EP0716631A1 - Packaging material including a silica layer and a polyolefin layer - Google Patents

Packaging material including a silica layer and a polyolefin layer

Info

Publication number
EP0716631A1
EP0716631A1 EP95924377A EP95924377A EP0716631A1 EP 0716631 A1 EP0716631 A1 EP 0716631A1 EP 95924377 A EP95924377 A EP 95924377A EP 95924377 A EP95924377 A EP 95924377A EP 0716631 A1 EP0716631 A1 EP 0716631A1
Authority
EP
European Patent Office
Prior art keywords
ethylene
meth
acrylate
unsaturated
grafted
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
EP95924377A
Other languages
German (de)
French (fr)
Inventor
Patrice Breant
Philippe Tordjeman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema SA
Original Assignee
Elf Atochem SA
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 Elf Atochem SA filed Critical Elf Atochem SA
Priority to EP05076517A priority Critical patent/EP1609593A3/en
Publication of EP0716631A1 publication Critical patent/EP0716631A1/en
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • C09J123/0884—Epoxide containing esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to a packaging material comprising a layer of silicon oxide and a layer of polyolefin.
  • It relates more particularly to a structure comprising a film covered with silicon oxide and a polyolefin film, an adhesion binder being disposed between the silicon oxide and the polyolefin film.
  • a structure comprising a film covered with silicon oxide and a polyolefin film, an adhesion binder being disposed between the silicon oxide and the polyolefin film.
  • One can, for example, on the side of the polyolefin film hot paste this material on cardboard, then cover each side of the assembly obtained with a polyethylene sheet.
  • JP 03099842 published on April 25, 1991 describes EVOH ⁇ / inyl silane films covered with silicon oxide onto which a polypropylene sheet is bonded using a urethane adhesive.
  • JP 05330568 published on December 14, 1993 describes polyester films coated with silica onto which an ethylene resin sheet is glued using an adhesive which is an ethylene-maleic anhydride-ethyl acrylate copolymer.
  • the present invention is a material comprising a film covered with silicon oxide and a polyolefin film, such that the binder placed between the silicon oxide and the polyolefin film is chosen from:
  • the film covered with silicon oxide is known from the prior art. It is for example a polyester film such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) or polyamide (PA).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PA polyamide
  • the polyolefin film is made of polyethylene, polypropylene or ethylene copolymers such as for example ethylene-propylene, ethylene butene, ethylene hexene, ethylene - (meth) acrylate or ethylene-vinyl acetate copolymers.
  • the polyolefins which are grafted with alkoxysilanes can be chosen from: - homopolymers of ethylene, or of propylene;
  • alkyl (meth) acrylate - copolymers of ethylene and at least one alkyl (meth) acrylate.
  • the alkyl group of alkyl (meth) acrylate has up to 10 carbon atoms and can be linear, branched or cyclic.
  • alkyl (meth) acrylate there may be mentioned in particular n-butyl acrylate, methyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, l cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate.
  • acrylates ethyl acrylate, methyl acrylate, n-butyl acrylate and methyl methacrylate are preferred.
  • - copolymers of ethylene and an alphaolefin such as butene or hexene are preferred.
  • APAO - amorphous polyalphaolefins
  • the APAOs derived from ethylene, propylene, butene or hexene are used.
  • ethylene propylene butene copolymers with a high butene content or ethylene propylene butene copolymers with a high propylene content or homo or copolymers of butene are used.
  • ethylene / alkyl (meth) acrylate copolymers are used.
  • CH 2 CR 1 - CO - O - Y - Si (OR) 3 the (meth) acryloxyalkyltrialcoxysilanes (or (meth) acrylsilanes) in which: R is an alkyl having from 1 to 5 carbon atoms or an alkoxyl - R 2 OR 3 in which R 2 and R 3 are alkyls having at most 5 carbon atoms for the whole R 2 and R 3 .
  • Ri is hydrogen or methyl.
  • Y is an alkylene having from 1 to 5 carbon atoms.
  • vinylsilanes such as trimethoxyvinylsilane, triethloxyvinylsilane, triprbpoxyvinylsilane, tributoxyvinylsilane, tripentoxyvinylsilane, tris ( ⁇ -methoxyethoxy) -vinylsilane, allylsilanesilanesilanesilanesiloxy, triethoxylanesilane, triethoxyallylsilane, triethoxyallylsilane, triethoxyallylsoxyane , withthacryloxyméthylméthoxysilane, acryloxyéthyltriméthoxysilane, usethacryloxyméthylméthoxysilane, acryloxyéthyltriméthoxysilane, acryloxyéthyltriméthoxysilane, orthacryloxyéthyltriméthoxysilane, acryloxyéthyltriméthoxysilane, methacryloxy
  • CH 2 CH - Si - (OCH 2 CH 3 ) 3 vinyltriethoxysilane (VTEO)
  • CH 2 CH - Si - (OCH 2 OCH 2 CH 3 ) 3 vinyltrimethoxyethoxysilane (VTMOEO) and (3- (methacryloxy) propyl) trimethoxysilane.
  • CH 2 C (CH 3 ) - CO - 0 - (CH 2 ) 3 - Si (OCH 3 ) 3
  • Polyolefins can be grafted in the molten state in the presence of radical initiator (s).
  • the grafting reaction is carried out in a single or twin screw extruder fed with polyolefins in a feed hopper, for example in the form of granules; ue in the first zone of the extruder, one proceeds to the melting polyolefins by c: .. f wise and in a second zone, the reactants are introduced in the mass foncue polyolefins.
  • the radical initiators can be chosen from peroxides, peracids, peresters, peracetals. They are generally used in an amount of 0.01% to 0.5% by mass relative to the polyolefins to be grafted.
  • peroxides peracids
  • peresters peracetals. They are generally used in an amount of 0.01% to 0.5% by mass relative to the polyolefins to be grafted.
  • the reagent introduction zone is long enough and at a temperature low enough to ensure good dispersion of the reactants and the lowest possible thermal decomposition of the radical initiator.
  • the actual grafting reaction takes place in a third zone of the extruder at a temperature capable of ensuring the total decomposition of the radical initiator; before the outlet of the melt at the head of the extruder, a degassing zone is provided where the decomposition products of the initiator and the unreacted vinylsilane are degassed, for example under vacuum.
  • the grafted polyolefins are recovered at the extruder outlet, for example in the form of granulated rods after cooling in cold air.
  • the weight ratio of the grafts to the grafted polymer is generally between 0.1 and 5% and preferably 0.15 to 2.5%.
  • the polyolefins which are grafted with unsaturated epoxides can be chosen from the same group as those which are grafted with unsaturated alkoxysilanes.
  • ethylene / alkyl (meth) acrylate copolymers are used.
  • unsaturated epoxides there may be mentioned in particular glycidyl esters and ethers, glycidyl itaconate, vinyl glycidyl ether, allyl glycidyl ether, vinylcyclohexenemonoxide.
  • unsaturated epoxides very particularly preferred is acrylate and glycidyl methacrylate.
  • acrylate and glycidyl methacrylate are particularly preferred.
  • the same process can be used as for grafting the unsaturated alkoxysilanes.
  • the epoxide can be chosen from the same family as those already mentioned for the binders which are polyolefins grafted with unsaturated epoxides.
  • This copolymer of ethylene and at least one unsaturated epoxide can also comprise an alkyl (meth) acrylate or vinyl acetate.
  • the alkyl (meth) acrylate can be chosen from the same family as mentioned above for the possible comonomers of the polyolefins grafted with unsaturated alkoxysilanes.
  • copolymers of ethylene and of at least one unsaturated epoxide mention may be made of copolymers of ethylene, of an alkyl (meth) acrylate and of glycidyl methacrylate containing by weight 2 to 10% preferably 6 to 8% glycidyl methacrylate and at least 50% ethylene.
  • coil 1 and coil 2 the layer of silicon oxide deposited in plasma is 200 angstroms and PET 12 microns.
  • b ethylene-butyl acrylate-maleic anhydride copolymer with 3% maleic anhydride with 15% acrylate with a melt index of 5 dg / min.
  • ç ethylene-methyl acrylate copolymer identical to grafted at 0.45% by weight with vinyltrimethoxysilane.
  • the peel strength of the silicon oxide coated PET binder complexes was measured.
  • Ethylene / methyl acrylate binders of the same composition as the binder were prepared with different grafting rates of vinyltrimethoxysilane.
  • the grafting rate is by weight of graft relative to the grafted polymer.
  • the binder / PET film complex coated with silicon oxide was prepared by heat sealing.
  • the thickness of the binder film is 350 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A material including a silica-coated film, a polyolefin film and a binder arranged between the silica and the polyolefin films and selected from polyolefins grafted with unsaturated alkoxysilanes, polyolefins grafted with unsaturated epoxides, or copolymers of ethylene and at least one unsaturated epoxide. Said material is particularly useful for making food packaging.

Description

MATERIAU D'EMBALLAGE COMPRENANT UNE COUCHE D'OXYDE DE SILICIUM ET UNE COUCHE DE PACKAGING MATERIAL COMPRISING A LAYER OF SILICON OXIDE AND A LAYER OF
POLYOLEFINEPOLYOLEFIN
DescriptionDescription
La présente invention concerne un matériau d'emballage comprenant une couche d'oxyde de silicium et une couche de polyoléfine.The present invention relates to a packaging material comprising a layer of silicon oxide and a layer of polyolefin.
Elle concerne plus particulièrement une structure comprenant un film recouvert d'oxyde de silicium et un film de polyoléfine, un liant d'adhésion étant disposé entre l'oxyde de silicium et le film de polyoléfine. On peut, par exemple, du côté du film de polyoléfine coller à chaud ce matériau sur du carton, puis recouvrir chaque face de l'ensemble obtenu avec une feuille de polyethylene.It relates more particularly to a structure comprising a film covered with silicon oxide and a polyolefin film, an adhesion binder being disposed between the silicon oxide and the polyolefin film. One can, for example, on the side of the polyolefin film hot paste this material on cardboard, then cover each side of the assembly obtained with a polyethylene sheet.
Ces matériaux sont utiles pour fabriquer des emballages de liquides alimentaires en forme de briques.These materials are useful for making packages of food liquids in the form of bricks.
JP 03099842 (KOKAI) publié le 25 Avril 1991 décrit des films d'EVOHΛ/inyl silane recouverts d'oxyde de silicium sur lesquels on colle une feuille de polypropylène à l'aide d'un adhésif uréthane.JP 03099842 (KOKAI) published on April 25, 1991 describes EVOHΛ / inyl silane films covered with silicon oxide onto which a polypropylene sheet is bonded using a urethane adhesive.
JP 05330568 (KOKAI) publié le 14 Décembre 1993 décrit des films de polyester recouverts de silice sur lesquels on colle une feuille de résine éthylénique à l'aide d'un adhésif qui est un copolymère éthylène-anhydride maléique- acrylate d'éthyle.JP 05330568 (KOKAI) published on December 14, 1993 describes polyester films coated with silica onto which an ethylene resin sheet is glued using an adhesive which is an ethylene-maleic anhydride-ethyl acrylate copolymer.
On a maintenant trouvé qu'on pouvait obtenir des matériaux undélaminables en utilisant des liants à base de polyoléfines greffées silanes ou epoxydes.It has now been found that undelaminable materials can be obtained by using binders based on polyolefins grafted with silanes or epoxides.
La présente invention est un matériau comprenant un film recouvert d'oxyde de silicium et un film de polyoléfine, tel que le liant disposé entre l'oxyde de silicium et le film de polyoléfine est choisi parmi :The present invention is a material comprising a film covered with silicon oxide and a polyolefin film, such that the binder placed between the silicon oxide and the polyolefin film is chosen from:
- les polyoléfines greffées avec des alcoxysilanes insaturés, ou - les polyoléfines greffées avec des epoxydes insaturés, ou- polyolefins grafted with unsaturated alkoxysilanes, or - polyolefins grafted with unsaturated epoxides, or
- les copolymères de l'éthylène et d'au moins un epoxyde insaturé. Le film recouvert d'oxyde de silicium est connu de l'art antérieur. C'est par exemple un film de polyester tel que le polyethylene téréphtalate (PET) ou le polybutylène téréphtalate (PBT) ou de polyamide (PA).- copolymers of ethylene and at least one unsaturated epoxide. The film covered with silicon oxide is known from the prior art. It is for example a polyester film such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) or polyamide (PA).
Le film de polyoléfine est en polyethylene, polypropylène ou des copolymères de l'éthylène tels que par exemple des copolymères éthylène- propylène, éthylène butène, éthylène hexène, éthylène -(méth)acrylate d'alkyle ou éthylène-acétate de vinyle.The polyolefin film is made of polyethylene, polypropylene or ethylene copolymers such as for example ethylene-propylene, ethylene butene, ethylene hexene, ethylene - (meth) acrylate or ethylene-vinyl acetate copolymers.
S'agissant du liant, les polyoléfines qu'on greffe avec des alcoxysilanes peuvent être choisies parmi : - les homopolymères de l'éthylène, ou du propylene ;As regards the binder, the polyolefins which are grafted with alkoxysilanes can be chosen from: - homopolymers of ethylene, or of propylene;
- les copolymères de l'éthylène et de l'acétate de vinyle ;- copolymers of ethylene and vinyl acetate;
- les copolymères de l'éthylène et d'au moins un (méth)acrylate d'alkyle. Le groupement alkyle du (méth)acrylate d'alkyle a jusqu'à 10 atomes de carbone et peut être linéaire, ramifié ou cyclique. A titre d'illustration du (méth)acrylate d'alkyle, on peut citer notamment l'acrylate de n-butyle, l'acrylate de méthyle, l'acrylate d'isobutyle, l'acrylate d'éthyl-2 hexyle, l'acrylate de cyclohexyle, le méthacrylate de méthyle, le méthacrylate d'éthyle. Parmi ces (méth)acrylates, on préfère l'acrylate d'éthyle, l'acrylate de méthyle, l'acrylate de n-butyle et le méthacrylate de méthyle. - les copolymères de l'éthylène et d'une alphaoléfine telle que le butène ou l'héxène.- copolymers of ethylene and at least one alkyl (meth) acrylate. The alkyl group of alkyl (meth) acrylate has up to 10 carbon atoms and can be linear, branched or cyclic. By way of illustration of the alkyl (meth) acrylate, there may be mentioned in particular n-butyl acrylate, methyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, l cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate. Among these (meth) acrylates, ethyl acrylate, methyl acrylate, n-butyl acrylate and methyl methacrylate are preferred. - copolymers of ethylene and an alphaolefin such as butene or hexene.
- les polyalphaoléfines amorphes (APAO). De préférence, on utilise les APAO dérivées de l'éthylène, du propylene, du butène ou de l'héxène. On utilise avantageusement soit des copolymères éthylène propylene butène à haute teneur en butène, soit des copolymères éthylène propylene butène à haute teneur en propylene soit des homo ou copolymères du butène.- amorphous polyalphaolefins (APAO). Preferably, the APAOs derived from ethylene, propylene, butene or hexene are used. Advantageously, either ethylene propylene butene copolymers with a high butene content or ethylene propylene butene copolymers with a high propylene content or homo or copolymers of butene are used.
On utilise avantageusement des copolymères éthylène / (méth)acrylate d'alkyle.Advantageously, ethylene / alkyl (meth) acrylate copolymers are used.
Parmi les alcoxysilanes portant une insaturation, on peut citer :Among the unsaturated alkoxysilanes, there may be mentioned:
CH2 = CH — Si(OR)3 les vinyltrialcoxysilanesCH 2 = CH - Si (OR) 3 vinyltrialcoxysilanes
CH2 = CH — CH2 — Si(OR)3 les allyltrialcoxysilanesCH 2 = CH - CH 2 - Si (OR) 3 allyltrialcoxysilanes
CH2 = CR1 — CO — O — Y — Si (OR)3 les (méth)acryloxyalkyltrialcoxysilanes (ou (méth)acrylsilanes) dans lesquels : R est un alkyl ayant de 1 à 5 atomes de carbone ou un alcoxyle — R2OR3 dans lequel R2 et R3 sont des alkyles ayant au plus 5 atomes de carbone pour l'ensemble R2 et R3.CH 2 = CR 1 - CO - O - Y - Si (OR) 3 the (meth) acryloxyalkyltrialcoxysilanes (or (meth) acrylsilanes) in which: R is an alkyl having from 1 to 5 carbon atoms or an alkoxyl - R 2 OR 3 in which R 2 and R 3 are alkyls having at most 5 carbon atoms for the whole R 2 and R 3 .
Ri est un hydrogène ou un méthyle. Y est un alkylène ayant de 1 à 5 atomes de carbone.Ri is hydrogen or methyl. Y is an alkylene having from 1 to 5 carbon atoms.
On utilise par exemple des vinylsilanes tels que le triméthoxyvinylsilane, triéthloxyvinylsilane, triprbpoxyvinylsilane, tributoxyvinylsilane, tripentoxyvinylsilane, tris(β-méthoxyéthoxy)-vinylsilane, des allylsilanes tels que le triméthoxyallylsilane, triéthoxyallylsilane, thpropoxyallylsilane, tributoxyallylsilane, tripentoxyallylsilane, des acrylsilanes tels que l'acryloxyméthyltriméthoxysilane, méthacryloxyméthylméthoxysilane, acryloxyéthyltriméthoxysilane, méthacryloxyméthylméthoxysilane, acryloxyéthyltriméthoxysilane, méthacryloxyéthyltriméthoxysilane, acryloxypropyltriméthoxysilane, méthacryloxypropyltriméthoxysilane, acryloxybutyltriméthoxysilane, méthacryloxybutylméthoxysilane, acryloxyéthyltriéthoxysilane, méthacryloxyéthyltriéthoxysilane, méthacryloxyéthyltripropoxysilane, acryloxypropylt butoxysilane, ou le méthacryloxypropyltripentoxysilane.Use is made, for example, of vinylsilanes such as trimethoxyvinylsilane, triethloxyvinylsilane, triprbpoxyvinylsilane, tributoxyvinylsilane, tripentoxyvinylsilane, tris (β-methoxyethoxy) -vinylsilane, allylsilanesilanesilanesilanesiloxy, triethoxylanesilane, triethoxyallylsilane, triethoxyallylsilane, triethoxyallylsoxyane , méthacryloxyméthylméthoxysilane, acryloxyéthyltriméthoxysilane, méthacryloxyméthylméthoxysilane, acryloxyéthyltriméthoxysilane, méthacryloxyéthyltriméthoxysilane, acryloxy, methacryloxypropyltrimethoxysilane, acryloxybutyltriméthoxysilane, méthacryloxybutylméthoxysilane, acryloxyéthyltriéthoxysilane, méthacryloxyéthyltriéthoxysilane, méthacryloxyéthyltripropoxysilane, acryloxypropylt butoxysilane, or méthacryloxypropyltripentoxysilane.
On peut aussi utiliser des mélanges de ces produits.Mixtures of these products can also be used.
On utilise de préférence :We preferably use:
CH2 = CH — Si — <OCH3)3 vinyltriméthoxysilane (VTMO)CH 2 = CH - Si - <OCH 3 ) 3 vinyltrimethoxysilane (VTMO)
CH2 = CH — Si — (OCH2CH3)3 vinyltriéthoxysilane (VTEO)CH 2 = CH - Si - (OCH 2 CH 3 ) 3 vinyltriethoxysilane (VTEO)
CH2 = CH — Si — (OCH2OCH2CH3)3 vinyltriméthoxyéthoxysilane (VTMOEO) et le (3-(méthacryloxy)propyl)triméthoxysilane. CH2 = C (CH3) — CO — 0 — (CH2)3 — Si (OCH3)3 CH 2 = CH - Si - (OCH 2 OCH 2 CH 3 ) 3 vinyltrimethoxyethoxysilane (VTMOEO) and (3- (methacryloxy) propyl) trimethoxysilane. CH 2 = C (CH 3 ) - CO - 0 - (CH 2 ) 3 - Si (OCH 3 ) 3
On peut procéder au greffage à l'état fondu des polyoléfines en présence d'initiateur(s) radicalaire(s).Polyolefins can be grafted in the molten state in the presence of radical initiator (s).
La réaction de greffage est mise en oeuvre dans une extrudeuse mono ou double vis alimentée par des polyoléfines dans une trémie d'alimentation, par exemple sous forme de granulés ; dans u e première zone de l'extrudeuse, on procède à la fusion des polyoléfines par ch:.. ffage et dans une seconde zone, on introduit les réactifs au sein de la masse foncue des polyoléfines.The grafting reaction is carried out in a single or twin screw extruder fed with polyolefins in a feed hopper, for example in the form of granules; ue in the first zone of the extruder, one proceeds to the melting polyolefins by c: .. f wise and in a second zone, the reactants are introduced in the mass foncue polyolefins.
Les initiateurs radicalaires peuvent être choisis parmi les peroxydes, péracides, péresters, péracétals. On les utilise en général à raison de 0,01 % à 0,5 % en masse par rapport aux polyoléfines à greffer. A titre d'exemple, on peut citer • The radical initiators can be chosen from peroxides, peracids, peresters, peracetals. They are generally used in an amount of 0.01% to 0.5% by mass relative to the polyolefins to be grafted. By way of example, we can cite •
- le peroxyde de dicumyle (DICUP),- dicumyl peroxide (DICUP),
- le 2,5-diméthyl 2,5-ditertiobutylperoxyhexane (DHBP)- 2,5-dimethyl 2,5-ditertiobutylperoxyhexane (DHBP)
- l'α.α' (ditertiobutylperoxyisopropyl) benzène (Y1490). On préfère dissoudre l'initiateur radicalaire dans le vinylalcoxysilane liquide avant de les introduire, par exemple au moyen d'une pompe doseuse, dans les polyoléfines à l'état fondu.- α.α '(ditertiobutylperoxyisopropyl) benzene (Y1490). It is preferred to dissolve the radical initiator in the liquid vinylalkoxysilane before introducing them, for example by means of a metering pump, into the polyolefins in the molten state.
On préfère que la zone d'introduction des réactifs soit suffisamment longue et à une température suffisamment basse pour assurer une bonne dispersion des réactifs et une décomposition thermique de l'initiateur radicalaire la plus faible possible.It is preferred that the reagent introduction zone is long enough and at a temperature low enough to ensure good dispersion of the reactants and the lowest possible thermal decomposition of the radical initiator.
La réaction de greffage proprement dite a lieu dans une troisième zone de l'extrudeuse à une température apte à assurer la décomposition totale de l'initiateur radicalaire ; avant la sortie de la masse fondue en tête d'extrudeuse, une zone de dégazage est prévue où les produits de décomposition de l'initiateur et le vinylsilane qui n'a pas réagi sont dégazés par exemple sous vide.The actual grafting reaction takes place in a third zone of the extruder at a temperature capable of ensuring the total decomposition of the radical initiator; before the outlet of the melt at the head of the extruder, a degassing zone is provided where the decomposition products of the initiator and the unreacted vinylsilane are degassed, for example under vacuum.
On récupère les polyoléfines greffées en sortie d'extrudeuse par exemple sous forme de joncs granulés après refroidissement sous air froid. Le rapport pondéral des greffons au polymère greffé est en général compris entre 0,1 et 5 % et de préférence 0,15 à 2,5 %.The grafted polyolefins are recovered at the extruder outlet, for example in the form of granulated rods after cooling in cold air. The weight ratio of the grafts to the grafted polymer is generally between 0.1 and 5% and preferably 0.15 to 2.5%.
Les polyoléfines qu'on greffe avec des epoxydes insaturés peuvent être choisies dans le même groupe que celles qu'on greffe avec des alcoxysilanes insaturés. On utilise avantageusement les copolymères éthylène / (méth)acrylate d'alkyle.The polyolefins which are grafted with unsaturated epoxides can be chosen from the same group as those which are grafted with unsaturated alkoxysilanes. Advantageously, ethylene / alkyl (meth) acrylate copolymers are used.
A titre d'exemple d'epoxydes insaturés, on peut citer notamment les esters et les éthers de glycidyle, l'itaconate de glycidyle, le vinylglycidyléther, l'allylglycidyléther, le vinylcyclohéxènemonoxide.By way of example of unsaturated epoxides, there may be mentioned in particular glycidyl esters and ethers, glycidyl itaconate, vinyl glycidyl ether, allyl glycidyl ether, vinylcyclohexenemonoxide.
On peut citer aussi les esters et les éthers de glycidyle alicycliques tels que le 2-cyclohexène-1-glycidyléther, le cyclohéxène-4,5-diglycidylcarboxylate, le cyclohégène-4-glycidyl carboxylate, le 5-norbornène-2-méthyl-2-glycidyl carboxylate et l'endocis-bicyclo (2,2,1)-5-heptène-2,3 diglycidyl dicarboxylate.Mention may also be made of alicyclic glycidyl esters and ethers such as 2-cyclohexene-1-glycidylether, cyclohexene-4,5-diglycidylcarboxylate, cyclohegene-4-glycidyl carboxylate, 5-norbornene-2-methyl-2 -glycidyl carboxylate and endocis-bicyclo (2,2,1) -5-heptene-2,3 diglycidyl dicarboxylate.
Parmi ces epoxydes insaturés, on préfère tout particulièrement l'acrylate et le méthacrylate de glycidyle. Pour greffer les epoxydes insaturés sur les polyoléfines, on peut utiliser le même procédé que pour greffer les alcoxysilanes insaturés.Among these unsaturated epoxides, very particularly preferred is acrylate and glycidyl methacrylate. To graft the unsaturated epoxides on the polyolefins, the same process can be used as for grafting the unsaturated alkoxysilanes.
S'agissant du troisième type de liant, à savoir les copolymères de l'éthylène et d'au moins un epoxyde insaturé, on peut choisir l'epoxyde parmi la même famille que ceux déjà cités pour les liants qui sont des polyoléfines greffées avec des epoxydes insaturés. Ce copolymère de l'éthylène et d'au moins un epoxyde insaturé peut aussi comprendre un (méth)acrylate d'alkyle ou de l'acétate de vinyle. Le (méth) acrylate d'alkyle peut être choisi dans la même famille que citée plus haut pour les comonomères éventuels des polyoléfines greffées avec des alcoxysilanes insaturés. A titre d'exemple de copolymères de l'éthylène et d'au moins un epoxyde insaturé, on peut citer les copolymères de l'éthylène, d'un (méth)acrylate d'alkyle et de méthacrylate de glycidyle contenant en poids 2 à 10 % de préférence 6 à 8 % de méthacrylate de glycidyle et au moins 50 % d'éthylène.As regards the third type of binder, namely the copolymers of ethylene and of at least one unsaturated epoxide, the epoxide can be chosen from the same family as those already mentioned for the binders which are polyolefins grafted with unsaturated epoxides. This copolymer of ethylene and at least one unsaturated epoxide can also comprise an alkyl (meth) acrylate or vinyl acetate. The alkyl (meth) acrylate can be chosen from the same family as mentioned above for the possible comonomers of the polyolefins grafted with unsaturated alkoxysilanes. By way of example of copolymers of ethylene and of at least one unsaturated epoxide, mention may be made of copolymers of ethylene, of an alkyl (meth) acrylate and of glycidyl methacrylate containing by weight 2 to 10% preferably 6 to 8% glycidyl methacrylate and at least 50% ethylene.
Exemple 1Example 1
On a préparé deux bobines de film PET revêtu d'oxyde de silicium qu'on appelle bobine 1 et bobine 2, la couche d'oxyde de silicium déposée en plasma fait 200 ângstroms et le PET 12 microns.We prepared two reels of PET film coated with silicon oxide called coil 1 and coil 2, the layer of silicon oxide deposited in plasma is 200 angstroms and PET 12 microns.
On a préparé différents liants qu'on a soit coextrudé, soit thermoscellé sur les films des bobines 1 et 2.Various binders were prepared which were either coextruded or heat sealed on the films of coils 1 and 2.
Composition des liants : a copolymère éthylène-acrylate de méthyle à 29 % d'acrylate de méthyle et d'indice de fluidité sous une charge de 2,16 kg à 190° C = 3 dg/mn. b copolymère éthylène-acrylate de butyle-anhydride maléique à 3 % d'anhydride maléique à 15 % d'acrylate d'indice de fluidité 5 dg/mn. ç copolymère éthylène-acrylate de méthyle identique à a greffé à 0,45 % en poids par du vinyltriméthoxysilane.Composition of binders: an ethylene-methyl acrylate copolymer containing 29% methyl acrylate and a melt index under a load of 2.16 kg at 190 ° C. = 3 dg / min. b ethylene-butyl acrylate-maleic anhydride copolymer with 3% maleic anhydride with 15% acrylate with a melt index of 5 dg / min. ç ethylene-methyl acrylate copolymer identical to grafted at 0.45% by weight with vinyltrimethoxysilane.
On a mesuré la force de pelage des complexes liant / film PET revêtu oxyde de silicium. The peel strength of the silicon oxide coated PET binder complexes was measured.
Les résultats sont rassemblés dans le tableau 1 suivant :The results are collated in the following table 1:
Tableau 1Table 1
Exemple 2 Example 2
On a préparé des liants éthylène/acrylate de méthyle de même composition que le liant a avec différents taux de greffage de vinyltriméthoxysilane. Le taux de greffage est en poids de greffon par rapport au polymère greffé.Ethylene / methyl acrylate binders of the same composition as the binder were prepared with different grafting rates of vinyltrimethoxysilane. The grafting rate is by weight of graft relative to the grafted polymer.
Le complexe liant / film de PET revêtu d'oxyde de silicium a été préparé par thermoscellage.The binder / PET film complex coated with silicon oxide was prepared by heat sealing.
L'épaisseur du film de liant est de 350 μm. The thickness of the binder film is 350 μm.
On a mesuré la force de pelage, les résultats figurent sur le tableau 2.The peel strength was measured, the results are shown in Table 2.
Tableau 2Table 2
Taux de 0 0,06 0,1 0,2 0,25 0,3 0,45 silane greffésRate of 0.06 0.1 0.2 0.25 0.3 0.45 grafted silane
Force de pelage en N/25 mm < 0,5 0,5 1 ,8 3,5 3,3 4,5 5 à 180° C Peel strength in N / 25 mm <0.5 0.5 1, 8 3.5 3.3 4.5 5 at 180 ° C

Claims

Revendications claims
1. Matériau comprenant un film recouvert d'oxyde de silicium et un film de polyoléfine, tel que le liant disposé entre l'oxyde de silicium et le film de polyoléfine est choisi parmi :1. Material comprising a film covered with silicon oxide and a polyolefin film, such that the binder placed between the silicon oxide and the polyolefin film is chosen from:
- les polyoléfines greffées avec des alcoxysilanes insaturés ; ou- polyolefins grafted with unsaturated alkoxysilanes; or
- les polyoléfines greffées avec des epoxydes insaturés, ou - les copolymères de l'éthylène et d'au moins un epoxyde insafuré.- polyolefins grafted with unsaturated epoxides, or - copolymers of ethylene and of at least one unsaturated epoxide.
2. Matériau selon la revendication 1 caractérisé en ce que le liant est un copolymère éthylène/(méth)acrylate d'alkyle greffé par des vinyltrialcoxysilanes, des allyltrialcoxysilanes ou des (méth)acryloxyalkyltrialcoxysilanes.2. Material according to claim 1 characterized in that the binder is an ethylene / (meth) alkyl acrylate copolymer grafted with vinyltrialcoxysilanes, allyltrialcoxysilanes or (meth) acryloxyalkyltrialcoxysilanes.
3. Matériau selon la revendication 1 ou 2 caractérisé en ce que le film recouvert d'oxyde de silicium est en polyethylene téréphtalate et le film de polyoléfine est en polyethylene.3. Material according to claim 1 or 2 characterized in that the film covered with silicon oxide is made of polyethylene terephthalate and the polyolefin film is made of polyethylene.
4. Matériau selon l'une des revendications 1 à 3 caractérisé en ce que le liant est un copolymère éthylène-(méth)acrylate d'alkyle greffé par le (méth)acrylate de glycidyle.4. Material according to one of claims 1 to 3 characterized in that the binder is an ethylene- (meth) alkyl acrylate copolymer grafted with (meth) glycidyl acrylate.
5. Matériau selon l'une des revendications 1 à 3 caractérisé en ce que le liant est un copolymère éthylène-(méth)acrylate d'alkyle - (méth)acrylate de glycidyle. 5. Material according to one of claims 1 to 3 characterized in that the binder is an ethylene- (meth) alkyl acrylate - (meth) acrylate glycidyl.
EP95924377A 1994-06-30 1995-06-28 Packaging material including a silica layer and a polyolefin layer Ceased EP0716631A1 (en)

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