IE910109A1 - Barrier film consisting of an alloy based on an¹ethylene-vinyl alcohol copolymer, its preparation, its use¹especially in packaging - Google Patents

Barrier film consisting of an alloy based on an¹ethylene-vinyl alcohol copolymer, its preparation, its use¹especially in packaging

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Publication number
IE910109A1
IE910109A1 IE010991A IE10991A IE910109A1 IE 910109 A1 IE910109 A1 IE 910109A1 IE 010991 A IE010991 A IE 010991A IE 10991 A IE10991 A IE 10991A IE 910109 A1 IE910109 A1 IE 910109A1
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IE
Ireland
Prior art keywords
evoh
film according
film
ethylene
layer
Prior art date
Application number
IE010991A
Original Assignee
Atochem
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 Atochem filed Critical Atochem
Publication of IE910109A1 publication Critical patent/IE910109A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Abstract

Barrier films consisting wholly or partially of an alloy based on an ethylene-vinyl alcohol copolymer, a polypropylene and a compatibilising agent. These films have an improved resistance to hot water and to superheated steam and can be employed for packaging and especially for the packaging of foodstuffs.

Description

The present invention relates to the field of films and more particularly so-called barrier films which resist hot water and superheated steam and are intended for food packaging.
To ensure preservation of food products it is necessary to ensure not only protection against dust but also against moisture, against some gases such as oxygen and carbon dioxide and against odours.
Polymeric resins are employed for this 10 purpose; these are known as barrier resins, which have gas and water vapour permeability properties, that is to say they are more or less permeable to gases and to water vapour.
The films generally consist of one or more 15 layers consisting of polymers which are impervious to gases and of polymers which are impervious to water vapour.
Thus, when permeability to oxygen must be low, use is made of polymers whose barrier properties in respect of this gas are very high, such as ethylene-vinyl alcohol (EVOH) copolymers, which are recognised as being excellent IE 91109 - 2 materials in this respect.
If a sufficient protection against water vapour is to be obtained, a barrier layer consisting of polyolefins such as polypropylene is employed.
Since the requirements of imperviousness to gases and to water vapour vary from one form of packaging to another and from one food product to another, the films employed may consist of one or more polymer layers which have different gas and water vapour permeability properties.
To improve the quality of "fresh food products and to increase their preservation time, the food products must be packaged aseptically. Many processes exist for this purpose. For example, pasteurisation and sterilisation may be mentioned.
In these processes the packaging - or the packaged food product - is subjected to the action of hot water (85°C-100°C) or to the action of superheated steam for periods ranging from a few seconds to several hours. For example, in the case of sterilisation the temperature reaches 121°C or even 135°C-140°C. It is then necessary for the packaging consisting of a film which has one or more barrier layers to withstand mechanically the combined action of water and of temperature, as well as the pressures, which may reach 3 to 4 bars.
It has been found that at the time of the sterilisation or under the effect of hot water, certain films, especially those based on EVOH, undergo degradation, ¢91109 - 3 which is seen as creasing of the affected layer or even a total delamination of the multilayer film.
A film which has an improved resistance to hot water and to superheated steam has now been found, according to the present invention, which is characterised in that it consists wholly or partially of an alloy (or blend) comprising at least one ethylene-vinyl alcohol (EVOH) copolymer, at least one propylene polymer and at least one compatibilising agent.
The film according to the invention is generally characterised in that the alloy contains at least 30 % by weight of EVOH. Among these films preference will be given to those made from alloys comprising: - 42.5 % to 99.5 % by weight of EVOH - 42.5 % to 0.4 % by weight of propylene polymer - 0.1 % to 15 % by weight of compatibilising agent.
The EVOH composition of the alloy is characterised by the fact that the matrix or dispersing phase is EVOH. The propylene polymer may be dispersed in the form of more or less spherical nodules or of small cylindrical rods.
The adhesion between the phases is preferably ensured by a graft copolymer based on an a-monoolefin referred to as a compatibilising agent, which is described in European Patent Application No. 0,342,066.
Among the compatibilising agents mentioned in the IE 91109 - 4 European patent application mentioned as reference above, preference is given to the compatibilising agents of formula AMXP: - AM denotes a backbone copolymer obtained by 5 copolymerising propylene and one or more a-olefins, - X is chosen from the group consisting of citraconic anhydride, fumaric acid, mesaconic acid, the anhydride of 3-allylsuccinic acid and maleic anhydride, P denotes a polyamide oligomer derived from 10 caprolactam, 11-aminoundecanoic acid or dodecalactam.
The EVOH is a copolymer consisting essentially of ethylene and vinyl alcohol units and may contain small quantities of other monomer units, in particular of vinyl ester units. These copolymers may be obtained by saponification or partial or complete alcoholysis of ethylene-vinyl ester copolymer. Among the vinyl esters, vinyl acetate is the preferred monomer. The degree of saponification or of alcoholysis is desirably at least 90 mol% and is preferably from 94 to 99.5 %. The molar proportion of ethylene in the EVOH is desirably from 3 to 75 % and preferably from 10 to 50 %.
The propylene polymer (hereafter referred to simply as polypropylene) is a polymer consisting essentially of propylene units. It may contain quantities (generally not exceeding 40 mol%) of another monomer unit, in particular ethylene and/or one or more α-olefins containing 4 to 6 carbon atoms. In particular, a homopolypropylene or a block IE 91109 propylene copolymer with 0.5 to 30 mol% of ethylene, or a random copolymer of propylene and ethylene containing 0.1 to 30 mol% of ethylene is employed.
Small quantities of other compounds of the 5 stabiliser, antistatic agent or lubricant type and other polymeric compounds may be optionally added to three main constituents, which are EVOH, polypropylene and the compatibilising agent.
Since the constituents are generally in the form of powder or granules, the preparation of the blend/alloy can be carried out in solution or in the molten state by means of a conversion machine of the single-screw or counter- or corotative twin-screw extruder type or a roll mill.
Monolayer films according to the invention will generally consist wholly of the alloy.
Multilayer films consist of at least one layer of alloy, the other layer or layers usually consisting of polyethylene (PE), polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET) and polycarbonate (PC).
A coextrusion binder, which ensures better adhesion between the layers must be employed in the case of some polymers.
In the multilayer films according to the invention the alloy layer may be external or internal.
IE 91109 The following films may be mentioned as examples of multilayer films according to the invention: - PP/alloy/PP - PP/coextrusion binder/alloy - PP/coextrusion binder/alloy/coextrusion binder/PP - PA/alloy.
The films according to the invention may be obtained by flat extrusion or by film blowing at temperatures of, say, 200°C to 260°C.
Apart from the coextrusion techniques using a flat die or an annular die, the films in accordance with the invention can be processed by techniques such as extrusion coating and extrusion lamination, the latter technique making it possible, for example, to combine a film and a sheet of metal such as aluminium.
The films according to the invention which are produced from the alloy exhibit an improved resistance to hot water and to superheated steam.
Thus, the single-layer or multilayer films 20 subjected to superheated steam at temperatures of 100°C to 140°C at pressures from 1 to 4 bars, retain their transparency and have a virtually intact surface appearance, whereas the same films consisting wholly or partially of EVOH become opaque and are striated, distorted or delaminated.
The films according to the invention consisting IE 91109 - 7 wholly or partially of the alloy can be used in the production of various packagings; most particularly they can be employed for the manufacture of pouches, flexible envelopes, small tubs or pots, for example, for food packaging.
The films in accordance with the invention can also be employed for the manufacture of membranes employed in the medical field, in techniques such as haemodialysis or plasmaphoresis.
The following Examples further illustrate the present invention.
- Tests 1 to 5 a) Five compositions are produced with the aid of a corotative twin-screw extruder with the following proportions of the constituents: - EVOH: 99.3 % hydrolysed ethylene-vinyl acetate copolymer containing 32 mol% of ethylene with a melt index of 3.2 g/10 minutes measured at 210°C under 2.16 kg, - PP: random ethylene-propylene copolymer 20 containing 3 % by weight of ethylene of MI 2 g/10 minutes, measured at 230°C under 2.16 kg, - compatibilising agent: graft copolymer as shown in Table I, prepared according to Example 1 of European Patent Application No. 0,342,066.
In this table: A is a unit derived from propylene M is a unit derived from ethylene IE 91109 X is a unit derived from maleic anhydride P is a caprolactam oligomer of molecular mass 2,700, determined by potentiometric determination of the end amine functional groups. b) These compositions are then extruded in the form of a 20-μπι thick film by means of a singlescrew extruder at a temperature ranging from 210°C to 230"C.
These films are inspected using a scanning 10 electron microscopy (SEM) after cryogenic fracture. (see Table I).
Because of the orientation due to the film extrusion, the disperse phase is in the form of small rods which are oriented in the extrusion direction: the size of the small rods is measured on the fractures after dissolving the disperse phase in xylene.
The assessment of the adhesion between phases is made qualitatively on the fractures.
TABLE I TESTS comcom5 comparati- COMPOSITION OF THE ALLOY (% by weight) SEM INSPECTION OF THE ALLOY AS 20-pm THICK FILM EVOH PP COMPATIBILISING AGENT 85 15 0 The PP is distributed in the EVOH matrix in the form of small cylindrical rods from 0.7 to 5 μτα in crosssection. No adhesion between phases. 80.75 14.25 ^63^136 ^0.65 : 4 EVOH cont. 29 molZ of ethylene : 1 5 The PP is distributed in the EVOH matrix in the form of small cylindrical rods from 0.5 to 3 pm in crosssection. A weak adhesion exists between phases. 80.75 14.25 ^663^136¾. 91 1*0.87 : 5 The PP is distributed in the EVOH matrix in the form of small cylindrical rods from 0.1 to 2 pm in cross-section. A strong adhesion exists between phases. 85.5 9.5 ^663^136^2.91 ^0.87 : 5 The PP is distributed in the form of the EVOH matrix in small cylindrical rods from 0.05 to 1. 5 pm in crosssection. A strong adhesion exists between phases. 9.5 85.5 ^663^136^^2.91 ^0.87 : 5 The EVOH is distributed in the PP matrix in the form of small cylindrical rods from 0.1 to 2 pm in cross-section. A strong adhesion exists between phases.
IE 91109 c) . Hot water resistance of single-layer films 1) Film composition - Example 1 (Comparative) Composition of the single-layer film: 100 % of ethylene-vinyl alcohol copolymer containing 32 % of ethylene (melt index: 3.2 g/10 minutes, measured at 210°C under 2.16 kg) - Example 2 Composition of the single-layer film according to the invention: 100 % of the alloy which has the following composition by weight: EVOH of Example 1: 80.75 % PP: random ethylene-propylene copolymer containing 3 % of ethylene (MI: 10-230eC/2.16 kg): 14.25 % compatibilising agent Ag^Mxg^.gxPo.e?: 5 % - Example 3 (Comparative) Composition of the single-layer film: 100 % of ethylene-vinyl alcohol copolymer containing 44 mol% of ethylene (MI: 3.5-210/2.16 kg).
- Example 4 Composition of the single-layer film according to the invention: 100 % of the alloy which has the following weight composition: IE 91109 EVQH of Example 3 : 80.75 % polypropylene of Example 2 s 14.25 % compatibilising agent of Example 2 : 5 % - Example 5 Film which has the composition of the film of Example 2, but obtained by blow extrusion. 2) Conditions of the hot water behaviour tests The films are stretched in a transparency frame and are then immersed for 30 minutes in a bath of distilled water at constant temperature and gently stirred using a bar magnet.
- Assessment of the results At the end of the test, film appearance and 15 transparency are assessed according to the following arbitrary classifications Appearance: A : unchanged Transparency B : streaked from 1: unchanged C : creased to D : holed 4: opaque Thus a film which is unchanged in appearance and opaque will be classified as A4.
IE 91109 The results are listed in Table II EXAMPLES Water temperature 80°C 90°C 95°C ''\iunder 1 bar) 1 (Comparative) Al D4 D4 2 Al B3 C3 3 (Comparative) Al Al D4 4 Al A2 B2 5 Al Al A2 TABLE II The single-layer films according to the invention - Examples 2, 4 and 5 - exhibit a better behaviour towards hot water than the single-layer films based on EVOH - Examples 1 and 3. The best results are obtained with the alloy based on EVOH containing 32 mol% of ethylene (Example 5).
IE 91109 d) Superheated steam (sterilisation) resistance 1) Film composition - Example 6 (Comparative) Composition of the single-layer film: as Example 1.
- Example 7 Composition of the single-layer film: as Example 2. 2) - Conditions of the superheated steam behaviour tests The tests carried out at a temperature equal to or higher than 100°C were performed in an autoclave.
The films, stretched in a stainless steel frame (5 x 5 cm), are arranged in the autoclave and subjected for 30 minutes to the test conditions which may take place either in saturated steam or in superheated water.
In the case where the test is carried out using superheated water the water, is preheated in a storage vessel adjoining the autoclave and is then quickly introduced into the autoclave by means of a device designed for this purpose.
In the case of the tests carried out with superheated steam the pressures range from 1 to 3 bars.
- Assessments of the results The arbitrary classification mentioned above in the case of the hot water behaviour tests is employed.
IE 91109 Results - Temperature of the superheated steam: 120°C - Example 6 (Comparative) D4 - Example 7 BI e) Resistance of three-laver films to superheated steam 1) Film composition Three-layer films whose composition and thicknesses are listed in Table III are obtained by blow coextrusion.
EXAMPLES LAYER COMPOSITION 8 9 Layer 1 : copolymer X 40 pm 40 pm Layer 2 s EVOH of Example 3 10 pm Layer 2 : alloy of Example 2 10 pm Layer 3 : copolymer X 40 pm 40 pm TABLE III In this table, copolymer X denotes a coextrusion binder (propylene-ethylene copolymer grafted with maleic anhydride).
IE 91109 , 15 These tests were carried out on a three-layer blow coextrusion equipment. 2) Coextrusion conditions - Extruder 1 (copolymer X) temperature: 210°C - 230°C screw speed: 132 rev/min - Extruder 2 (copolymer X) temperature: 210°C - 230°C screw speed: 122 rev/min - Extruder 3 (alloy or EVOH) temperature: 210°C - 230°C - Die: diameter : 150 mm blow ratio : 8.12 temperature : 220 °C - Draw speed: 8.83 m/min The results are collated in Table IV.
EXAMPLES Temperature of the superheated steam 120°C 133°C θ A4 A4 9 A2 A3 TABLE IV f) Resistance of five-layer films to superheated IE 91109 Ζ steam 1) Film composition Five-layer films whose composition and thicknesses are collated in Table V are obtained by flat coextrusion.
LAYER EXAMPLES 10 1 11 12 COMPOSITION Layer 1: PP 75 pm 50 pm 50 pm Layer 2: coextrusion binder 20 pm 10 pm 10 pm Layer 3: alloy of Example 2 20 pm 10 pm Layer 3: EVOH cont. 38 mol% of ethylene 10 pm Layer 4: coextrusion binder 20 pm 10 pm 10 pm Layer 5: PP 75 pm 50 pm 50 pm TABLE V 2) - Coextrusion conditions IE 91109 These tests were carried out on a five-layer coextrusion equipment.
- Extruder (PP) temperature: 200°C - 245°C - Extruder (coextrusion binder) temperature: 220°C - 245°C - Extruder (EVOH or alloy) temperature: 215°C - 245°C - Die gap: 0.7 mm, width 2 m temperature: 2 5 0 °C The results are collated in Table VI.
EXAMPLES TEMPERATURE OF THE -^SUPERHEATED STEAM 130°C 10 Al 11 Al 12 C4 TABLE VI IE 91109

Claims (12)

1. A film which comprises a blend of at least one ethylene-vinyl alcohol (EVOH) copolymer, at least one propylene polymer and at least one compatibilising agent.
2. A film according to claim 1 in which the blend comprises 5 at least 30% by weight of EVOH.
3. A film according to claim 1 or 2 in which the blend comprises: 42.5% to 99.5% by weight of EVOH 0.2% to 42.5% by weight of propylene polymer 10 0.1% to 15 % by weight of compatibilising agent.
4. A film according to any one of claims 1 to 3 in which the compatibilising agent is a graft copolymer of formula AMXP in which: 15 AM denotes units of a backbone copolymer obtained by copolymerising propylene and one or more α-olefins, X denotes units derived from citraconic anhydride, fumaric acid, mesaconic acid, the anhydride of 20 3-allylsuccinic acid or maleic anhydride, and P denotes units of a polyamide oligomer derived from caprolactam, 11-aminoundecanoic acid or dodecalactam.
5. A film according to any one of claims 1 to 4 in which the molar proportion of ethylene in the EVOH is from IE 91109 -193% to 75%.
6. A film according to claim 5 in which the molar proportion of ethylene in the EVOH is from 10% to 50%. 57.
7.A multilayer film comprising at least one layer which is a film as claimed in any one of claims 1 to 6.
8. A multilayer film according to claim 7 in which the other layer or layers consist of polyethylene, polypropylene, polyamide, polyethylene terephthalate or 10 polycarbonate.
9. A film according to claim 1 or 7 substantially as described in any one of Examples 2, 4, 5 and 7 to 12.
10. Use of a film according to any one of claims 1 to 9 as packaging material. 15
11. Use of a film according to claim 10 for packaging a foodstuff.
12. A material or article whenever packaged using a film as claimed in any one of claims 1 to 9.
IE010991A 1990-01-15 1991-01-14 Barrier film consisting of an alloy based on an¹ethylene-vinyl alcohol copolymer, its preparation, its use¹especially in packaging IE910109A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR9000384A FR2657070A1 (en) 1990-01-15 1990-01-15 BARRIER FILM COMPRISING AN ALLOY BASED ON A VINYL ETHYLENE ALCOHOL COPOLYMER, ITS PREPARATION AND PARTICULAR USE IN PACKAGING

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IE910109A1 true IE910109A1 (en) 1991-07-17

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JP (1) JPH0757834B2 (en)
KR (1) KR0165125B1 (en)
CN (2) CN1035680C (en)
AT (1) ATE135726T1 (en)
AU (1) AU649641B2 (en)
CA (1) CA2034093C (en)
DE (1) DE69118000T2 (en)
DK (1) DK0441666T3 (en)
ES (1) ES2085444T3 (en)
FI (1) FI103280B (en)
FR (1) FR2657070A1 (en)
GR (1) GR3020026T3 (en)
IE (1) IE910109A1 (en)
IL (1) IL96911A (en)
NO (1) NO910153L (en)
PT (1) PT96475A (en)
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EP1022309A1 (en) 1999-01-19 2000-07-26 Elf Atochem S.A. Ethylene-vinyl alcohol copolymer composition and its use
DE10234783A1 (en) * 2002-07-30 2004-02-19 Cfs Gmbh Kempten Foil with a gas barrier layer
DE602004025047D1 (en) * 2004-04-09 2010-02-25 Vibac Spa POLYPROPYLENE-BASED MULTILAYER FILM WITH LOCKING PROPERTIES
CN1293137C (en) * 2005-03-31 2007-01-03 方墉 Total biodegradable film and preparation method
CN101633761B (en) * 2009-08-27 2012-08-08 洛阳石化聚丙烯有限责任公司 Isolating polypropylene composite material and preparation method thereof
JP5337078B2 (en) * 2010-03-01 2013-11-06 共同印刷株式会社 Ethylene-vinyl alcohol polymer alloy composition, film comprising the composition, packaging material comprising the film, and method for producing the composition
WO2011125739A1 (en) * 2010-03-31 2011-10-13 株式会社クラレ Multilayered structure, laminate and methods for producing same
EP2692780B1 (en) * 2011-03-30 2016-11-16 Kuraray Co., Ltd. method for producing ethylene-vinyl alcohol copolymer resin, ethylene-vinyl alcohol copolymer resin, and laminate
US9416208B2 (en) 2011-03-30 2016-08-16 Kuraray Co., Ltd. Method for producing ethylene-vinyl alcohol copolymer resin, ethylene-vinyl alcohol copolymer resin, and laminate
DE102016201498B4 (en) 2016-02-01 2017-08-17 Norbert Kuhl OXYGEN-CONTAINED FOOD CONTAINER
CN115028916A (en) * 2022-06-08 2022-09-09 广州丽盈塑料有限公司 High-barrier light plastic for plastic packaging container and preparation method thereof

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CN1121089A (en) 1996-04-24
CN1062278C (en) 2001-02-21
CA2034093A1 (en) 1991-07-16
DE69118000T2 (en) 1996-09-05
AU649641B2 (en) 1994-06-02
ATE135726T1 (en) 1996-04-15
EP0441666B1 (en) 1996-03-20
CN1035680C (en) 1997-08-20
JPH04211443A (en) 1992-08-03
EP0441666A3 (en) 1991-08-21
FI103280B1 (en) 1999-05-31
ES2085444T3 (en) 1996-06-01
FI103280B (en) 1999-05-31
AU6935591A (en) 1991-07-18
ZA91294B (en) 1991-10-30
FI910184A (en) 1991-07-16
DE69118000D1 (en) 1996-04-25
GR3020026T3 (en) 1996-08-31
DK0441666T3 (en) 1996-07-22
CA2034093C (en) 1999-12-14
FR2657070A1 (en) 1991-07-19
KR910014436A (en) 1991-08-31
FI910184A0 (en) 1991-01-14
CN1054082A (en) 1991-08-28
IL96911A0 (en) 1992-03-29
NO910153L (en) 1991-07-16
JPH0757834B2 (en) 1995-06-21
IL96911A (en) 1994-12-29
NO910153D0 (en) 1991-01-14
KR0165125B1 (en) 1999-03-20
EP0441666A2 (en) 1991-08-14
PT96475A (en) 1991-10-15

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