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WO2004063273A1 - Films polymeres et emballages produits a partir de ces derniers - Google Patents

Films polymeres et emballages produits a partir de ces derniers Download PDF

Info

Publication number
WO2004063273A1
WO2004063273A1 PCT/GB2004/000063 GB2004000063W WO2004063273A1 WO 2004063273 A1 WO2004063273 A1 WO 2004063273A1 GB 2004000063 W GB2004000063 W GB 2004000063W WO 2004063273 A1 WO2004063273 A1 WO 2004063273A1
Authority
WO
WIPO (PCT)
Prior art keywords
film according
film
polyethylene
density polyethylene
cyclic olefin
Prior art date
Application number
PCT/GB2004/000063
Other languages
English (en)
Inventor
Roy Christopherson
Stephen Summers
Original Assignee
Amcor Flexibles Winterbourne Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Amcor Flexibles Winterbourne Ltd filed Critical Amcor Flexibles Winterbourne Ltd
Publication of WO2004063273A1 publication Critical patent/WO2004063273A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms

Definitions

  • This invention concerns polymeric films and packages produced therefrom and in particular films and packages having linear tear open properties.
  • US4098406 discloses using blends of 12 to 95wt% of an ionomer resin, for example Surlyn, and from 5 to 88wt% of polyethylene optionally containing units derived from vinyl acetate to produce films having linear tear properties, particularly when used to make heat sealed packages.
  • an ionomer resin for example Surlyn
  • polyethylene optionally containing units derived from vinyl acetate
  • a polymeric film having linear tear properties the film having been produced by blowing or casting and comprising a layer of a blend of a cyclic olefin copolymer and a polyethylene.
  • films in accordance with the present invention consisting of a core layer of the blend and two outer layers of different polymers from the core layer can be torn relatively easily along substantially straight lines substantially along the direction of blowing or casting, with or without the presence of a starter cut or nick, but with relative difficulty perpendicular thereto even with a starter cut or nick.
  • the tear properties of films of the present invention are particularly surprising in the light of US6111019 which describes compression molded films produced from melt blends of LLDPE and ethylene/norbornene copolymers which have high tear strengths which require a modified Elmendorf tear test to measure them.
  • films of the present invention have exhibited good water vapor and oxygen barrier properties when compared with prior art films having linear tear properties.
  • the puncture resistance of films of the present invention are in general comparable with those of analogous films which do not contain a cyclic olefin copolymer.
  • the cyclic olefin copolymer used in the blend will usually have a glass transition temperature T of greater than 30°C but less than 220 °C.
  • a preferred range of glass transition temperatures for these copolymers is from 50 to 175°C, a particularly preferred range being from 65 to 160°C.
  • Preferred cyclic olefin copolymers for use in accordance with the present invention are cyclic olefin/ethylene copolymers and more preferably norbornene/ethylene copolymers.
  • the norbornene content of these polymers is preferably from 20 to 80 weight percent.
  • other cyclic olefin copolymers can be used containing units derived from norbornene or other cyclic olefins.
  • the polyethylene used in the blend can be selected from a wide variety of polyethylenes, for example those having densities in the range of from 0.915g/cm 3 to 0.935g/cm 3 .
  • the polyethylene can be selected from linear low density polyethylenes, linear medium density polyethylenes, and low density polyethylenes.
  • the weight ratio of the cyclic olefin copolymer to the polyethylene used in the blends can be varied over a wide range, for example from 10 to 90 wt% of the cyclic olefin copolymer and from 90 to 10 wt% of the polyethylene.
  • Films in accordance with the present invention preferably include at least one further polymeric layer, and more preferably at least two further polymeric layers with the layer of the blend between two of such layers.
  • the use of at least one polymeric layer on each side of the layer of the blend in general serves to provide physical protection to the layer of the blend.
  • the further polymeric layers are preferably formed from polyolefins which optionally contain units derived from vinyl acetate, for example low density polyethylene, linear low density polyethylene, linear medium density polyethylene, and ethylene/vinyl acetate copolymers.
  • Films in accordance with the present invention can be produced by blowing or casting using known methods for producing polymeric films, for example by extruding melts of the polymers required for the respective layer or layers, and then either cooling them to form a cast film or blowing them in a so-called bubble process.
  • Cast films will usually be produced using a linear slot die and blown films will usually be produced using an annular die.
  • the films When the films are produced by casting as opposed to blowing, they are generally not stretched during or after extrusion, but in general they will be oriented to a greater or lesser degree in the direction of extrusion. ⁇
  • the blown bubble is preferably subjected to expansion ratios in the machine and cross directions of at least 1.1:1, but they can be up to 2:1.
  • the expansion ratio in the machine direction is preferably greater than that in the transverse direction.
  • Films in accordance with the present invention in general exhibit particularly good linear tear properties along the machine direction used to produce them, that is whether they are merely cast or are blown. Tearing of the films in other directions will in general be less satisfactory due to relatively high tear strengths in these directions.
  • Films in accordance with the present invention can be produced to a variety of thicknesses, the particular thickness generally being determined by the end use to which the films are to be put. However, they will usually be at least 50 ⁇ m thick, but they can be 150 ⁇ m thick or more. Blown films of the present invention are preferably from 50 to 80 ⁇ m thick, and cast films of the present invention are preferably from 100 to 150 ⁇ m thick.
  • the blend of a cyclic olefin copolymer and a polyethylene preferably forms a core layer from 15 to 60 ⁇ m thick, the films preferably having two outer layers which can be of the same or different thicknesses, for example one can be from 20 to 25 ⁇ m thick with the other being from 25 to 60 ⁇ m thick.
  • films having core layers formed from a blend of a cyclic olefin copolymer and a polyethylene, where the core layer represent less than 40% of the total thickness of the films have good linear tear properties in the direction of blowing or casting combined with good water vapor barrier properties.
  • Packages in accordance with the present invention are preferably in the form of bags, in particular with top and bottom faces made of the same material.
  • the packages can include breathable patches sealed thereto, for example to allow the ingress of a sterilant gas and/or for the balancing the pressure within the packages with the outside air.
  • the oxygen transmission rate and the water vapor properties of the film used to form breathable packages is then relatively unimportant.
  • a mono-layered film was produced by extruding a linear low density polyethylene through a slot die, the resulting film being 12 ⁇ m thick.
  • a three layered film was produced by coextruding through a slot die a melt of a blend of 80wt% of the linear low density polyethylene used in Example 1 and 20wt% of the cyclic olefin copolymer sold by Hoechst AG as COC8007 to form a core layer of the film, the two outer layers of the film being formed from the same linear low density polyethylene.
  • the total thickness of the resulting film was 12 ⁇ m, the core layer being 48 ⁇ m thick, with one outer layer being 18 ⁇ m thick and the other being 60 ⁇ m thick.
  • a three layered film was produced in a similar manner to that of Example 2 except that the core layer was formed from 70wt% of the same linear low density polyethylene and 30wt% of the same cyclic olefin copolymer.
  • the total film thickness was 126 ⁇ m, the core and outer layers being of the same thickness as in Example 2.
  • a mono-layered film was produced by extruding a linear medium density polyethylene through a slot die, the resulting film being 126 ⁇ m thick.
  • a three layered film was produced by coextruding through a slot die a melt of a blend of 80wt% of the linear medium density polyethylene used in Example 4 and 20wt% of the cyclic olefin copolymer sold by Hoechst AG as COC8007 to form a core layer of the film, the two outer layers of the film being formed from the same linear low density polyethylene.
  • the total thickness of the resulting film was 126 ⁇ m, the core layer being 48 ⁇ m thick, with one outer layer being 18 ⁇ m thick and the other being 60 ⁇ m thick.
  • a three layered film was produced in a similar manner to that of Example 5 except that the core layer was formed from 70wt% of the same linear medium density polyethylene and 30wt% of the same cyclic olefin copolymer.
  • the total film thickness was 126 ⁇ m, the core and outer layers being of the same thickness as in Example 2.
  • Table 1 shows that the films in accordance with the present invention had considerably lower tear strengths in the machine direction (MD) compared with the cross direction (CD) , both tear strengths being less than for mono-layer films produced from the respective linear polyethylenes alone.
  • the films of the present invention also had lower water vapor transmission rates than those of the comparison films.
  • a mono-layer film was produced by extruding a melt of Surlyn 1652 (Trade Mark) through a ring die and blowing it to produce a film 70um thick, the blow up ratio in the machine and cross directions being 1.45:1.
  • a three layer film was produced by coextruding through a ring die a core layer consisting of 90wt% of Surlyn 1652 and 10wt% of an ethylene/vinyl acetate copolymer (4.5wt% vinyl acetate), with one outer layer formed from linear low density polyethylene and the other being formed from the ethylene/vinyl acetate copolymer of the core layer and blowing up the resultant bubble at a blow up ratio in the machine and cross directions of 1.45:1.
  • the core layer of the resulting film was 23 ⁇ m thick, the outer layer formed from linear low density polyethylene was 23 ⁇ m thick, and the other outer layer was 24 ⁇ m thick, the total thickness of the film being 70 ⁇ m.
  • a mono-layer film was produced by extruding a melt of the linear low density polyethylene used in Example 1-6 through a ring die and blowing it to produce a film 70 ⁇ m thick, the blow up ratio in the machine and cross directions being 1.45:1.
  • a three layer film was produced by coextruding through a ring die a core layer of a blend of 72wt% of the linear low density polyethylene used in Examples 1-6 with 28wt% of the cyclic olefin copolymer used in Examples 2, 3, 5 and 6, and two outer layers of the linear low density polyethylene, the extrudate being blown up a blow up ratio of 1.45 in both the machine and cross directions.
  • the resulting film had a core layer 23 ⁇ m thick, with one outer layer being 23 ⁇ m thick and the other being 24 ⁇ m thick.
  • Examples 7 and 9 were repeated except that the films produced had a thickness of 58 ⁇ m.
  • Example 8 was repeated, except that the film produced had a core layer 19 ⁇ m thick and the two outer layers were respectively 19 and 20 ⁇ m thick, the total thickness of the film being 58 ⁇ m thick.
  • the mean Elmendorf tear strength of this film in both the machine (MD) and cross (CD) directions, and the force required to puncture this film were measured and the results are shown in Table 2.
  • the films of the present invention had particularly low Elmendorf tear strengths in the machine direction compared with the comparison films of the same thickness.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un film polymère possédant des propriétés de déchirement linéaire, que l'on produit par soufflage ou coulage et qui comprend une couche d'un mélange d'un copolymère d'oléfine cyclique et d'un polyéthylène. Les films qui sont composés d'une couche principale dudit mélange et de deux couches extérieures de polymères différents de la couche principale peuvent être déchirés relativement facilement le long de lignes sensiblement droites sensiblement dans la direction du soufflage ou du coulage, avec ou sans la présence d'une découpe ou d'une entaille initiale de déchirement, mais avec une difficulté relative dans le sens perpendiculaire à la direction précitée, même en présence d'une découpe ou d'une entaille initiale.
PCT/GB2004/000063 2003-01-10 2004-01-09 Films polymeres et emballages produits a partir de ces derniers WO2004063273A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0300512A GB2397065A (en) 2003-01-10 2003-01-10 Polymeric film with linear tear properties
GB0300512.1 2003-01-10

Publications (1)

Publication Number Publication Date
WO2004063273A1 true WO2004063273A1 (fr) 2004-07-29

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PCT/GB2004/000063 WO2004063273A1 (fr) 2003-01-10 2004-01-09 Films polymeres et emballages produits a partir de ces derniers

Country Status (2)

Country Link
GB (1) GB2397065A (fr)
WO (1) WO2004063273A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102452205A (zh) * 2010-11-03 2012-05-16 上海富森实业有限公司 一种直线易撕裂薄膜
CN103009742A (zh) * 2012-12-03 2013-04-03 安徽省宁国双津(集团)实业有限公司 一种线性易撕、高阻隔湿纸巾的包装薄膜
KR20140089510A (ko) * 2011-08-23 2014-07-15 후타마키 필름즈 게르마니 게엠베하 운트 코. 카게 선형 인열 전파를 갖는 다층 필름
WO2018198794A1 (fr) * 2017-04-26 2018-11-01 Dic株式会社 Film de scellement et matériau d'emballage
CN109648968A (zh) * 2018-12-18 2019-04-19 江门市蓬江区华龙包装材料有限公司 一种双向易撕膜
CN110785284A (zh) * 2017-05-19 2020-02-11 埃克森美孚化学专利公司 包含环状-烯烃共聚物芯的收缩膜
CN114368208A (zh) * 2022-01-28 2022-04-19 佛山市南海利达印刷包装有限公司 哑光薄膜及其生产方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8522978B2 (en) 2006-12-01 2013-09-03 Cryovac, Inc. Stress concentrator for opening a flexible container
US10202229B2 (en) 2007-05-21 2019-02-12 Cryovac, Inc. Easy opening packaging article made from heat-shrinkable film exhibiting directional tear
US10189621B2 (en) 2007-05-21 2019-01-29 Cryovac, Inc. Bag made from high-strength heat-shrinkable film exhibiting directional tear, and process utilizing same
JP6205483B2 (ja) * 2013-04-25 2017-09-27 インフィアナ・ジャーマニー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンディートゲゼルシャフト 線状引き裂き伝播抵抗を有する多層フィルム
CN104129120A (zh) * 2014-07-10 2014-11-05 安徽双津实业有限公司 一种线性易撕包装用未拉伸镀铝薄膜
CN105313414A (zh) * 2015-10-22 2016-02-10 安徽双津实业有限公司 一种线性易撕未拉伸聚乙烯薄膜
EP3649163B1 (fr) 2017-07-06 2024-08-07 ExxonMobil Chemical Patents Inc. Compositions de polyéthylène comprenant des copolymères d'oléfine cyclique
US11441023B2 (en) 2018-04-27 2022-09-13 Exxonmobil Chemical Patents Inc. Polyethylene films and methods of making the same

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JPH10237234A (ja) * 1997-02-24 1998-09-08 Tamapori Kk 包装用フィルム
WO1998044043A1 (fr) * 1997-03-31 1998-10-08 Exxon Chemical Patents Inc. Melanges de polyethylene lineaire a faible densite (lldpe) avec un copolymere d'ethylene-norbornene pour des resines a tenacite et aptitude a la mise en oeuvre ameliorees pour la production de films
WO2001066639A1 (fr) * 2000-03-08 2001-09-13 Rexam Medical Packaging Ltd Films polymeres et emballages produits a partir de ceux-ci
EP1295908A1 (fr) * 2001-09-25 2003-03-26 Transpac N.V. Film polymérique à déchirure controlée

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EP0120562A2 (fr) * 1983-01-27 1984-10-03 Exxon Research And Engineering Company Mélanges élastomères transparents de polypropylène
US4808665A (en) * 1987-10-13 1989-02-28 Monsanto Company Crosslinked blends
JP3307457B2 (ja) * 1993-03-18 2002-07-24 出光興産株式会社 防水シート
US5942587A (en) * 1997-11-21 1999-08-24 Exxon Chemical Patents Inc. Ethylene polymers with a norbornene comonomer for LLDPE like resins of improved toughness and processibility for film production
JP3953713B2 (ja) * 2000-07-21 2007-08-08 三菱樹脂株式会社 包装用ストレッチフィルム

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JPH10237234A (ja) * 1997-02-24 1998-09-08 Tamapori Kk 包装用フィルム
WO1998044043A1 (fr) * 1997-03-31 1998-10-08 Exxon Chemical Patents Inc. Melanges de polyethylene lineaire a faible densite (lldpe) avec un copolymere d'ethylene-norbornene pour des resines a tenacite et aptitude a la mise en oeuvre ameliorees pour la production de films
WO2001066639A1 (fr) * 2000-03-08 2001-09-13 Rexam Medical Packaging Ltd Films polymeres et emballages produits a partir de ceux-ci
EP1295908A1 (fr) * 2001-09-25 2003-03-26 Transpac N.V. Film polymérique à déchirure controlée

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* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 14 31 December 1998 (1998-12-31) *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102452205A (zh) * 2010-11-03 2012-05-16 上海富森实业有限公司 一种直线易撕裂薄膜
KR20140089510A (ko) * 2011-08-23 2014-07-15 후타마키 필름즈 게르마니 게엠베하 운트 코. 카게 선형 인열 전파를 갖는 다층 필름
KR101988209B1 (ko) * 2011-08-23 2019-06-13 인피아나 게르마니 게엠베하 운트 코. 카게 선형 인열 전파를 갖는 다층 필름
CN103009742A (zh) * 2012-12-03 2013-04-03 安徽省宁国双津(集团)实业有限公司 一种线性易撕、高阻隔湿纸巾的包装薄膜
WO2018198794A1 (fr) * 2017-04-26 2018-11-01 Dic株式会社 Film de scellement et matériau d'emballage
JP6424997B1 (ja) * 2017-04-26 2018-11-21 Dic株式会社 シーラントフィルム及び包装材
CN110785284A (zh) * 2017-05-19 2020-02-11 埃克森美孚化学专利公司 包含环状-烯烃共聚物芯的收缩膜
US11141961B2 (en) 2017-05-19 2021-10-12 Exxonmobil Chemical Patents Inc. Shrink films comprising a cyclic-olefin copolymer core
CN109648968A (zh) * 2018-12-18 2019-04-19 江门市蓬江区华龙包装材料有限公司 一种双向易撕膜
CN114368208A (zh) * 2022-01-28 2022-04-19 佛山市南海利达印刷包装有限公司 哑光薄膜及其生产方法

Also Published As

Publication number Publication date
GB0300512D0 (en) 2003-02-12
GB2397065A (en) 2004-07-14

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