolefine resine composition KR20020046391A (en)

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US4842930A (en) * 1986-07-19 1989-06-27 Wolff Walsrode Aktiengesellschaft Heat-sealable multi-layer films of polyolefins
US5623021A (en) * 1994-03-24 1997-04-22 Montell North America Inc. Crystalline prophylene copolymer compositions having a low seal temperature and good ink adhesion
US5837369A (en) * 1995-09-28 1998-11-17 Pcd Polymere Gesellschaft M.B.H. Multilayer polypropylene-based packaging film and its use
US5888660A (en) * 1995-11-16 1999-03-30 Soten S.R.L. Heat-shrinkable co-extruded multilayer polyolefin film having an improved heat seal resistance
EP0936247A1 (en) * 1998-02-10 1999-08-18 Mitsui Chemicals, Inc. Polypropylene resin composition and non-stretched film thereof
KR100247363B1 (en) * 1995-09-14 2000-03-15 나까니시 히로유끼 Polyolefin composition and molded article thereof
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JPS5815547A (en) * 1981-07-22 1983-01-28 Showa Denko Kk Ethylenic copolymer composition
US4842930A (en) * 1986-07-19 1989-06-27 Wolff Walsrode Aktiengesellschaft Heat-sealable multi-layer films of polyolefins
US5623021A (en) * 1994-03-24 1997-04-22 Montell North America Inc. Crystalline prophylene copolymer compositions having a low seal temperature and good ink adhesion
KR100247363B1 (en) * 1995-09-14 2000-03-15 나까니시 히로유끼 Polyolefin composition and molded article thereof
US5837369A (en) * 1995-09-28 1998-11-17 Pcd Polymere Gesellschaft M.B.H. Multilayer polypropylene-based packaging film and its use
US5888660A (en) * 1995-11-16 1999-03-30 Soten S.R.L. Heat-shrinkable co-extruded multilayer polyolefin film having an improved heat seal resistance
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JP2000129053A (en) * 1998-10-28 2000-05-09 Mitsui Chemicals Inc Polypropylene resin composition and its non-stretched film

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