EP1177248A1 - Composite sheet - Google Patents

Composite sheet

Info

Publication number
EP1177248A1
EP1177248A1 EP99918934A EP99918934A EP1177248A1 EP 1177248 A1 EP1177248 A1 EP 1177248A1 EP 99918934 A EP99918934 A EP 99918934A EP 99918934 A EP99918934 A EP 99918934A EP 1177248 A1 EP1177248 A1 EP 1177248A1
Authority
EP
European Patent Office
Prior art keywords
layer
composite sheet
coating
substrate
film
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.)
Withdrawn
Application number
EP99918934A
Other languages
German (de)
French (fr)
Inventor
Jenny S. Hartley
Julian Neal Robinson
Stephen William Sankey
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.)
DuPont Teijin Films US LP
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1177248A1 publication Critical patent/EP1177248A1/en
Withdrawn legal-status Critical Current

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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/052—Forming heat-sealable coatings
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings

Definitions

  • This invention relates to a composite sheet, and in particular to a composite sheet suitable for use as a packaging material.
  • the present invention provides a composite sheet comprising a substrate layer, a coating layer comprising a layer mineral, and a metallic layer.
  • the invention also provides a method of producing a composite sheet by forming a substrate layer, applying a coating layer comprising a layer mineral, and applying a metallic layer.
  • a substrate layer for use in the production of a composite sheet according to the invention suitably comprises any film or web material, such as paper, paperboard, or synthetic paper.
  • the substrate is formed from polymeric material, which is preferably capable of forming a self-supporting opaque, or preferably transparent, film or sheet.
  • a self-supporting film or sheet is meant a film or sheet capable of independent existence in the absence of a supporting base.
  • the substrate layer of a composite sheet according to the invention may be formed from any film-forming, polymeric material.
  • Suitable thermoplastics, synthetic, materials include a homopolymer or a copolymer of a 1-olefine, such as ethylene, propylene or butene-1 , especially polypropylene, a polyamide, a polycarbonate, and particulariy a synthetic linear polyester which may be obtained by condensing one or more dicarboxylic acids or their lower aikyl (up to 6 carbon atoms) diesters, eg terephthalic acid, isophthalic acid, phthaiic acid, 2,5-, 2,6- or 2,7- naphthalenedicarboxylic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, 4,4'-diphenyldicarboxylic acid, hexahydro-terephthalic acid or 1 ,2-bis-p-carboxyphenoxyethane (
  • a polyethylene terephthalate or polyethylene naphthalate film is preferred.
  • a polyethylene terephthalate film is particulariy preferred, especially such a film which has been biaxially oriented by sequential stretching in two mutually pe ⁇ endicular directions, typically at a temperature in the range 70 to 125 ⁇ C, and preferably heat set, typically at a temperature in the range 150 to 250 ,, C, for example as described in GB-A-838,708.
  • the substrate may also comprise a polyarylether or thio analogue thereof, particularly a polyaryletherketone, polyarylethersuiphone, polyaryletheretherketone, polyaryletherethersulphone, or a copolymer or thioanalogue thereof. Examples of these polymers are disclosed in EP-A-1879, EP-A-184458 and US-A-4008203.
  • the substrate may comprise a poly(arylene sulphide), particularly poiy-p-phenylene sulphide or copolymers thereof. Blends of the aforementioned polymers may also be employed.
  • thermoset resin substrate materials include addition - polymerisation resins - such as acrylics, vinyls, bis-maieimides and unsaturated polyesters, formaldehyde condensate resins - such as condensates with urea, melamine or phenols, cyanate resins, functionalised polyesters, polyamides or polyimides.
  • addition - polymerisation resins - such as acrylics, vinyls, bis-maieimides and unsaturated polyesters, formaldehyde condensate resins - such as condensates with urea, melamine or phenols, cyanate resins, functionalised polyesters, polyamides or polyimides.
  • the preferred polymeric film substrate for production of a composite sheet according to the invention may be unoriented, or uniaxially oriented, but is preferably biaxially oriented by drawing in two mutually pe ⁇ endicular directions in the plane of the film to achieve a satisfactory combination of mechanical and physical properties.
  • Simultaneous biaxial orientation may be effected by extruding a thermoplastics polymeric tube which is subsequently quenched, reheated and then expanded by internal gas pressure to induce transverse orientation, and withdrawn at a rate which will induce longitudinal orientation.
  • Sequential stretching may be effected in a stenter process by extruding the thermoplastics substrate material as a flat extrudate which is subsequently stretched first in one direction and then in the other mutually pe ⁇ endicular direction. Generally, it is preferred to stretch firstly in the longitudinal direction, ie the forward direction through the film stretching machine, and then in the transverse direction.
  • a stretched substrate film may be, and preferably is, dimensionally stabilised by heat-setting under dimensional restraint at a temperature above the glass transition temperature thereof.
  • the substrate is suitably of a thickness from 6 to 300, particularly from 6 to 100, and especially from 6 to 25 ⁇ m.
  • the layer mineral preferably comprises platelets of a film-forming, 2:1 phyllosilicate layer mineral.
  • the layer mineral preferably comprises platelets of a film-forming, 2:1 phyllosilicate layer mineral.
  • platelets as used in this specification means tiny particles of the layer mineral obtained by subjecting the mineral to a chemical delaminating process to form an aqueous colloidal dispersion of high aspect ratio particles of the mineral from which a film can be formed.
  • the layer mineral is selected from the group consisting of smectites, preferably hectorite and montmorillonite, and particularly vermiculite.
  • vermiculite as used in this specification means all materials known mineralogically and commercially as vermiculite. Vermiculite ore being a naturally-occuring mineral contains a mixture of phases (eg vermiculite, biotite, hydrobiotite etc) and a mixture of interlayer cations (eg Mg 2+ , Ca 2+ , K + ). Production of aqueous suspensions or slurries of vermiculite platelets rely on ion exchange (normally incomplete) to generate adequate macroscopic swelling.
  • vermiculite gel can then be milled to produce a film-forming aqueous suspension of vermiculite platelets.
  • treatment of vermiculite particles with one or more aqueous solutions of metal (especially alkali metal) salts or alkyl ammonium salts followed by swelling in water and then milling to delaminate the vermiculite is well known and is described for example in GB-A-1016385,
  • a preferred embodiment of the invention comprises a coating layer of vermiculite platelets wherein greater than 50%, preferably 55 to 99.9%, more preferably 60 to 99%, and particulariy 70 to 95% by number of the platelets have a particle size (by which is meant the size of the maximum width of a platelet) in the range 0.5 to 5.0 ⁇ m. It is also preferred that 80 to 99.9%, more preferably 85 to 99.9%, and especially 90 to 99.9% by number of the vermiculite platelets have a particle size in the range 0.1 to 5.0 ⁇ m.
  • the mean particle size (by which is meant the mean value of the maximum width of the platelets) of vermiculite platelets is preferably 1.0 to 3.0 ⁇ m, more preferably 1.2 to 2.2 ⁇ m, and especially 1.3 to 1.6 ⁇ m. It is also preferred that the vermiculite platelets have a thickness in the range from approximately 10 to 60 A, especially from approximately 25 to 40 A. In addition, it is preferred that from 60 to 100%, more preferably from 70 to 99%, and particulariy from 90 to 95% by number of vermiculite platelets have a thickness in the range 10 to 60 A.
  • the mean thickness of vermiculite platelets is preferably 25 to 50 A, more preferably 25 to 40 A, and especially 25 to 30 A.
  • the coating layer can comprise a substantially continuous layer of platelets of any practical thickness, suitably up to 5 ⁇ m, preferably up to 2 ⁇ m, and more preferably up to 0.5 ⁇ m
  • composite sheets exhibiting desired properties, for example improved barrier property against atmospheric oxygen comprise a substantially continuous layer of platelets at very low thicknesses, eg as low as 0.01 ⁇ m, especially in the range from 0.02 ⁇ m to 0.3 ⁇ m, and particulariy in the range from 0.1 ⁇ m to 0.25 ⁇ m.
  • the coating layer additionally comprises at least one material which may be any polymer known in the art to be capable of forming a continuous, preferably uniform coating.
  • the polymeric material is preferably an organic resin and may be any film-forming polymeric or oiigomeric species or precursor therefor that assists in forming a film of the layer mineral and does not disrupt the film-forming capability thereof.
  • a suitable polymeric resin component of the coating layer comprises an acrylic or methacrylic resin, preferably thermoset and preferably comprising a polymer comprising at least one monomer derived from an ester of acrylic acid and/or an ester of methacrylic acid, especially an alkyl ester of (meth)acrylic acid where the alkyl group contains up to ten carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, terbutyl, hexyl, 2-ethylhexyl, heptyl, and n-octyl.
  • an acrylic or methacrylic resin preferably thermoset and preferably comprising a polymer comprising at least one monomer derived from an ester of acrylic acid and/or an ester of methacrylic acid, especially an alkyl ester of (meth)acrylic acid where the alkyl group contains up to ten carbon atoms such as methyl,
  • the acrylic resin preferably comprises greater than 50 mole %, and preferably less than 98 mole %, especially from 70 to 96 mole %, and particulariy from 80 to 94 mole % of at least one monomer derived from an ester of acrylic acid and/or an ester of methacrylic acid, and/or derivatives thereof.
  • Polymers derived from an alkyl acrylate, for example ethyl acrylate and butyl acryiate, together with an alkyl methacrylate are preferred.
  • Polymers comprising ethyl acrylate and methyl methacrylate are particularly preferred.
  • the acrylate monomer is preferably present in a proportion in the range 30 to 65 mole %, and the methacrylate monomer is preferably present in a proportion in the range of 20 to 60 mole %.
  • a preferred acrylic resin derived from 3 monomers comprises 35 to 60 mole % of ethyl acrylate/ 30 to 55 mole % of methyl methacryiate/2 to 20 mole % of methacrylamide, and especially comprising approximate molar proportions 46/46/8% respectively of ethyl acrylate/methyl methacrylate/acrylamide or methacrylamide, the latter polymer being particularly effective when thermoset - for example, in the presence of about 25 weight % of a methylated melamine-formaldehyde resin.
  • the acrylic resin is preferably present in the coating layer in the range from 0.5 to 50% by weight of the coating layer.
  • the coating layer is formed from a composition comprising a cross-linking agent, by which is meant a material which reacts chemically to form a polymeric resin during formation of the coating layer, preferably forming covalent bonds, both with itself and with the surface of the underlying layer to form cross-links thereby improving adhesion thereto.
  • the cross-linking agent is suitably an organic material, preferably a monomeric and/or oiigomeric species, and particulariy monomeric, prior to formation of the coating layer.
  • the molecular weight of the cross-linking agent is preferably less than 5000, more preferably less than 2000, especially less than 1000, and particularly in the range from 250 to 500.
  • cross-linking agent should preferably be capable of internal cross-linking in order to provide protection against solvent penetration.
  • Suitable cross-linking agents may comprise epoxy resins, alkyd resins, amine derivatives such as hexamethoxymethyl melamine, and/or condensation products of an amine, eg melamine, diazine, urea, cyclic ethylene urea, cyclic propylene urea, thiourea, cyclic ethylene thiourea, aziridines, alkyl melamines, aryl melamines, benzo guanamines, guanamines, alkyl guanamines and aryl guanamines, with an aldehyde, eg formaldehyde.
  • a preferred cross-linking agent is the condensation product of melamine with formaldehyde.
  • the condensation product may optionally be alkoxylated.
  • a catalyst is also preferably employed to facilitate cross-linking action of the cross-linking agent.
  • Preferred catalysts for cross-linking melamine formaldehyde include para toluene sulphonic acid, maleic acid stabilised by reaction with a base, and mo ⁇ holinium paratoluene sulphonate.
  • the coating layer preferably comprises greater than 20% and less than 80%, more preferably greater than 25% and less than 70%, particularly greater than 30% and less than 60%, and especially greater than 30% and less than 50% by weight of the layer of the resin derived by cross-linking the cross-linking agent.
  • the coating layer preferably comprises greater than 20% and less than 80%, more preferably greater than 30% and less than 75%, particularly greater than 40% and less than 70%, and especially greater than 50% and less than 70% by weight of the layer of the layer mineral.
  • the coating layer is formed by applying the coating composition, comprising the layer mineral, and preferably the cross-linking agent, as a slurry or dispersion and removing the dispersion medium to form a coherent layer.
  • the dispersion medium comprises water and the slurry or dispersion comprises between 0.5% and 20%, more especially between 1% and 10%, by weight of the layer mineral.
  • the coating layer composition may be applied before, during or after the stretching operation in the production of an oriented film.
  • the coating layer composition may, for example, be applied to the film substrate between the two stages (longitudinal and transverse) of a thermoplastics film biaxial stretching operation.
  • Such a sequence of stretching and coating may be suitable for the production of a coated linear polyester film substrate, which is preferably firstly stretched in the longitudinal direction over a series of rotating rollers, coated, and then stretched transversely in a stenter oven, preferably followed by heat setting.
  • the coating composition is preferably applied to an already oriented film substrate, such as a biaxially oriented polyester, particularly polyethylene terephthalate film, which is preferably subjected to heating.
  • the temperature to which the coated film is heated depends, inter alia on the composition of the substrate layer.
  • a coated polyester, especially polyethylene terephthalate, substrate is suitably heated from 100 ⁇ C to 240°C, preferably from 150 ⁇ C to 180 ⁇ C, in order to dry the aqueous medium, or the solvent in the case of solvent-applied compositions, and for cross-linking of the layer to occur and also to assist in coalescing and forming the coating into a continuous and uniform layer.
  • a coated polyolefin, especially polypropylene is suitably heated in the range 85 ⁇ C to 95 ⁇ C.
  • the coating layer composition is preferably applied to the substrate by any suitable conventional technique such as gravure coating, dip coating, bead coating, reverse roller coating or slot coating.
  • the coating layer is preferably applied to the substrate at a dry coat weight within the range 0.25 to 50 mgdnr 2 , more preferably 0.5 to 20 mgd ⁇ r 2 , especially 1.0 to 5.0 mgdnr 2 .
  • each coating layer preferably has a coat weight within the preferred ranges.
  • Deposition of the metallic layer may be effected by conventional metallising techniques, for example by deposition from a suspension of finely-divided metallic particles in a suitable liquid vehicle, or by electron beam evaporation, electroless plating, or preferably by a vacuum deposition process in which a metal is evaporated onto the adherent resin surface in a chamber maintained under conditions of high vacuum.
  • Suitable metals include palladium, titanium, chromium, nickel, copper (and alloys thereof, such as bronze), silver, gold, cobalt and zinc, but aluminium is preferred.
  • the metallic layer is conveniently deposited in a thickness from monoatomic proportions to about 50 ⁇ m or greater, although a preferred range is from 0.005 to 15.0 ⁇ m, and particulariy from 0.01 to 0.5 ⁇ m.
  • each metallic layer preferably has a thickness within the preferred ranges.
  • the position of the layers, ie substrate, coating and metallic, of a composite sheet according to the invention is not critical, although it is preferred that the coating layer is adhered either directly or indirectly to the surface of the substrate.
  • the metallic layer is preferably adhered either directly or indirectly to the surface of the coating layer, or more preferably adhered either directly or indirectly to the surface of the substrate remote from the coating layer.
  • the coating layer may be adhered either directly or indirectly to the surface of the metallic layer.
  • At least one additional primer layer is applied to the substrate layer prior to coating with the layer mineral coating layer and/or metallic layer.
  • the presence of the primer layer can result in an improvement in the adhesion of the coating or metallic layer to the substrate and/or an improvement in barrier properties, particularly oxygen barrier.
  • the primer layer comprises at least one polymeric resin which may be any polymer known in the art to be capable of forming a continuous, preferably uniform, coating, being adherent to the supporting substrate, and preferably exhibiting optical clarity.
  • Polymeric resins which are suitable for forming the primer layer include all the materials disclosed herein for use in the coating layer.
  • a preferred polymeric resin component of the primer layer which is particularly suitable for use in conjunction with a coating layer, comprises a copolymer comprising acrylamide and/or a derivative thereof, such as a lower alkoxy, preferably n-butoxy, and/or methacrylamide and/or a derivative thereof, such as a lower alkoxy, preferably n-butoxy, and at least one other ethylenically unsaturated comonomer copolymerisable therewith, including acrylic acid and its esters, including alkyl esters, for example methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl-hexyl acrylate, isobutyl acrylates, hexy!
  • acrylates and octyl acrylates methacrylic acid and its esters for example methyl methacrylate, ethyl methacrylate and butyl methacrylate.
  • suitable monomers include acrylo ⁇ itrile, styrene, monomethyl styrene, vinyl toluene, maleic anhydride, and vinyl ethers.
  • Styrene and alkyl acrylates are particulariy preferred monomers. Dienes such as butadiene or chloroprene may also be present in the primer layer copolymer.
  • the copolymer preferably comprises at least one free functional acid (for example a pendant carboxyl or sulphonate group) group, that is a group other than those involved in the polymerisation reaction by which the copolymer is formed, such as acrylic acid, methacrylic acid, maleic acid and itaconic acid.
  • at least one free functional acid for example a pendant carboxyl or sulphonate group
  • acrylic acid methacrylic acid, maleic acid and itaconic acid.
  • up to 25%, preferably up to 10%, and especially up to 5% by weight of comonomer containing a free functional acid group may be employed.
  • a preferred copolymer is derived from up to 90% by weight of styrene, up to 80% by weight of an alkyl acrylate, up to 15% by weight of methacrylic acid, and from 5% to 40% by weight of acrylamide which has been condensed with a solution of formaldehyde in n-butanol containing from 0.2 to 3 equivalents of formaldehyde for each amide group in the copolymer.
  • a particulariy preferred copolymer comprises styrene/2-ethyl hexyl acrylate/methacrylic acid/n-butoxymethyl acrylamide in a ratio of 20 to 40/30 to 50/1 to 5/20 to 35 % by weight.
  • GB-A-1174328 and GB-A-1134876 describe suitable methods for the synthesis of the aforementioned primer layer copolymers.
  • the polymeric resin of the primer layer is preferably compatible with, and includes, an additional acidic component, such as sulphuric, nitric, acetic acid or any mineral acid, such as hydrochloric acid, in the primer layer coating composition.
  • the additional acidic component is preferably present in the primer layer coating composition in a concentration range from 0.5 to 15, more preferably 1 to 10, and especially 4 to 8% by weight relative to the weight of the polymeric resin. Sulphuric acid is a preferred acidic component.
  • a primer layer which is particularly suitable for use in conjunction with a metallic layer comprises an acrylic or methacrylic polymer comprising up to 35 mole %, preferably in the range from 7 to 25 mole %, more preferably 10 to 20 mole % of at least one monomer containing a free ca ⁇ oxyl group.
  • a free carboxyl group is meant a group, other than those involved in the polymerisation reaction by which the polymer is formed, of formula C0 2 R, wherein R is preferably hydrogen, ammonium, substituted ammonium, and/or a metal, preferably an alkali metal such as lithium, sodium or potassium.
  • Ethylenically unsaturated monomers can be employed to provide the free carboxyl groups, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and derivatives thereof.
  • a preferred acrylic polymer comprises 30 to 40 mole % of methyl methacrylate/40 to 50 mole % of butyl acrylate/ 5 to 15 mole % of styrene/ 10 to 20 mole % of acrylic acid and/or methacrylic acid.
  • the molecular weight of polymeric resin of the primer layer can vary over a wide range but the weight average molecular weight is preferably within the range 10,000 to 300,000, and more preferably within the range 15,000 to 100,000.
  • the polymer(s) of the primer layer coating composition is generally water-insoluble.
  • the primer layer composition including the water-insoluble polymer may nevertheless be applied to the substrate as an aqueous dispersion or alternatively as a solution in an organic solvent.
  • the primer layer coating medium may be applied before, during or after any stretching operation used in the production of a polymeric substrate.
  • the primer layer composition may be applied to the polymeric film substrate between the two stages (longitudinal and transverse) of a biaxial stretching operation.
  • Such a sequence of stretching and coating is suitable for the production of a primed linear polyester film substrate, such as a coated polyethylene terephthalate film, which is preferably firstly stretched in the longitudinal direction over a series of rotating rollers, coated, and then stretched transversely in a stenter oven, preferably followed by heat setting.
  • a primed linear polyester film substrate such as a coated polyethylene terephthalate film
  • a series of rotating rollers coated, and then stretched transversely in a stenter oven, preferably followed by heat setting.
  • the primer layer coating composition may be applied as an aqueous dispersion or solution in an organic solvent by any suitable conventional coating technique such as dip coating, bead coating, reverse roller coating or slot coating.
  • the exposed surface thereof Prior to deposition of the primer layer, coating layer or metallic layer onto the substrate, the exposed surface thereof may, if desired, be subjected to a chemical or physical surface-modifying treatment to improve the bond between that surface and the subsequently applied layer.
  • a preferred treatment because of its simplicity and effectiveness, which is particularly suitable for the treatment of a polyolefin substrate, is to subject the exposed surface of the substrate to a high voltage electrical stress accompanied by corona discharge.
  • the substrate may be pre-treated with an agent known in the art to have a solvent or swelling action on the substrate polymer.
  • Such agents which are particulariy suitable for the treatment of a polyester substrate, include a halogenated phenol dissolved in a common organic solvent eg a solution of p-chloro-m-cresol, 2,4-dichlorophenol, 2,4,5- or 2,4,6-trichlorophenol or 4-chlororesorcinol in acetone or methanol.
  • a common organic solvent eg a solution of p-chloro-m-cresol, 2,4-dichlorophenol, 2,4,5- or 2,4,6-trichlorophenol or 4-chlororesorcinol in acetone or methanol.
  • the primer layer may also be applied directly on, for example, the coating layer prior to applying the metal layer, or alternatively on the metal layer prior to applying the coating layer.
  • the primer layer is preferably applied at a coat weight within the range 0.1 to 10 mgdrrr 2 , especially 1.0 to 6 mgdnr 2 .
  • the thickness of the primer layer is desirably at least 0.005 ⁇ m and preferably should not greatly exceed about 1.0 ⁇ m.
  • all the primer layers preferably have a coat weight within the preferred ranges. Modification of the surface of the primer layer, eg by flame treatment, ion bombardment, electron beam treatment, ultra-violet light treatment or preferably by corona discharge, may improve the adhesion of the subsequently applied coating layer comprising a layer mineral or metallic layer, but may not be essential to the provision of satisfactory adhesion.
  • the preferred treatment by corona discharge may be effected in air at atmospheric pressure with conventional equipment using a high frequency, high voltage generator, preferably having a power output of from 1 to 20 kw at a potential of 1 to 100 kv.
  • Discharge is conveniently accomplished by passing the film over a dielectric support roller at the discharge station at a linear speed preferably of 1.0 to
  • the discharge electrodes may be positioned 0.1 to 10.0 mm from the moving film surface.
  • the composite sheet additionally comprises a heat-sealable layer.
  • the heat-sealable layer may be suitably coated on, or laminated to, any of the layers of a composite film according to the invention, in order to form a packaging film laminate.
  • the heat-sealable layer is preferably applied either directly or indirectly, to the layer mineral coating layer, and more preferably to the metallic layer, of the composite film.
  • the heat-sealable layer comprises polymeric material which preferably should be capable of forming a heat-seal bond to itself or to any of the layers of the composite film, by heating to soften the polymeric material of the heat-sealable layer and applying pressure without softening or melting the material of the substrate layer.
  • the heat-sealable layer suitably has a heat-seal strength to itself of greater than 500 g/25 mm (196 Nnr 1 ), preferably in the range from 800 to 5000 g/25 mm (314 to 1960 Nm 1 ), more preferably 1000 to 4000 g/25 mm (392 to 1568 Nnr 1 ), and particulariy 1500 to
  • the heat-seal strength can be measured by sealing the heat-sealable layer to itself at 140°C for 1 second under a pressure of 103 kPa (15 psi), cooling to room temperature, and measuring the force required under linear tension per unit width of seal to peel the sealed films apart at a constant speed of 4.23 mm/second.
  • a heat-sealable layer suitably comprises a polyester or polyolefin resin.
  • Suitable polyesters include copolyester resins, especially those derived from one or more dibasic aromatic carboxylic acids, such as terephthalic acid, isophthalic acid and hexahydroterephthalic acid, and one or more glycols, such as ethylene glycol, diethylene glycol, triethylene glycol and neopentyl glycol.
  • Typical copolyesters which provide satisfactory heat-sealable properties are those of ethylene terephthalate and ethylene isophthalate, especially in the molar ratios of from 50 to 90 mole % ethylene terephthalate and correspondingly from 50 to 10 mole % ethylene isophthalate.
  • a polyolefin resin, particulariy polyethylene is a preferred component of the heat-sealable layer.
  • Formation of a heat-sealable layer may be effected by applying a polymeric resin as an aqueous dispersion or solution in an organic solvent, by any suitable conventional coating technique such as dip coating, bead coating, reverse roller coating or slot coating. Alternatively, the heat-sealable layer may be extrusion coated.
  • a preformed heat-sealable layer film, particulariy a polyethylene film is laminated to a composite sheet according to the invention, by passing through a heated nip roll.
  • the heat-sealable layer preferably has a thickness of up to 100 ⁇ m, more preferably greater than 10 ⁇ m, and especially from 35 ⁇ m to 70 ⁇ m.
  • the heat-sealable layer may be joined to the composite film by means of an optional additional adherent layer.
  • the adherent layer may comprise a thermosetting adhesive, such as a two component polyurethane adhesive.
  • the adherent layer may be a flexible layer, comprising a thermoplastic or rubbery polymeric resin material.
  • a flexible adherent layer preferably exhibits a tensile modulus (1% secant modulus) of less than 2.0 MPa, preferably in the range from 0.05 MPa to 1.5 MPa, more preferably in the range from 0.1 MPa to 1.0
  • the flexible adherent layer also preferably has a percentage elongation to break (%ETB) in the range from 300% to 10,000%, more preferably in the range from 600% to 4000%, particulariy in the range from 800% to 2000%, and especially in the range from 1200% to 1700%.
  • Suitable flexible adherent layer polymeric resins are natural and synthetic rubbers, eg where 1 ,4-polyisoprene is a major component.
  • polymeric resins include poiyte ⁇ e resins, isoprene-piperylene copolymers, styrene-butadiene copolymers, styrene-isoprene block copolymers, rubbery branched or radial block copolymers of conjugated dienes and vinyl aromatic hydrocarbons, cyclic monoolefin copolymers, carboxyl-containing chloroprene polymers, ethylene-vinyl acetate-diolefin-ester copolymers, polyisocyanate modified natural or synthetic rubber, and non-thermoset polyurethane resins.
  • the polymeric resin of the adherent layer is a styrene-butadiene copolymer, preferably a block copolymer.
  • the molar ratio of styrene:butadiene is preferably in the range from 0.1 to 10:1 , more preferably in the range from 0.5 to 3:1 , and especially in the range from 1.2 to 1.6:1.
  • the molecular weight of polymeric resin of the adherent layer can vary over a wide range but the weight average molecular weight is preferably within the range 5,000 to 1,000,000, more preferably within the range 10,000 to 500,000, and especially within the range 20,000 to 300,000.
  • the adherent layer coating composition may comprise other materials used to modify the properties of the resultant adherent layer, such as antioxidants, plasticisers, and tackifying resins.
  • the polymer(s) of the adherent layer coating composition may be water-soluble or water-insoluble.
  • the adherent layer composition including any water-insoluble polymer may nevertheless be applied to the coating layer surface as an aqueous dispersion or alternatively as a solution in an organic solvent.
  • the adherent layer composition is preferably applied by any suitable conventional technique such as dip coating, bead coating, reverse roller coating or slot coating.
  • the adherent layer is preferably dried by heating from 70 ⁇ C to 160 ⁇ C, preferably from 80°C to 100 ⁇ C, in order to dry the aqueous medium, or the solvent in the case of solvent-applied compositions, and to assist in coalescing and forming the adherent composition into a continuous and uniform layer.
  • the adherent layer is preferably applied at a coat weight within the range 10 to 200 mgdnr 2 , more preferably 20 to 150 mgdnr 2 , and especially 50 to 100 mgdm '2 .
  • the thickness of the dried adherent layer is preferably in the range from 1 ⁇ m to 20 ⁇ m, more preferably 2 ⁇ m to 15 ⁇ m, and especially 5 ⁇ m to 10 ⁇ m.
  • a composite sheet according to the invention suitably has an oxygen permeability of less than 1 , preferably less than 0.5, more preferably less than 0.1 , particulariy less than 0.05, and especially less than 0.01 cc m 2 /day.
  • One or more of the layers of a composite sheet according to the invention may conveniently contain any of the additives conventionally employed in the manufacture of polymeric films.
  • agents such as dyes, pigments, voiding agents, lubricants, anti-oxidants, anti-blocking agents, surface active agents, slip aids, gloss-improvers, prodegradants, ultra-violet light stabilisers, viscosity modifiers and dispersion stabilisers may be inco ⁇ orated into one or more of the aforementioned layers as appropriate.
  • a substrate may comprise a particulate filler, such as silica, of small particle size.
  • a filler, if employed in a substrate layer should be present in a small amount, not exceeding 0.5%, preferably less than 0.2%, by weight of the substrate.
  • Preferred composite sheets comprise the following layers, in order, (a) metallic/substrate/coating,
  • any of the above structures (a) to (d) may have an additional heat-sealable layer on either one or both of the outer surfaces thereof, either adhered directly thereto or by means of an optional intermediate adherent layer.
  • Composite sheets according to the invention may be used for packaging any oxygen and/or water sensitive products such as food and drink, pharmaceuticals, seeds, photographic films etc.
  • Figure 1 is a schematic sectional elevation, not to scale, of a composite sheet having a substrate, metallic and layer mineral coating layers.
  • Figure 2 is a similar schematic elevation of a composite sheet as shown in Figure 1 , with an additional primer layer between the substrate and metallic layers.
  • FIG 3 is a similar schematic elevation of a composite sheet as shown in Figure 2, with additional adherent and heat-sealable layers.
  • the composite sheet comprises a substrate layer (1) having a metallic layer (2) bonded to one surface (3) thereof.
  • a layer mineral coating layer (4) is bonded to the remote surface (5) of the metallic layer
  • the composite sheet of Figure 2 further comprises an additional primer layer (6), sandwiched between the substrate layer (1) and metallic layer (2).
  • the composite sheet of Figure 3 further comprises an additional adherent layer (7), bonded to the remote surface (8) of the coating layer (4) and an additional heat-sealable layer (9) bonded to the remote surface (10) of the adherent layer (7).
  • the invention is further illustrated by reference to the following examples.
  • Example 1
  • a polyethylene terephthalate film was melt extruded, cast onto a cooled rotating drum and stretched in the direction of extrusion to approximately 3 times its original dimensions.
  • the cooled stretched film was then coated with an aqueous primer layer composition containing the following ingredients: Methyl methacrylate/butyl acrylate/styrene/ 60 g
  • (acrylic acid or methacrylic acid) polymer of approximately 35/37/12/16 mole %.
  • Hexamethoxy methyl melamine 12 g (commercially available as 'Cymel' 300)
  • the polyethylene terephthalate film was coated on one side only.
  • the primed film was passed into a stenter oven, where the film was dried and stretched in the sideways direction to approximately 3 times its original dimensions.
  • the biaxially stretched primed film was heat set at a temperature of about 200°C by conventional means.
  • Substrate thickness was 23 ⁇ m
  • primer layer thickness was 0.03 to 0.05 ⁇ m with a coat weight of approximately 0.3 to 0.5 mgdnr 2 .
  • the primer layer of the film was metallised by a conventional evaporative method to give a layer of aluminium of approximately 0.05 ⁇ m.
  • a vermiculite suspension was prepared in accordance with the following method:
  • vermiculite ore (ex-Carolina, US) was refluxed with 1 litre of 1 N lithium citrate solution at 80 ⁇ C for four hours and left at room temperature for five days. This resulted in the exchange of 45.3 mEq/100 g of lithium cations in the ore.
  • the ion-exchanged vermiculite ore was washed 5 times with deionised water to remove the excess salts and left overnight to swell in a large volume (ie 10 times the volume of vermiculite) of deionised water.
  • the swollen vermiculite was milled for 40 minutes in a Greaves high-shear mixer at 7200 ⁇ m to produce a suspension of vermiculite platelets.
  • the platelet suspension was then sieved by passing through a mechanically agitated filter having a pore size of 106 ⁇ m.
  • the biaxially oriented polyethylene terephthalate substrate/primer layer/metallic layer structure was coated on the metallic layer using a gravure coater, with a coating layer composition comprising the following ingredients:
  • Vermiculite 6 1 (7.5% w/w aqueous dispersion)
  • the coated film was dried at 180°C, and the dry coat weight of the coating layer was approximately 2 mgdnr 2 .
  • the thickness of the coating layer was approximately 0.2 ⁇ m.
  • the remote surface of the layer mineral coating layer was coated, using a gravure coater, with an adherent layer composition comprising the following ingredient:
  • the adherent layer coated film was dried at 90°C, and the dry coat weight of the adherent layer was approximately 100 mgdnr 2 .
  • the thickness of the adherent layer was approximately 8 ⁇ m.
  • the adherent layer surface of the composite sheet was laminated with a 50 ⁇ m heat-sealable layer of polyethylene film, by passing the two films through a nip heated at 70 ⁇ C.
  • the oxygen barrier property of the final composite sheet was determined by measuring the oxygen permeability using a Mocon 1050 (Modem Controls Inc.) test instrument.
  • a sample of the composite sheet was placed in the machine with the nitrogen carrier gas (containing 1 % hydrogen) flowing both above and below the sheet, in order that a background reading can be obtained.
  • the nitrogen above the sheet was replaced by oxygen, and the amount of oxygen able to permeate through the sheet was measured in a carrier gas by using a sensor.
  • the oxygen permeability was 0.01 cc/m 2 /day.
  • the oxygen permeability of uncoated polyethylene terephthalate film was also measured and found to be 50.0 cc/m 2 /day.

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Abstract

A composite sheet has a substrate layer, a coating layer and a metallic layer. The substrate layer is preferably a polyester film. The coating layer contains a layer mineral, preferably vermiculite. The composite sheet exhibits improved oxygen barrier properties and is suitable for use as a packaging film, particularly when laminated to a heat-sealable layer, preferably of polyethylene.

Description

Composite Sheet
This invention relates to a composite sheet, and in particular to a composite sheet suitable for use as a packaging material.
There is a commercial requirement for packaging materials, especially films for packaging edible products, which exhibit barrier properties, particulariy oxygen and water barrier. Films having a coating layer containing platelet materials, or a metal layer or a polyvinyiidene chloride layer have been disclosed as having oxygen barrier properties. Unfortunately, the barrier properties of the aforementioned materials are not sufficient for all commercial requirements. Coated materials comprising layer minerals have been used to impart a variety of properties to film substrate materials, such as flame retardancy, antistatic property and gas, particularly oxygen, barrier, as disclosed, for example in Japanese Unexamined Patent Application No 62-181144, EP-A-235926 and US-A-3499820.
We have now devised a composite sheet comprising a layer mineral coating layer and a metallic layer which surprisingly exhibits improved barrier, particularly to oxygen, properties.
Accordingly, the present invention provides a composite sheet comprising a substrate layer, a coating layer comprising a layer mineral, and a metallic layer.
The invention also provides a method of producing a composite sheet by forming a substrate layer, applying a coating layer comprising a layer mineral, and applying a metallic layer.
A substrate layer for use in the production of a composite sheet according to the invention suitably comprises any film or web material, such as paper, paperboard, or synthetic paper. In a preferred embodiment of the invention the substrate is formed from polymeric material, which is preferably capable of forming a self-supporting opaque, or preferably transparent, film or sheet.
By a "self-supporting film or sheet" is meant a film or sheet capable of independent existence in the absence of a supporting base.
The substrate layer of a composite sheet according to the invention may be formed from any film-forming, polymeric material. Suitable thermoplastics, synthetic, materials include a homopolymer or a copolymer of a 1-olefine, such as ethylene, propylene or butene-1 , especially polypropylene, a polyamide, a polycarbonate, and particulariy a synthetic linear polyester which may be obtained by condensing one or more dicarboxylic acids or their lower aikyl (up to 6 carbon atoms) diesters, eg terephthalic acid, isophthalic acid, phthaiic acid, 2,5-, 2,6- or 2,7- naphthalenedicarboxylic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, 4,4'-diphenyldicarboxylic acid, hexahydro-terephthalic acid or 1 ,2-bis-p-carboxyphenoxyethane (optionally with a monocarboxylic acid, such as pivalic acid) with one or more glycols, particularly an aliphatic glycol, eg ethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, neopentyl glycol and 1 ,4-cyclohexanedimethanol. A polyethylene terephthalate or polyethylene naphthalate film is preferred. A polyethylene terephthalate film is particulariy preferred, especially such a film which has been biaxially oriented by sequential stretching in two mutually peφendicular directions, typically at a temperature in the range 70 to 125βC, and preferably heat set, typically at a temperature in the range 150 to 250,,C, for example as described in GB-A-838,708.
The substrate may also comprise a polyarylether or thio analogue thereof, particularly a polyaryletherketone, polyarylethersuiphone, polyaryletheretherketone, polyaryletherethersulphone, or a copolymer or thioanalogue thereof. Examples of these polymers are disclosed in EP-A-1879, EP-A-184458 and US-A-4008203. The substrate may comprise a poly(arylene sulphide), particularly poiy-p-phenylene sulphide or copolymers thereof. Blends of the aforementioned polymers may also be employed.
Suitable thermoset resin substrate materials include addition - polymerisation resins - such as acrylics, vinyls, bis-maieimides and unsaturated polyesters, formaldehyde condensate resins - such as condensates with urea, melamine or phenols, cyanate resins, functionalised polyesters, polyamides or polyimides.
The preferred polymeric film substrate for production of a composite sheet according to the invention may be unoriented, or uniaxially oriented, but is preferably biaxially oriented by drawing in two mutually peφendicular directions in the plane of the film to achieve a satisfactory combination of mechanical and physical properties.
Simultaneous biaxial orientation may be effected by extruding a thermoplastics polymeric tube which is subsequently quenched, reheated and then expanded by internal gas pressure to induce transverse orientation, and withdrawn at a rate which will induce longitudinal orientation. Sequential stretching may be effected in a stenter process by extruding the thermoplastics substrate material as a flat extrudate which is subsequently stretched first in one direction and then in the other mutually peφendicular direction. Generally, it is preferred to stretch firstly in the longitudinal direction, ie the forward direction through the film stretching machine, and then in the transverse direction. A stretched substrate film may be, and preferably is, dimensionally stabilised by heat-setting under dimensional restraint at a temperature above the glass transition temperature thereof. The substrate is suitably of a thickness from 6 to 300, particularly from 6 to 100, and especially from 6 to 25 μm.
The layer mineral preferably comprises platelets of a film-forming, 2:1 phyllosilicate layer mineral. For information on the composition and structure of phyllosilicate layer minerals, reference can be made to "Clay Minerals: Their Structure,
Behaviour & Use", Proceedings of a Royal Society Discussion Meeting, 9 & 10 November 1983, London, The Royal Society, 1984 (particulariy pages 222-223, 232-235).
The term "platelets" as used in this specification means tiny particles of the layer mineral obtained by subjecting the mineral to a chemical delaminating process to form an aqueous colloidal dispersion of high aspect ratio particles of the mineral from which a film can be formed.
Preferably, the layer mineral is selected from the group consisting of smectites, preferably hectorite and montmorillonite, and particularly vermiculite. The term "vermiculite" as used in this specification means all materials known mineralogically and commercially as vermiculite. Vermiculite ore being a naturally-occuring mineral contains a mixture of phases (eg vermiculite, biotite, hydrobiotite etc) and a mixture of interlayer cations (eg Mg2+, Ca2+, K+). Production of aqueous suspensions or slurries of vermiculite platelets rely on ion exchange (normally incomplete) to generate adequate macroscopic swelling. The swollen, fully- or partially-exchanged vermiculite gel can then be milled to produce a film-forming aqueous suspension of vermiculite platelets. Treatment of vermiculite particles with one or more aqueous solutions of metal (especially alkali metal) salts or alkyl ammonium salts followed by swelling in water and then milling to delaminate the vermiculite is well known and is described for example in GB-A-1016385,
GB-A-1119305, GB-A-1585104 and GB-A-1593382, and in US-A-4130687.
A preferred embodiment of the invention comprises a coating layer of vermiculite platelets wherein greater than 50%, preferably 55 to 99.9%, more preferably 60 to 99%, and particulariy 70 to 95% by number of the platelets have a particle size (by which is meant the size of the maximum width of a platelet) in the range 0.5 to 5.0 μm. It is also preferred that 80 to 99.9%, more preferably 85 to 99.9%, and especially 90 to 99.9% by number of the vermiculite platelets have a particle size in the range 0.1 to 5.0 μm. The mean particle size (by which is meant the mean value of the maximum width of the platelets) of vermiculite platelets is preferably 1.0 to 3.0 μm, more preferably 1.2 to 2.2 μm, and especially 1.3 to 1.6 μm. It is also preferred that the vermiculite platelets have a thickness in the range from approximately 10 to 60 A, especially from approximately 25 to 40 A. In addition, it is preferred that from 60 to 100%, more preferably from 70 to 99%, and particulariy from 90 to 95% by number of vermiculite platelets have a thickness in the range 10 to 60 A. The mean thickness of vermiculite platelets is preferably 25 to 50 A, more preferably 25 to 40 A, and especially 25 to 30 A.
Although the coating layer can comprise a substantially continuous layer of platelets of any practical thickness, suitably up to 5 μm, preferably up to 2 μm, and more preferably up to 0.5 μm, composite sheets exhibiting desired properties, for example improved barrier property against atmospheric oxygen, comprise a substantially continuous layer of platelets at very low thicknesses, eg as low as 0.01 μm, especially in the range from 0.02 μm to 0.3 μm, and particulariy in the range from 0.1 μm to 0.25 μm.
In a preferred embodiment of the invention the coating layer additionally comprises at least one material which may be any polymer known in the art to be capable of forming a continuous, preferably uniform coating. The polymeric material is preferably an organic resin and may be any film-forming polymeric or oiigomeric species or precursor therefor that assists in forming a film of the layer mineral and does not disrupt the film-forming capability thereof.
A suitable polymeric resin component of the coating layer comprises an acrylic or methacrylic resin, preferably thermoset and preferably comprising a polymer comprising at least one monomer derived from an ester of acrylic acid and/or an ester of methacrylic acid, especially an alkyl ester of (meth)acrylic acid where the alkyl group contains up to ten carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, terbutyl, hexyl, 2-ethylhexyl, heptyl, and n-octyl. The acrylic resin preferably comprises greater than 50 mole %, and preferably less than 98 mole %, especially from 70 to 96 mole %, and particulariy from 80 to 94 mole % of at least one monomer derived from an ester of acrylic acid and/or an ester of methacrylic acid, and/or derivatives thereof. Polymers derived from an alkyl acrylate, for example ethyl acrylate and butyl acryiate, together with an alkyl methacrylate are preferred. Polymers comprising ethyl acrylate and methyl methacrylate are particularly preferred The acrylate monomer is preferably present in a proportion in the range 30 to 65 mole %, and the methacrylate monomer is preferably present in a proportion in the range of 20 to 60 mole %.
A preferred acrylic resin, derived from 3 monomers comprises 35 to 60 mole % of ethyl acrylate/ 30 to 55 mole % of methyl methacryiate/2 to 20 mole % of methacrylamide, and especially comprising approximate molar proportions 46/46/8% respectively of ethyl acrylate/methyl methacrylate/acrylamide or methacrylamide, the latter polymer being particularly effective when thermoset - for example, in the presence of about 25 weight % of a methylated melamine-formaldehyde resin. The acrylic resin is preferably present in the coating layer in the range from 0.5 to 50% by weight of the coating layer.
In a particulariy preferred embodiment of the invention the coating layer is formed from a composition comprising a cross-linking agent, by which is meant a material which reacts chemically to form a polymeric resin during formation of the coating layer, preferably forming covalent bonds, both with itself and with the surface of the underlying layer to form cross-links thereby improving adhesion thereto. The cross-linking agent is suitably an organic material, preferably a monomeric and/or oiigomeric species, and particulariy monomeric, prior to formation of the coating layer. The molecular weight of the cross-linking agent is preferably less than 5000, more preferably less than 2000, especially less than 1000, and particularly in the range from 250 to 500. Additionally, the cross-linking agent should preferably be capable of internal cross-linking in order to provide protection against solvent penetration. Suitable cross-linking agents may comprise epoxy resins, alkyd resins, amine derivatives such as hexamethoxymethyl melamine, and/or condensation products of an amine, eg melamine, diazine, urea, cyclic ethylene urea, cyclic propylene urea, thiourea, cyclic ethylene thiourea, aziridines, alkyl melamines, aryl melamines, benzo guanamines, guanamines, alkyl guanamines and aryl guanamines, with an aldehyde, eg formaldehyde. A preferred cross-linking agent is the condensation product of melamine with formaldehyde. The condensation product may optionally be alkoxylated. A catalyst is also preferably employed to facilitate cross-linking action of the cross-linking agent. Preferred catalysts for cross-linking melamine formaldehyde include para toluene sulphonic acid, maleic acid stabilised by reaction with a base, and moφholinium paratoluene sulphonate.
The coating layer preferably comprises greater than 20% and less than 80%, more preferably greater than 25% and less than 70%, particularly greater than 30% and less than 60%, and especially greater than 30% and less than 50% by weight of the layer of the resin derived by cross-linking the cross-linking agent. The coating layer preferably comprises greater than 20% and less than 80%, more preferably greater than 30% and less than 75%, particularly greater than 40% and less than 70%, and especially greater than 50% and less than 70% by weight of the layer of the layer mineral. The coating layer is formed by applying the coating composition, comprising the layer mineral, and preferably the cross-linking agent, as a slurry or dispersion and removing the dispersion medium to form a coherent layer. Preferably, the dispersion medium comprises water and the slurry or dispersion comprises between 0.5% and 20%, more especially between 1% and 10%, by weight of the layer mineral.
The coating layer composition may be applied before, during or after the stretching operation in the production of an oriented film. The coating layer composition may, for example, be applied to the film substrate between the two stages (longitudinal and transverse) of a thermoplastics film biaxial stretching operation. Such a sequence of stretching and coating may be suitable for the production of a coated linear polyester film substrate, which is preferably firstly stretched in the longitudinal direction over a series of rotating rollers, coated, and then stretched transversely in a stenter oven, preferably followed by heat setting. The coating composition is preferably applied to an already oriented film substrate, such as a biaxially oriented polyester, particularly polyethylene terephthalate film, which is preferably subjected to heating.
The temperature to which the coated film is heated depends, inter alia on the composition of the substrate layer. A coated polyester, especially polyethylene terephthalate, substrate is suitably heated from 100βC to 240°C, preferably from 150βC to 180βC, in order to dry the aqueous medium, or the solvent in the case of solvent-applied compositions, and for cross-linking of the layer to occur and also to assist in coalescing and forming the coating into a continuous and uniform layer. In contrast, a coated polyolefin, especially polypropylene, is suitably heated in the range 85βC to 95βC.
The coating layer composition is preferably applied to the substrate by any suitable conventional technique such as gravure coating, dip coating, bead coating, reverse roller coating or slot coating.
The coating layer is preferably applied to the substrate at a dry coat weight within the range 0.25 to 50 mgdnr2, more preferably 0.5 to 20 mgdπr2, especially 1.0 to 5.0 mgdnr2. For a composite sheet having more than one coating layer, each coating layer preferably has a coat weight within the preferred ranges.
Deposition of the metallic layer may be effected by conventional metallising techniques, for example by deposition from a suspension of finely-divided metallic particles in a suitable liquid vehicle, or by electron beam evaporation, electroless plating, or preferably by a vacuum deposition process in which a metal is evaporated onto the adherent resin surface in a chamber maintained under conditions of high vacuum. Suitable metals include palladium, titanium, chromium, nickel, copper (and alloys thereof, such as bronze), silver, gold, cobalt and zinc, but aluminium is preferred.
The metallic layer is conveniently deposited in a thickness from monoatomic proportions to about 50 μm or greater, although a preferred range is from 0.005 to 15.0 μm, and particulariy from 0.01 to 0.5 μm. For a composite sheet having more than one metallic layer, each metallic layer preferably has a thickness within the preferred ranges.
The position of the layers, ie substrate, coating and metallic, of a composite sheet according to the invention is not critical, although it is preferred that the coating layer is adhered either directly or indirectly to the surface of the substrate. The metallic layer is preferably adhered either directly or indirectly to the surface of the coating layer, or more preferably adhered either directly or indirectly to the surface of the substrate remote from the coating layer. In an alternative structure, the coating layer may be adhered either directly or indirectly to the surface of the metallic layer.
In an embodiment of the invention, at least one additional primer layer is applied to the substrate layer prior to coating with the layer mineral coating layer and/or metallic layer. The presence of the primer layer can result in an improvement in the adhesion of the coating or metallic layer to the substrate and/or an improvement in barrier properties, particularly oxygen barrier.
The primer layer comprises at least one polymeric resin which may be any polymer known in the art to be capable of forming a continuous, preferably uniform, coating, being adherent to the supporting substrate, and preferably exhibiting optical clarity. Polymeric resins which are suitable for forming the primer layer include all the materials disclosed herein for use in the coating layer.
A preferred polymeric resin component of the primer layer, which is particularly suitable for use in conjunction with a coating layer, comprises a copolymer comprising acrylamide and/or a derivative thereof, such as a lower alkoxy, preferably n-butoxy, and/or methacrylamide and/or a derivative thereof, such as a lower alkoxy, preferably n-butoxy, and at least one other ethylenically unsaturated comonomer copolymerisable therewith, including acrylic acid and its esters, including alkyl esters, for example methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl-hexyl acrylate, isobutyl acrylates, hexy! acrylates and octyl acrylates; methacrylic acid and its esters for example methyl methacrylate, ethyl methacrylate and butyl methacrylate. Other suitable monomers include acryloπitrile, styrene, monomethyl styrene, vinyl toluene, maleic anhydride, and vinyl ethers. Styrene and alkyl acrylates are particulariy preferred monomers. Dienes such as butadiene or chloroprene may also be present in the primer layer copolymer. The copolymer preferably comprises at least one free functional acid (for example a pendant carboxyl or sulphonate group) group, that is a group other than those involved in the polymerisation reaction by which the copolymer is formed, such as acrylic acid, methacrylic acid, maleic acid and itaconic acid. Suitably up to 25%, preferably up to 10%, and especially up to 5% by weight of comonomer containing a free functional acid group may be employed. A preferred copolymer is derived from up to 90% by weight of styrene, up to 80% by weight of an alkyl acrylate, up to 15% by weight of methacrylic acid, and from 5% to 40% by weight of acrylamide which has been condensed with a solution of formaldehyde in n-butanol containing from 0.2 to 3 equivalents of formaldehyde for each amide group in the copolymer. A particulariy preferred copolymer comprises styrene/2-ethyl hexyl acrylate/methacrylic acid/n-butoxymethyl acrylamide in a ratio of 20 to 40/30 to 50/1 to 5/20 to 35 % by weight. GB-A-1174328 and GB-A-1134876 describe suitable methods for the synthesis of the aforementioned primer layer copolymers.
The polymeric resin of the primer layer is preferably compatible with, and includes, an additional acidic component, such as sulphuric, nitric, acetic acid or any mineral acid, such as hydrochloric acid, in the primer layer coating composition. The additional acidic component is preferably present in the primer layer coating composition in a concentration range from 0.5 to 15, more preferably 1 to 10, and especially 4 to 8% by weight relative to the weight of the polymeric resin. Sulphuric acid is a preferred acidic component.
A primer layer which is particularly suitable for use in conjunction with a metallic layer comprises an acrylic or methacrylic polymer comprising up to 35 mole %, preferably in the range from 7 to 25 mole %, more preferably 10 to 20 mole % of at least one monomer containing a free caΦoxyl group. By a free carboxyl group is meant a group, other than those involved in the polymerisation reaction by which the polymer is formed, of formula C02R, wherein R is preferably hydrogen, ammonium, substituted ammonium, and/or a metal, preferably an alkali metal such as lithium, sodium or potassium. Ethylenically unsaturated monomers can be employed to provide the free carboxyl groups, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid and derivatives thereof. A preferred acrylic polymer comprises 30 to 40 mole % of methyl methacrylate/40 to 50 mole % of butyl acrylate/ 5 to 15 mole % of styrene/ 10 to 20 mole % of acrylic acid and/or methacrylic acid.
The molecular weight of polymeric resin of the primer layer can vary over a wide range but the weight average molecular weight is preferably within the range 10,000 to 300,000, and more preferably within the range 15,000 to 100,000. The polymer(s) of the primer layer coating composition is generally water-insoluble. The primer layer composition including the water-insoluble polymer may nevertheless be applied to the substrate as an aqueous dispersion or alternatively as a solution in an organic solvent. The primer layer coating medium may be applied before, during or after any stretching operation used in the production of a polymeric substrate. In particular, the primer layer composition may be applied to the polymeric film substrate between the two stages (longitudinal and transverse) of a biaxial stretching operation. Such a sequence of stretching and coating is suitable for the production of a primed linear polyester film substrate, such as a coated polyethylene terephthalate film, which is preferably firstly stretched in the longitudinal direction over a series of rotating rollers, coated, and then stretched transversely in a stenter oven, preferably followed by heat setting.
The primer layer coating composition may be applied as an aqueous dispersion or solution in an organic solvent by any suitable conventional coating technique such as dip coating, bead coating, reverse roller coating or slot coating.
Prior to deposition of the primer layer, coating layer or metallic layer onto the substrate, the exposed surface thereof may, if desired, be subjected to a chemical or physical surface-modifying treatment to improve the bond between that surface and the subsequently applied layer. A preferred treatment, because of its simplicity and effectiveness, which is particularly suitable for the treatment of a polyolefin substrate, is to subject the exposed surface of the substrate to a high voltage electrical stress accompanied by corona discharge. Alternatively, the substrate may be pre-treated with an agent known in the art to have a solvent or swelling action on the substrate polymer. Examples of such agents, which are particulariy suitable for the treatment of a polyester substrate, include a halogenated phenol dissolved in a common organic solvent eg a solution of p-chloro-m-cresol, 2,4-dichlorophenol, 2,4,5- or 2,4,6-trichlorophenol or 4-chlororesorcinol in acetone or methanol.
The primer layer may also be applied directly on, for example, the coating layer prior to applying the metal layer, or alternatively on the metal layer prior to applying the coating layer.
The primer layer is preferably applied at a coat weight within the range 0.1 to 10 mgdrrr2, especially 1.0 to 6 mgdnr2. The thickness of the primer layer is desirably at least 0.005 μm and preferably should not greatly exceed about 1.0 μm. For composite sheets containing more than one primer layer, all the primer layers preferably have a coat weight within the preferred ranges. Modification of the surface of the primer layer, eg by flame treatment, ion bombardment, electron beam treatment, ultra-violet light treatment or preferably by corona discharge, may improve the adhesion of the subsequently applied coating layer comprising a layer mineral or metallic layer, but may not be essential to the provision of satisfactory adhesion.
The preferred treatment by corona discharge may be effected in air at atmospheric pressure with conventional equipment using a high frequency, high voltage generator, preferably having a power output of from 1 to 20 kw at a potential of 1 to 100 kv. Discharge is conveniently accomplished by passing the film over a dielectric support roller at the discharge station at a linear speed preferably of 1.0 to
500 m per minute. The discharge electrodes may be positioned 0.1 to 10.0 mm from the moving film surface.
In a preferred embodiment of the invention the composite sheet additionally comprises a heat-sealable layer. The heat-sealable layer may be suitably coated on, or laminated to, any of the layers of a composite film according to the invention, in order to form a packaging film laminate. The heat-sealable layer is preferably applied either directly or indirectly, to the layer mineral coating layer, and more preferably to the metallic layer, of the composite film.
The heat-sealable layer comprises polymeric material which preferably should be capable of forming a heat-seal bond to itself or to any of the layers of the composite film, by heating to soften the polymeric material of the heat-sealable layer and applying pressure without softening or melting the material of the substrate layer. The heat-sealable layer suitably has a heat-seal strength to itself of greater than 500 g/25 mm (196 Nnr1), preferably in the range from 800 to 5000 g/25 mm (314 to 1960 Nm 1), more preferably 1000 to 4000 g/25 mm (392 to 1568 Nnr1), and particulariy 1500 to
3000 g/25 mm (588 to 1176 Nnr1). The heat-seal strength can be measured by sealing the heat-sealable layer to itself at 140°C for 1 second under a pressure of 103 kPa (15 psi), cooling to room temperature, and measuring the force required under linear tension per unit width of seal to peel the sealed films apart at a constant speed of 4.23 mm/second.
A heat-sealable layer suitably comprises a polyester or polyolefin resin. Suitable polyesters include copolyester resins, especially those derived from one or more dibasic aromatic carboxylic acids, such as terephthalic acid, isophthalic acid and hexahydroterephthalic acid, and one or more glycols, such as ethylene glycol, diethylene glycol, triethylene glycol and neopentyl glycol. Typical copolyesters which provide satisfactory heat-sealable properties are those of ethylene terephthalate and ethylene isophthalate, especially in the molar ratios of from 50 to 90 mole % ethylene terephthalate and correspondingly from 50 to 10 mole % ethylene isophthalate. A polyolefin resin, particulariy polyethylene is a preferred component of the heat-sealable layer. Formation of a heat-sealable layer may be effected by applying a polymeric resin as an aqueous dispersion or solution in an organic solvent, by any suitable conventional coating technique such as dip coating, bead coating, reverse roller coating or slot coating. Alternatively, the heat-sealable layer may be extrusion coated. Preferably a preformed heat-sealable layer film, particulariy a polyethylene film, is laminated to a composite sheet according to the invention, by passing through a heated nip roll.
The heat-sealable layer preferably has a thickness of up to 100 μm, more preferably greater than 10 μm, and especially from 35 μm to 70 μm.
The heat-sealable layer may be joined to the composite film by means of an optional additional adherent layer. The adherent layer may comprise a thermosetting adhesive, such as a two component polyurethane adhesive.
Alternatively, the adherent layer may be a flexible layer, comprising a thermoplastic or rubbery polymeric resin material. A flexible adherent layer preferably exhibits a tensile modulus (1% secant modulus) of less than 2.0 MPa, preferably in the range from 0.05 MPa to 1.5 MPa, more preferably in the range from 0.1 MPa to 1.0
MPa, particulariy in the range from 0.2 MPa to 0.7 MPa, and especially in the range from 0.25 MPa to 0.45 MPa. The flexible adherent layer also preferably has a percentage elongation to break (%ETB) in the range from 300% to 10,000%, more preferably in the range from 600% to 4000%, particulariy in the range from 800% to 2000%, and especially in the range from 1200% to 1700%. Suitable flexible adherent layer polymeric resins are natural and synthetic rubbers, eg where 1 ,4-polyisoprene is a major component. Other preferred polymeric resins include poiyteφβπe resins, isoprene-piperylene copolymers, styrene-butadiene copolymers, styrene-isoprene block copolymers, rubbery branched or radial block copolymers of conjugated dienes and vinyl aromatic hydrocarbons, cyclic monoolefin copolymers, carboxyl-containing chloroprene polymers, ethylene-vinyl acetate-diolefin-ester copolymers, polyisocyanate modified natural or synthetic rubber, and non-thermoset polyurethane resins.
In a preferred embodiment of the invention, the polymeric resin of the adherent layer is a styrene-butadiene copolymer, preferably a block copolymer. The molar ratio of styrene:butadiene is preferably in the range from 0.1 to 10:1 , more preferably in the range from 0.5 to 3:1 , and especially in the range from 1.2 to 1.6:1. The molecular weight of polymeric resin of the adherent layer can vary over a wide range but the weight average molecular weight is preferably within the range 5,000 to 1,000,000, more preferably within the range 10,000 to 500,000, and especially within the range 20,000 to 300,000. The adherent layer coating composition may comprise other materials used to modify the properties of the resultant adherent layer, such as antioxidants, plasticisers, and tackifying resins.
The polymer(s) of the adherent layer coating composition may be water-soluble or water-insoluble. The adherent layer composition including any water-insoluble polymer may nevertheless be applied to the coating layer surface as an aqueous dispersion or alternatively as a solution in an organic solvent.
The adherent layer composition is preferably applied by any suitable conventional technique such as dip coating, bead coating, reverse roller coating or slot coating. The adherent layer is preferably dried by heating from 70βC to 160βC, preferably from 80°C to 100βC, in order to dry the aqueous medium, or the solvent in the case of solvent-applied compositions, and to assist in coalescing and forming the adherent composition into a continuous and uniform layer.
The adherent layer is preferably applied at a coat weight within the range 10 to 200 mgdnr2, more preferably 20 to 150 mgdnr2, and especially 50 to 100 mgdm'2. The thickness of the dried adherent layer is preferably in the range from 1 μm to 20 μm, more preferably 2 μm to 15 μm, and especially 5 μm to 10 μm.
A composite sheet according to the invention suitably has an oxygen permeability of less than 1 , preferably less than 0.5, more preferably less than 0.1 , particulariy less than 0.05, and especially less than 0.01 cc m2/day.
One or more of the layers of a composite sheet according to the invention, ie substrate, primer, coating, metallic, adherent and/or heat-sealable layer(s), may conveniently contain any of the additives conventionally employed in the manufacture of polymeric films. Thus, agents such as dyes, pigments, voiding agents, lubricants, anti-oxidants, anti-blocking agents, surface active agents, slip aids, gloss-improvers, prodegradants, ultra-violet light stabilisers, viscosity modifiers and dispersion stabilisers may be incoφorated into one or more of the aforementioned layers as appropriate. In particular, a substrate may comprise a particulate filler, such as silica, of small particle size. Desirably, a filler, if employed in a substrate layer, should be present in a small amount, not exceeding 0.5%, preferably less than 0.2%, by weight of the substrate.
Preferred composite sheets comprise the following layers, in order, (a) metallic/substrate/coating,
(b) metallic/primer/substrate/primer/coating (the primer layers may be the same or different),
(c) substrate/primer/metallic/coating, (d) substrate/coating/primer/metallic.
Any of the above structures (a) to (d) may have an additional heat-sealable layer on either one or both of the outer surfaces thereof, either adhered directly thereto or by means of an optional intermediate adherent layer.
Composite sheets according to the invention may be used for packaging any oxygen and/or water sensitive products such as food and drink, pharmaceuticals, seeds, photographic films etc.
The invention is illustrated by reference to the accompanying drawings in which:
Figure 1 is a schematic sectional elevation, not to scale, of a composite sheet having a substrate, metallic and layer mineral coating layers.
Figure 2 is a similar schematic elevation of a composite sheet as shown in Figure 1 , with an additional primer layer between the substrate and metallic layers.
Figure 3 is a similar schematic elevation of a composite sheet as shown in Figure 2, with additional adherent and heat-sealable layers. Referring to Figure 1 of the drawings, the composite sheet comprises a substrate layer (1) having a metallic layer (2) bonded to one surface (3) thereof. A layer mineral coating layer (4) is bonded to the remote surface (5) of the metallic layer
(2).
The composite sheet of Figure 2 further comprises an additional primer layer (6), sandwiched between the substrate layer (1) and metallic layer (2).
The composite sheet of Figure 3 further comprises an additional adherent layer (7), bonded to the remote surface (8) of the coating layer (4) and an additional heat-sealable layer (9) bonded to the remote surface (10) of the adherent layer (7). The invention is further illustrated by reference to the following examples. Example 1
A polyethylene terephthalate film was melt extruded, cast onto a cooled rotating drum and stretched in the direction of extrusion to approximately 3 times its original dimensions. The cooled stretched film was then coated with an aqueous primer layer composition containing the following ingredients: Methyl methacrylate/butyl acrylate/styrene/ 60 g
(acrylic acid or methacrylic acid) polymer of approximately 35/37/12/16 mole %.
Hexamethoxy methyl melamine 12 g (commercially available as 'Cymel' 300)
Ammonium nitrate 2 g
Synperonic NP 10 3 g
(an alkyl nonylphenol ethoxylated surfactant supplied by Imperial Chemical Industries)
Water added to give a coating composition of total volume 2 litres.
The polyethylene terephthalate film was coated on one side only. The primed film was passed into a stenter oven, where the film was dried and stretched in the sideways direction to approximately 3 times its original dimensions. The biaxially stretched primed film was heat set at a temperature of about 200°C by conventional means. Substrate thickness was 23 μm, primer layer thickness was 0.03 to 0.05 μm with a coat weight of approximately 0.3 to 0.5 mgdnr2. The primer layer of the film was metallised by a conventional evaporative method to give a layer of aluminium of approximately 0.05μm.
A vermiculite suspension was prepared in accordance with the following method:
100 g of vermiculite ore (ex-Carolina, US) was refluxed with 1 litre of 1 N lithium citrate solution at 80βC for four hours and left at room temperature for five days. This resulted in the exchange of 45.3 mEq/100 g of lithium cations in the ore. The ion-exchanged vermiculite ore was washed 5 times with deionised water to remove the excess salts and left overnight to swell in a large volume (ie 10 times the volume of vermiculite) of deionised water. The swollen vermiculite was milled for 40 minutes in a Greaves high-shear mixer at 7200 φm to produce a suspension of vermiculite platelets. The platelet suspension was then sieved by passing through a mechanically agitated filter having a pore size of 106 μm. The biaxially oriented polyethylene terephthalate substrate/primer layer/metallic layer structure was coated on the metallic layer using a gravure coater, with a coating layer composition comprising the following ingredients:
Vermiculite 6 1 (7.5% w/w aqueous dispersion)
Cymel 385 375 ml
(melamine formaldehyde of molecular weight 348)
Para toluene sulphonic acid 216 ml
(10% w/w aqueous solution)
Synperonic NP 10 100 ml
(10% w w aqueous solution of a nonyl phenol ethoxylate, supplied by ICI)
Demineralised water to 10 litres
The coated film was dried at 180°C, and the dry coat weight of the coating layer was approximately 2 mgdnr2. The thickness of the coating layer was approximately 0.2 μm.
The remote surface of the layer mineral coating layer was coated, using a gravure coater, with an adherent layer composition comprising the following ingredient:
Rubber based resin (Product No 10-2060, supplied by
Holden Surface Coatings Ltd, England)
The adherent layer coated film was dried at 90°C, and the dry coat weight of the adherent layer was approximately 100 mgdnr2. The thickness of the adherent layer was approximately 8 μm. The adherent layer surface of the composite sheet was laminated with a 50 μm heat-sealable layer of polyethylene film, by passing the two films through a nip heated at 70βC. The oxygen barrier property of the final composite sheet (substrate/primer/metallictcoating/adherent/heat-sealable layers) was determined by measuring the oxygen permeability using a Mocon 1050 (Modem Controls Inc.) test instrument. A sample of the composite sheet was placed in the machine with the nitrogen carrier gas (containing 1 % hydrogen) flowing both above and below the sheet, in order that a background reading can be obtained. The nitrogen above the sheet was replaced by oxygen, and the amount of oxygen able to permeate through the sheet was measured in a carrier gas by using a sensor. The oxygen permeability was 0.01 cc/m2/day. The oxygen permeability of uncoated polyethylene terephthalate film was also measured and found to be 50.0 cc/m2/day.
The above example illustrates the improved properties of a composite sheet according to the present invention.

Claims

Claims
1. A composite sheet comprising a substrate layer, a coating layer comprising a layer mineral, and a metallic layer.
2. A composite sheet according to claim 1 wherein the layer mineral comprises platelets of a film-forming, 2:1 phyllosilicate.
3. A composite sheet according to either one of claims 1 and 2 wherein the 2:1 phyllosilicate comprises vermiculite.
4. A composite sheet according to any one of the preceding claims wherein the coating layer additionally comprises a cross-linking agent.
5. A composite sheet according to any one of the preceding claims wherein an additional primer layer is present.
6. A composite sheet according to claim 5 wherein the primer layer improves the adhesion of the metallic layer and comprises an acrylic or methacrylic polymer comprising up to 35 mole % of at least one monomer containing a free carboxyl group.
7. A composite sheet according to any one of the preceding claims wherein an additional heat-sealable layer is present on at least one external surface.
8. A composite sheet according to claim 7 wherein the heat-sealable layer comprises polyethylene.
9. A composite sheet according to any one of the preceding claims wherein the substrate layer is a polymeric film.
10. A method of producing a composite sheet by forming a substrate layer, applying a coating layer comprising a layer mineral, and applying a metallic layer.
EP99918934A 1999-04-30 1999-04-30 Composite sheet Withdrawn EP1177248A1 (en)

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ITMI20021150A1 (en) * 2002-05-28 2003-11-28 Mipa S P A PROCESS FOR THE PREPARATION OF PARTIALLY METALLIC AND PRINTED PLASTIC FILMS
JP4931033B2 (en) * 2002-07-19 2012-05-16 日本テトラパック株式会社 LAMINATED MATERIAL, METHOD FOR PRODUCING LAMINATED MATERIAL, AND PACKAGING CONTAINER
EP2033986A1 (en) * 2007-09-03 2009-03-11 Alcan Technology & Management Ltd. Packaging part and method for its production
JP6408465B2 (en) * 2012-07-31 2018-10-17 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ Bonding method using a thin adhesive layer

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IT1187646B (en) * 1985-03-25 1987-12-23 Moplefan Spa POLYOLEFINIC FILMS HAVING IMPROVED WATERPROOFING CHARACTERISTICS WITH GASES AND VAPORS AND PROCEDURE FOR THEIR PRODUCTION
GB9112843D0 (en) * 1991-06-14 1991-07-31 Ici Plc Polymeric film
GB9112827D0 (en) * 1991-06-14 1991-07-31 Ici Plc Polymeric film
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