TW483826B - Composite sheet exhibiting improved oxygen barrier properties and suitable for use as a packaging material and method for producing same - Google Patents

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

483826 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (!) The present invention relates to a composite material, and in particular to a composite material suitable for use as a packaging material. There is a commercial need for packaging materials that exhibit barrier properties (particularly oxygen and water barriers), especially films that package edible products. Films having a coating layer 'or a metal layer or a polyvinylidene chloride layer containing a small plate-like substance have been disclosed due to their oxygen barrier properties. Unfortunately, none of the aforementioned Version 1 requirements are adequate. Coatings containing layer minerals have been used to impart various properties to film substrate materials, such as flame retardancy, antistatic properties, and gas (particularly oxygen) barriers, as disclosed in 'for example, Japanese Unexamined Patent Specification No. 62_181144, ep_a_ 235926 and US-A-3499820. We now come up with a composite material comprising a layered ore coating and a metal layer, which surprisingly shows enhanced barrier (especially oxygen) properties. Therefore, the present invention provides a composite material comprising a matrix layer, a coating layer containing a layered ore, and a metal layer. The present invention also provides a method for manufacturing a composite material, which is achieved by forming a substrate layer 'and applying a coating layer containing a layered ore and applying a metal layer. The matrix layer for use in the manufacture of the composite material according to the present invention suitably contains any film or fabric substance, such as paper, cardboard or synthetic paper. In a preferred embodiment of the present invention, the matrix is formed of a polymeric substance, which is more preferably capable of forming a self-framed opaque, or preferably transparent, film or layer. As for "self-supporting film or layer," it means a film or layer that can exist alone without a supporting base. -4- This paper size applies to China National Standard (CNS) A # specifications (21 × 297 mm) (Please read the precautions on the back before filling in this page}-Binding · Order 483826, Invention Description (Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs: Λ invention "The matrix layer of composite materials can be made of any polymer that forms a film ry. Suitable thermoplastic synthetic substances include homopolymers or fibers of 1-fluorene hydrocarbons (for example, B :: propane or butyl)], especially polypropylene, :: month; polycarbonate, and especially synthetic A linear polyether which can be obtained by condensing a dicarboxylic acid or a lower alkyl group (up to 6 carbon atoms) of a diester / aqueous acid or a low-carbon alkyl diacetate to include, for example, To _ 酉 = =, iso- 酉 酸 acid, 酉. Acid, 2,5., 2,6- or 2,74 dileic acid, trumpet capric acid, adipic acid, azelaic acid, 4,4, -di Phenyl dicarboxylic acid, hexa-p-phthalic acid, or phenoxyethyl alcohol with one or more diols (if necessary, monocarboxylic acid, such as pivalic acid), especially Group diols, ethylene glycol, i, 3-propanediol, 1,4-butanediol, neopentyl glycol and i, 4.2 hexanedimethanol. Polyethylene terephthalate and polyethylene glycol polyacetate are preferred. Ethylene terephthalate film is particularly good, especially the film made by ... at a temperature usually in the range of 70 to 125 ° C, by using two perpendicular to each other Continuous stretching in the direction and biaxial orientation, and preferably heat-set at a temperature typically in the range of 150 to 250 C, for example, as illustrated by GB-A-838,708. '' The matrix may also contain polyaryl ether or its thio Analogs, in particular polyarylfluorenone, polyaryl ether maple, polyaryl ether ketone ether, polyaryl ether maple ether, or copolymers or thio analogs thereof. Examples of such polymers are illustrated in Ερ 1879 , EP-A-184458 and US-A-4008203. The matrix may contain polyaromatic sulfides), especially poly-p-phenylene sulfides or their copolymers. Blends of the aforementioned polymers may also be used. Appropriate thermosetting resin matrix materials include addition polymerization resins _ hydrogen method A- (sub-example (please read the precautions on the back before filling out this page). --7 -5- This paper size applies to China National Standard (CNS) A4 specification (2 丨 〇 > < 297 mm) 峠 〇JO 厶 U 5. Description of invention (printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs) For example, acrylic acid, acetone A aldehyde condensation resin-Example \,-maleimide and unsaturated polyester, formazan resin, functionalized urea, melamine, or the condensation of hydrazone, chloric acid κ-- Permanent amine or polyimide. The blessings according to the present invention are non-orientated, or uniaxial 彳: The preferred polymeric film substrates used can be perpendicular to each other but preferably by pulling on two of the film planes. The biaxial orientation is achieved to achieve the mechanical and physical properties: two simultaneous biaxial orientation can be achieved by squeezing the thermoplastic polymer tube, followed by 'ten fires, reheating, and then expanding with inert gas pressure = ^ Citation: horizontal orientation effect, and then return at a speed that will cause the vertical fixed effect. Continuous stretching can be accomplished in the tenter method by extruding the thermoplastic matrix material as a planar extrudate and then stretching in one direction and then perpendicularly to the other. And reach. Generally, it is preferred to stretch first in the machine direction, i.e. through the front direction of the film stretcher, and then in the transverse direction. Stretching through the substrate film is preferred, and it is preferably directionally stable by thermally fixing at a temperature exceeding its glass transition temperature under size suppression. The thickness of the substrate is suitably 6 to 300, particularly 6 to 100, and particularly 6 to 25 m. The layered ore preferably includes a small piece of 2: 1 phyllosilicate ore that forms a film. For information about the composition and structure of the phytosilicate ore, you can refer to, Sticking a mineral: its structure, efficacy And uses, ("clay Minerals: Their Structure, Behaviour & Use") Proceedings of a Royal Society Discussion Meeting ^ 1983, November 9 & 10 'Xu Dun (1 ^ 〇11 (1011), the British Academy of Sciences (1 ^ 〇% 1 the direction of the soil) (please read the precautions on the back before filling this page)

、 1T ▼ Line 6- This paper size is applicable to Chinese National Standard (CNS) Α4 size (210X297mm) 483826 Printed Invention Note (Society), 1984 (Special Department 222-223) , Pages 232-235). As used in this specification / use, the term "small flakes" refers to the small particles of layered ore, which are formed by subjecting minerals to a chemical delamination method to form high aspect ratio particles of minerals from which films can be formed Water colloidal dispersion. The bedding ore is preferably selected from the group consisting of: green earth, preferably hectorite and montmorillonite, and especially vermiculite. When used in this specification, the term "vermiculite" refers to all substances known mineralogically and commercially as vermiculite. Vermiculite ore, a naturally occurring mineral, contains multiple phases (eg, vermiculite, black Mica, hydrogenated biotite, etc.) and mixtures of intercalated coatings (for example, Mg2, Ca2 +, κ +). 2 The manufacture of aqueous suspensions or sludges of small stone flakes depends on ion exchange (exchange) It is incomplete) in order to produce a proper gross expansion effect. The swollen king or the wounded father changed the vermiculite gel and then it could be milled to make a film-shaped vermiculite aqueous suspension. After the action of vermiculite particles treated with one or more aqueous solutions of a metal (especially an alkali metal) salt or an alkylammonium salt, the swelling effect in water is followed by milling to delaminate the vermiculite, etc. Known and described in, for example, GB_A1016385, gb_a iii93305, GB-A-1585104 and GB-A-1593382, and US-A-4130687. Preferred embodiments of the present invention include vermiculite chips Coating layer, more than 50%, preferably 55 to 99.9%, more preferably 60 to 99%, and especially 70 to 95% (in number) of small pieces have a particle size in the range of 0.5 to 5.0 microns (which means the maximum width of the small pieces). Jiadi '80 to 99.9%, more preferably 85 to 99.9%, and especially 90 to " • 9% (by quantity) vermiculite flakes are in the range of 0-1 to 50 microns

(Please read the precautions on the back before filling this page)-Binding _ Thread • J —--1 · ^ = 483826 A7 B7 V. Description of the invention (5 < Particle size. Flat area of vermiculite small pieces It is better to say that the size and the size (which means the small pieces < taking the average of the large width) is better. Η 乂 The range is 1.0 to 3.0 microns, more preferably 1.2 to 3.0 2.2 μm, and especially 3 ～ i on the soil · 6 锨. 斫 Preferably, the thickness of the vermiculite platelets is about 10 to 60 Å (from # 从 1), especially about 25 to 40 Angstroms. Inside. In addition, it is preferably from 60 to 100%, more preferably from 70 to 99%, and from 90 to 95% (by number) of worm-to-stone flakes having a thickness in the range of M · A. The average thickness of the vermiculite platelets is preferably 25 to 50 Angstroms, more preferably 25 to 40 Angstroms, and especially 25 to 30 Angstroms. Although the coating layer may comprise almost completely continuous small pieces of any practical thickness, the thickness is suitably up to 5 microns, preferably up to 2 microns: and more preferably up to 0.5 microns, but shows the desired properties (E.g., to improve the barrier properties against atmospheric oxygen) a composite material comprising an almost completely continuous layer of very low thickness platelets, for example, as low as 0.01 micron, especially between 0.02 micron to 0.3 In the micrometer range, and particularly in the range of 0.01 micrometer to 0.25 micrometer. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please read the notes on the back before filling this page) In the preferred embodiment of the present invention, the coating layer additionally contains at least An object that can be any polymer known in the art that forms a continuous, preferably uniform, coating. The polymer is preferably an organic resin, and can be any polymeric or oligomeric species or precursor that forms a film, so it helps to form a layer mineral film without disintegrating its ability to form a film. A suitable polymeric resin component of the coating layer comprises an acrylic or methacrylic acid resin, preferably thermosetting and preferably comprising at least one monomer derived from an ester of acetic acid and / or an ester of methacrylic acid Polymer, the ester of acrylic acid and / or the ester of methacrylic acid is especially one in which the alkyl group contains -8,483,826 A7 B7 printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs for consumer cooperation ) Alkyl esters of (meth) propanoic acid with up to ten carbon atoms, such alkyl groups, such as' methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , Tert-butyl, hexyl, 2-ethylhexyl, heptyl and n-octyl. The malonic acid resin preferably contains more than 50 mole%, and more preferably less than 98 mole%, especially from 70 to 96 mole%, and particularly from 80 to 94 mole. 0 / 〇 at least one monomer derived from an ester of malonic acid and / or an ester of methacrylic acid, and / or a derivative thereof. Polymers derived from alkyl acrylates (e.g., ethyl propionate and butyl propionate) together with alkyl methacrylate are preferred. Polymers containing ethyl propionate and methyl methylpropionate are particularly preferred. The acrylic monomer is preferably present at a ratio in the range of 30 to 65 mol%, and the fluorenylpropionate monomer is preferably present at a ratio in the range of 20 to 60 mol%. Preferred malonic acid resins are derived from 3 monomers, which include 35 to 60 mole% ethyl valerate / 30 to 55 mole% methyl methylpropionate / 2 to 20 mole % Methacrylamide, and especially the approximate molar ratio of individual ethyl acrylate / methyl methacrylic acid / promethamine or methamphetamine 46/46/8%, when hot The latter polymer is particularly effective at the time of fixing—for example, it is present at about 25% by weight of methylated melamine · formaldehyde resin. The malonate tree is preferably present in the coating layer in an amount ranging from 0.5 to 50% by weight of the coating layer. In a particularly preferred embodiment of the present invention, the coating layer is formed of a composition containing a cross-linking agent, which means a substance that chemically reacts to form a polymer resin during the formation of the coating layer. Jiaxi forms a covalent bond with itself and with the surface of the coated layer to form and thus increase its adhesion

(Please read the precautions on the back before filling this page}-Binding and Binding ▼ Printed by A7 '______B7____, a consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs — The adhesive is re-linked. Before the coating is formed, the cross-linking agent is appropriate The ground is a kind of shellfish, preferably monomers and / or oligomeric species, and particularly monomers, and the molecular weight of the coupling agent is preferably less than 5000, more preferably less than 2000, especially less than 2000. 1000, and especially in the range of 250 to 5000. In addition, in order to improve the protection against solvent penetration, the cross-linking agent should preferably be able to cross-link. The appropriate cross-linking agent may include epoxy resin, alkyd resin Amine derivatives, for example, hexamethoxymethylmelamine and / or condensation products of amines and aldehydes (eg, formaldehyde), the amines include, chloramine, Erhuang, urea, ciprofen urea, ciprofen urea, And urea, cycloethylene thiourea, aziridine, alkylmelamine, arylmelamine, phenylfluorenylamine, fluorenylamine, alkylfluorenylamine and arylfluorenylamine. Preferred crosslinking agents are Condensation product of melamine and formaldehyde. The condensation product may be alkoxylated if necessary. Preferably, a catalyst is also used to The cross-linking reaction of the cross-linking agent is carried out. The preferred catalysts for cross-linking melamine formaldehyde include p-toluenesulfonic acid, cis-butyric acid and morpho-p-toluene acid ester which are satisfied by reaction with a base. The coating layer preferably contains more than 20% and less than 80%, more preferably more than 25% and less than 70%, particularly more than 30% and less than 60%, and especially more than 30% and less than 50% (in terms of (By weight) a resin layer obtained by crosslinking with a cross-linking agent. The coating layer preferably contains more than 20% and less than 80%, more preferably more than 30% and less than 75%, especially more than 40% and less than 70%, and especially more than 50% and less than 70% (by weight) of the ore layer. The coating layer is formed by applying a coating group of the layered ore in the form of a slurry or dispersion and preferably the parent The dispersing medium is removed to form an adhesive layer. Preferably, the dispersing medium contains water and the slurry or dispersion contains between 0.5% and 20%, and more particularly between 1% and 10% (with Weight) layer ore. • 10- This paper size applies to China National Standard (CNS) A4 specification (210X297). '^-

J. ^^ Private clothing-(Please read the precautions on the back before filling out this page) Fee A7 Fifth, the description of the invention (8) The body coating and coating composition can be stretched before the orientation film is manufactured , Period, or, known later. The coating composition may, for example, apply to the film substrate between two steps (longitudinal and transverse) of a biaxial ^ -direction stretching operation of a thermoplastic film: this stretching * coating sequence may be suitable for coating. The IU at the linear polyacetate film is preferably coated on top of a series of rotating light and stretched in the longitudinal direction, and then stretched laterally in a stenter oven, preferably heat-fixed. The coating composition is preferably applied on an oriented film substrate, for example, biaxially oriented polyester, especially a polyethylene terephthalate film, and the vehicle is also heated. The temperature at which the coated film is heated is particularly dependent on the substrate layer and the mouth. The coating is overpolymerized in order to dry the aqueous medium, or in the case of a composition in which a solvent is applied, and to allow cross-linking of the layers and also to help the coatings join and form on a continuous and uniform layer. The ester (especially poly-p-g-ethylene glycolate) substrate is suitably heated to 1000 to 2400 tt, preferably 150 ° C to 180 ° c. In contrast, coated polyolefins, especially polypropylene, are suitably heated in the range of 85 ° C to 95 ° C. The coating composition is preferably applied to the substrate by any suitable conventional technique including, for example, gravure coating, dip coating, bead coating, reverse roll coating, and gap coating. Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The coating is preferably applied to the substrate with a dry coating weight within the range of 0-25 to 50 mgdnT2. More preferably, it is 05 to 20 mgdnT2, especially 1.0 to 5.0 mgdm · 2. For composites having more than one coating layer, each coating layer preferably has a coating weight within a preferred range. The deposition of the metal layer can be achieved by using conventional metal plating technology, for example, by suspending the metal particles finely dispersed in an appropriate liquid carrier. -11-This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297). (Xian) 5. Description of the invention (Jiawei ^ product effect, or by electron beam evaporation, vacuum hunting method, in which the metal is kept in the second plating, or evaporation of the adhesive resin surface than ΓΓ. Appropriate gold Γ Package: Vacuum conditions but rhenium, steel (and its alloys, such as 'yin copper'), silver, palladium, titanium, and yi are preferred. 〃, osmium, and zinc, although the preferred range is from 0.05 to 15 Pack "thickness deposition. For complex layers of more than one kind of metal or thicker metal layers, it is better to have a thick cut within a better range. Each layer of t, that is, substrate, coating The surface adhesion of the substrate layer of the metal layer and the metal layer-the best is to make the coating layer directly or indirectly to the surface. The metal layer is preferably directly or indirectly to the surface of the coating layer, or more directly or Indirectly adheres to the surface away from 1. Can be used in the other In the structure, coating: == the quality layer is adhered to the surface of the metal layer. The coating is directly or indirectly. 2: Hair: In a specific embodiment, the layer is coated with gold, and the layer is then applied to the matrix layer. Apply at least one additional preliminary layer. The presence of the preliminary reed foot can cause the adhesion of the coating or metal layer to the substrate and / or the barrier properties, especially the enhancement of the oxygen barrier. The more advanced preliminary layer contains at least one polymeric resin, It may be any polymer known in the art that can form a continuous, good uniform, coated layer, which is adhered to the support matrix, and preferably shows optical transparency. Polymer resins suitable for forming the preliminary layer include herein Reveals all substances used in the coating layer. It is a better polymeric resin that is especially suitable for the preparation layer used at the same time as the coating layer. 12 This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) 483826 A7 B7 V. Description of the invention (10) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling out this page). Lower alkoxy, preferably n-butoxy) and / or methacrylamide and / or derivatives thereof (for example, lower alkoxy, preferably n-butoxy) and at least one Copolymerizable with it < Other copolymers of genus unsaturated comonomers, including propionic acid and its esters, including alkyl esters, such as methyl acrylate, ethyl propionate, butyl propionate , 2-ethylhexyl acrylate, isobutyl propionate, hexanoic acid acrylate, and octyl acrylate; methylpropanoic acid and its esters, for example, methyl methylpropionate, methylpropionate Ethyl esters and butyl methyl propionate. Other suitable monomers include acrylonitrile, styrene, monoethyl styrene, ethyl ethyl toluene, cis-butanedioic anhydride, and ethyl ether. Styrene and malonic acid Alkyl esters are particularly preferred monomers. Difluorene (eg, succinimide or neoprene) may also be present in the preparation layer copolymer. The copolymer preferably contains at least one free functional acid (eg, pendant carboxyl group or sulfo group) group, that is, a group other than those contained in the polymerization reaction by which the copolymer is formed, for example, propylene Gallic acid, methacrylic acid, maleic acid and decomposed aconitic acid. Appropriately up to 25%, preferably up to 10%, and especially up to 5% (by weight) of comonomers containing free functional acid groups. Preferred co-monomer systems are derived from up to 90% by weight of acetofluorene, up to 80% by weight of propionate propionate, up to 1% by weight of methylpropionate, and 5% to 40% by weight of acrylamide. Promethazamine has been condensed with a formaldehyde solution in n-butanol, which contains 0.2 to 3 equivalents of formaldehyde to each acid amine group in the copolymer. Particularly preferred copolymers include acetophenone / 2 · ethylhexylpropionate / fluorenylpropionate / n-butane in a ratio of 20 to 40/30 to 50/1 to 5/20 to 35% by weight Oxymethylpropionamine. GB-A-1 174328 and GB-A-1 134876 explain the synthesis of the aforementioned preliminary layer copolymerization. 13- This paper size applies to China National Standard (CNS) A4 (210X297 mm). Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 483826 V. Appropriate method of invention description (μ). The polymeric resin of the preliminary layer is preferably coexisting with and containing an external acidic component of the preliminary layer coating, and the acidic component includes, for example, acid, nitric acid, acetic acid, or any inorganic acid such as chlorochloric acid. Additional acid: The component is preferably present in the preliminary layer coating composition at a concentration in the range of 0 to 15 with respect to the weight of the polymer resin, more preferably 1 to 10, and especially 4 to 8% by weight. In. Sulfuric acid is preferably an acidic component. The preparation layer particularly suitable for simultaneous use with the metal layer includes a polymer of propionic acid or methacrylic acid, which contains up to 35 mol%, preferably in the range of 7 to 25 mol%, more preferably 10 to 20 mole% of at least one free carboxyl group-containing monomer. As for the free carboxyl group means, other than those contained in the polymerization reaction by which the copolymer is formed, a group having the general formula c02R, wherein R is preferably hydrogen, ammonium, substituted perammonium, and / Or a metal, preferably an alkali metal, such as lithium, sodium or potassium. Unsaturated feminine monomers can be used to provide free carboxyl groups, such as, for example, valeric acid, methacrylic acid, cis-succinic acid, scaly aconite and its derivatives. Preferred malonic acid polymers contain 30 to 40 mole% methyl methacrylate / 40 to 50 mole% butyl acrylate / 5 to 15 mole% styrene / 10 to 20 mole Ear% acrylic and / or methacrylic acid. The molecular weight of the polymeric resin of the preliminary layer can be varied within a wide range, but the weight average molecular weight is preferably in the range of 10,000 to 300,000, and more preferably in the range of 15,000 to 100,000. The polymer of the preliminary coating composition is usually water-soluble. However, the preliminary layer composition comprising a water-soluble polymer may be applied to the substrate as an aqueous dispersion or alternatively as a solution in an organic solvent. -14 This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling out this page)-Binding and ordering, Ministry of Economic Affairs, Central Standards Bureau, Consumer Consumption, Printing A7 '----- —__ B7 V. Description of the invention (12), 2 The secondary coating medium can be used during or after the stretching operation used in the production of the polymer matrix. In particular, the preliminary layer composition can be applied to the polymer film substrate between two steps (longitudinal and lateral) of the double stretching operation. This sequence of stretching and coating is suitable for the preparation of linear poly (vinyl acetate) film substrates (such as coated poly (ethylene terephthalate) films). Preferably, it is first stretched and coated on a series of tops, and then stretched horizontally in a stenter oven, and preferably heat-fixed. The eight-layer coating composition can be applied in the form of an aqueous dispersion or a solution in an organic solvent by any suitable conventional coating technology, such as reverse / shell coating, bead coating, reverse coating, etc. Roll coating and gap coating. Before the preparation layer, coating layer, or metal layer is deposited on the substrate, if two are required, the exposed layer may be subjected to chemical or physical surface modification treatment to increase the bonding between the d surface and the subsequent application layer. Due to its simplicity and effectiveness, the preferred treatment (which is particularly suitable for the treatment of polyalkylene hydrocarbon substrates) is to expose the exposed surface of the substrate to high voltage electrical stress accompanied by corona discharge. Alternatively, the foundation can be pretreated with agents known in the art to have a solvent or swelling effect on the matrix polymer. Examples of such agents that are particularly suitable for the treatment of polymeric substrates include chemical compounds dissolved in common organic solvents. For example, p-chloro-m-cresol, 2,4-dichlorophenol, 2,4,5_ or 2,4,6-trichlorophenol or 4-chlororesorcinol in acetone or methanol . The preliminary layer can also be applied directly before, for example, the application of a metal layer.

On the coating, or alternatively, directly on the metal layer before the coating is applied. The J preparation layer is preferably in the range of (M to 10 mgdm · 2, especially 丨 〇 to 6 -15- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back first) (Fill in this page again) Binding and binding 483826 V. Description of the invention (13) Application of coating weight in the range of mgdm_2. The thickness of the preliminary layer is desirably at least 0.005 microns, and preferably not more than about 10 microns. For composites with more than one preparation layer, all the preparation layers should preferably have a coating weight within the range of. The improvement of the surface of the preparation layer can improve the adhesion of the subsequently applied coating layer (including the layer ore or metal layer). Force, but will not be satisfactory in nature ^ focus on the strength: supply, $ Hai improvement effects include, for example, by fire treatment, ion impact, electron beam treatment, ultraviolet treatment or preferably by corona discharge. The best treatment of corona discharge can be performed in the air and at atmospheric pressure using conventional equipment. The device uses a high frequency, high voltage generator, preferably at a potential of 1 to 100 kilovolts (kv). Kilowatt (kw) of energy output. The effect is achieved by passing the film through a dielectric support roller in a discharged state at a linear speed of better than 500-500 meters per minute. The discharge electrode can be placed away from the surface of the moving film O.iSW O 亳. In a preferred embodiment of the present invention, the composite material further includes a heat-sealable layer. In order to form a laminated layer of a packaging film, the heat-sealable layer may be appropriately coated on the layer, or a layer of On any layer of the composite film according to the present invention. The heat-sealable layer is preferably applied directly or indirectly to the layered ore coating layer of the composite film, and more preferably to the metal layer. The heat-sealable layer contains a polymer material, which should preferably be capable of forming a heat-seal bond to itself or any layer of the composite film, which is to soften the polymer material of the heat-sealable layer by heating, and then apply pressure but Does not soften or melt the matrix layer and combine them. The heat-sealing strength of the heat-sealable layer to itself is suitably greater than 500 g / 25 mm (196 Newton meters. 1), preferably at 800. To 5,000 grams of paper ruler wealth management (-16- 483826 A7 B7 economy Printed by the Central People's Republic of China Bureau for Consumer Cooperation. V. Description of invention (14) / 25 mm (314 to 1960 Nm · m), more preferably 1,000 to 4,000 g / 25¾ m ( 392 to 1568 Nm · ι), and in particular 1500 to 3,000 g / 25¾ m (588 to 1176 Nm · ι). Heat seal strength can be measured by the following steps: at 14 (TC And 103 kPa, the heat-sealable layer was sealed to itself for 1 second, cooled to room temperature, and then measured at a linear tension of 4 · 23 亳 m / s under a linear tension per unit seal width. The strength required to release the sealing film. The heat-sealable layer suitably contains a polyester or polyolefin resin. Suitable polyesters include copolymer resins, especially those derived from one or more dibasic aromatic carboxylic acids (e.g., p-phthalic acid, isophthalic acid, and hexahydrop-phthalic acid) and one or more glycols (for example, ^ Those of ethylene glycol monoethylene glycol, diethylene glycol, and neopentyl glycol). A typical copolyester system that provides seven people with negative heat-sealability is the one that has p-phthalic acid and ethyl isophthalate, which are the most important ones. 50 to 90 mol% of p-phthalic acid phthalate and correspondingly 50 to 10 mol% of mol of isophthalic acid. Polyolefin resin 'is particularly a preferred component of heat-sealable polyethylene. The formulation of the heat-sealable layer can be accomplished by applying a polymeric resin in the form of an aqueous dispersion or a solution in an organic solvent in any suitable conventional coating technique, including, for example, dip coating, bead coating Coating, reverse roll coating and gap coating. Alternatively, the heat-sealable layer may be applied by rubbing. The pre-formed heat-sealable film 'particularly a polyethylene film' is preferably laminated on the composite material according to the present invention by passing through a heated nip roll. The thickness of the heat-sealable layer is preferably up to 100 micrometers, more preferably greater than 10 micrometers, and especially from 35 micrometers to 70 micrometers. Standards are applicable to China (please read the precautions on the back before filling this page). ··· 11 -17 · 1 · 〇JO 厶 u V. Invention Description (printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs can be selected upon request The additional adhesive layer is bonded to the composite material. ㈣: Two containing thermosetting adhesives, such as%, two-component polyurethane adhesive. Alternatively, the adhesive layer can be used as a flex layer. It contains a thermoplastic or rubber U resin substance. The flexible adhesive layer preferably shows less than 20Mpa ^ 杬 modulus (1 /. Secant modulus), preferably within the Mpas 15 Mpa I ', more preferably at From 01 to 10 MPa, especially in the deafness range of MPa soil 0.7 MPa, and especially in the range of 0.25 MPa to 0.45 MPa. The percentage of the flexible adhesive layer is extended to break (Can tb). ^ Jia is also in the range of 300 / 〇 to 100,000%, more preferably in the range of Shizhang%, especially in the range of 800% to 2000%, and especially in the range of 1%. Dimensional% to 1700%. Suitable #flexible adhesive layer polymer resin and synthetic rubber, for example, the main component is M -Polyisoprene. Other preferred polymeric resins include polyterpene resins, isoprene · methylenediene copolymers, styrene-butadiene · butadiene copolymers, and phenethylamidine · isoprene · ene copolymers. Rubber, branched or radial block copolymers of polymers, conjugated diene and ethynyl aromatic hydrocarbons, cyclic monofluorene copolymers, chloroprene polymers containing carboxyl groups, ethylene-vinyl acetate-di Polyester copolymer, polycyanate modified natural and synthetic rubber, and non-thermosetting polyurethane resin. In a preferred embodiment of the present invention, the polymer resin of the adhesive layer is ethylene-butadiene copolymerization. It is preferably a block copolymer. Mole of phenethylated butadiene is more preferably in the range of 0.1 to 10: 1, more preferably in the range of 3: 1, and especially in the range of L2 to 1.6: 1 range. Celene pentisoester benzene 0.5 (Please read the precautions on the back before filling out this page)-Packing. Book-18-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) ) Printed A7 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -------- B7 V. Invention (16) Adhesive layer (The molecular weight of the polymer resin can be changed in a wide range, but the weight average knife I Chevrolet is in the range of 5,000 to 1,000,000, more preferably In the range of 10,000 to 500, GG0, and especially in the range of 2G, to the range of 0.001, the adhesive layer coating composition may include other materials for improving the properties of the produced adhesive layer, for example, Antioxidants, plasticizers and adhesive resins. The polymer of the adhesive layer coating composition may be water-soluble or insoluble

The Jc core composition comprising any water-soluble polymer-containing adhesive layer composition may be applied to the surface of the coating layer in an aqueous dispersion or alternatively, as a solution in an organic solvent. The adhesive layer composition is preferably implemented by any suitable conventional technique, including, for example, dip coating, bead coating, reverse roll coating, or gap coating. In order to dry the solvent in the case of a water-mediated or solvent-applied composition, and to help the adhesive composition bond and form on a continuous and uniform layer, the adhesive layer is preferably heated to 70 °. 0 to 16 °, preferably 80 to 100 ° C and dried. The adhesive layer is preferably applied at a coating weight in the range of 10 to 200 mgdm · 2, more preferably 20 to 150 mgdm ', and especially 50 to 100 mgdm · 2. The thickness of the dried over-adhesive layer is preferably in the range of 丨 micron to 20 micron ', more preferably in the range of 2 to 5 micron, and especially in the range of 5 to 0 micron. The composite material according to the present invention suitably has less than 1, preferably less than 0.5, more preferably less than 0.1, especially less than 0.05, and especially less than 0.01 cm3 / m2. / Day of oxygen permeability. -19- This paper size applies to Chinese National Standard (CNS) A4 specification (21〇χ297) Meal " —- (Please read the notes on the back before filling this page) • Installation · ^ 1 Central Bureau of Standards, Ministry of Economic Affairs Printed by the Consumer Cooperative, Invention Description (According to the present invention, one or more layers in the composite material, that is, the substrate, preparation, coating, metal, adhesive and / or heat-sealable layers, etc.

Any additive used in Ik. Thus, for example, dyes, pigments, voiding agents, lubricants, antioxidants, anti-blocking agents, surface activation agents, slip additives, gloss enhancers, predegradants, UV stabilizers, viscosity modifier # 1 and dispersion Medicaments such as stabilizers may be incorporated in or in the aforementioned layers as appropriate. In particular, the matrix may contain a special filler having a small particle size, such as I, oxidized crushed. If used in a matrix, the filler should desirably be present in a small amount 'which does not exceed 0.5% by weight of the matrix, preferably less than 0.2% by weight. A preferred composite material comprises the following layers in sequence, U) metal / substrate / coated, (b) metal / prepared / substrate / prepared / coated (prepared layers may be the same or different), (C) matrix / prepared / metal / Coated, (d) substrate / coated / prepared / metal. And any of the structures (a) to (d) may have an additional heat-sealable layer, which is adhered to one or both sides of the outer surface, directly or through an intermediate adhesive layer selected as required. The composite material according to the present invention can be used to package any oxygen and / or water sensitive products, such as food and beverages, pharmaceuticals, seeds, photographic films, and the like. The present invention is exemplified by referring to the accompanying drawings. Among them, FIG. 1 is a schematic cross-sectional front view of a composite material, which is not drawn according to the ratio, and includes layers such as a matrix, a metal, and a layered ore coating. (Please read the notes on the back before filling out this page). Binding · Binding · Lf -20 · V. Description of the invention (18 A7 B7 A schematic front view of a similar composite material with an additional preliminary layer between the base and the metal layer. Figure 3 Series and Figure 2 are schematic front views of a similar composite material with additional adhesion and heat sealable Refer to Figure 1 in the illustration. The composite material includes a matrix layer (1), which has a metal layer (2) adhered to a table 2 (3). The layer coating layer (4) is a metal layer (2). ) Is adhered to the far surface (5). The composite material of Fig. 2 further comprises an additional preparation layer (6), which is sandwiched between the matrix layer (1) and the metal layer (2). Fig. 3 < The composite material also contains additional The adhesive layer (7) and the additional heat-sealable layer (9) 'wherein the adhesive layer (7) is adhered to the far surface (8) of the coating layer (4), and the heat-sealable layer (9) is attached to the adhesive layer ( 7) Adhesion to the far surface (1Q). The present invention is further illustrated by referring to the following examples. Example 1 A polypara-urethane film is melt-extruded and cooled down. The drum is poured and stretched to three times its original size in the direction of extrusion. Then, the cooled stretched film is coated with a water preparation layer composition containing the following ingredients: about 3 5/37/12 / 16 mol% of methyl propionate 60 g of methyl methacrylate / butyl propionate / acetophenone / (propionic acid or methacrylic acid) polymer hexamethoxymethylmelamine 12 g (with 'west Meyer 1 ('Cymel, 300 commercial supply) ammonium nitrate 2 g Synperonic NP10 3 g This paper size applies Chinese National Standards (CNS) A4 specifications (21〇297297) m I .fli- ---, «^ n — ^ ϋ ϋϋ If ϋϋ n ϋϋ (Please read the notes on the back before filling out this page), order --------- 483826 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation of A7 _____ B7 V. Description of the invention (19) '~ (Phenyl nonylbenzene g ethoxylated surfactant supplied by Imperial Chemical Industries) Water was added to give a total volume of 2 Liters of coating composition. Coating on only one side of polyethylene terephthalate " g film. Preparing the film through the tenter oven, where, It is dried and stretched laterally to about 3 times its original size. Using a conventional machine, the biaxially stretched pre-film is heated at a temperature set at about 200 ° C. The substrate has a thickness of 23 microns and has The thickness of the preliminary layer of the coating weight of about 0.3 to 0.05 rngdnT2 is from 0.03 to 0.05 micron. The preliminary layer of the film is metallized by the evaporation method to give a coating of about 0.05 micron. The vermiculite suspension system was prepared according to the following method: 100 grams of vermiculite ore (ex-Carolina, USA) at 80 ° C, refluxed with 1 liter of 1 N citric acid for four hours, and then at Leave at room temperature for five days. This results in an exchange of 45 3 milliwatts / 100 grams of surface cations in the ore. The ion-exchanged vermiculite was washed 5 times with deionized water to remove excess salt, and then left overnight to inhale a large amount (ie, 10 times the volume of the insect-to-stone volume) of deionized water. The expanded vermiculite was milled in a Greaves high-shear mixer at 7200 rpm to produce a vermiculite platelet suspension. The small platelet suspension system was then screened by passing through a mechanically agitated filter with a pore size of 106 microns. The biaxially oriented poly (p-ethyl phthalate) matrix / preparation layer / metal layer structure uses a gravure coater to coat the metal layer with a coating composition containing the following ingredients: -22- ♦ (Please read the precautions on the back before filling in this page}. ¾ Clothes · Order Φ .1— I JT · This paper size applies to China National Standard (CNS) A4 (210X297 mm) 483826 A7 B7 Central Bureau of Standards, Ministry of Economic Affairs Printed by the Employees' Cooperative Cooperative 5. Description of the invention (20) Vermiculite (7.5% w / w aqueous dispersion) Cymel 385 (melamine formaldehyde with a molecular weight of 348) p-methylbenzenesulfonic acid (10% Weight / weight aqueous solution) Synperonic NP10 (10% weight / weight nonylphenol ethoxylated aqueous solution, supplied by ICI) Demineralized water was added to 10 liters so that the coated film was at 80 ° C The coating layer was dried and the dry coating weight of the coating layer was about 2 mgdm · 2, and the thickness of the coating layer was about 0.2 micrometers. The gravure coater was used to coat the adhesive layer composition containing the following ingredients on On the far surface of the ore coating: rubber-based resin (Product No. 10-2060 'by Hou Deng (Holden Surface Coatings Ltd, United Kingdom, supply) The adhesive coating film was dried at 90 ° C, and the dry coating weight of the adhesive layer was about 100 mgdm · 2. The thickness of the adhesive layer was about 8 microns. The 50 μm heat-sealable layer of polyethylene film is laminated on the surface of the adhesive layer of the composite material, which is achieved by passing the two films through a clip heated at 70 ° C. The finished composite material (matrix / Preparation / Metal / Coated / Adhesive / Heat-Sealable Layer) The properties of the oxygen barrier are determined by measuring the oxygen permeability using a Mocon 1050 (Modern Controls Inc.) tester -23- 6 liters 375 ml 216 ml 100 ml (Please read the notes on the back before filling in this page}-The size of the paper is bound to the Chinese National Standard (CNS) A4 (210X297 mm) 483826 5. Description of the invention (21 determination. In order to obtain a background reading, the composite material sample is placed in a machine with a flow through the membrane: a nitrogen carrier gas (containing 1% hydrogen). The nitrogen milk on the membrane is replaced by oxygen, and By using a measuring device, the permeation in the carrier gas is measured. The amount of oxygen. Oxygen permeability 4G G1 cm 3 / m 2 / day. The oxygen permeability of the uncoated poly-pure-gold film was also measured, 50.0 cm 3 / m 2 / day. This is an example of the previous example Explain the properties of the composite material according to the present invention. (Please read the notes on the back before filling this page) -HI | _ — ^ ϋr nil 1 ^ 1- ^ ii ^ n-Order

Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs -24- This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

483826 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs I A composite material, which includes a matrix layer, a coating layer containing a layer of ore, and a metal layer 'wherein the matrix layer forms a film polymer material, and the layer of ore contains a film forming 2: The 1-leaf silicate platelets and the metal layer have a thickness ranging from 0.005 to 15 microns. 2. The composite material according to item 1 of the patent application scope, wherein 2: 丨 phyllosilicate contains vermiculite. 3. The composite material according to item i or 2 of the scope of patent application, wherein the coating layer additionally contains a crosslinking agent. 4. The composite material according to item 丨 or 2 of the scope of patent application, in which there is an extra preparative layer. 5. The multi-layer according to item 5 of the scope of the patent application, wherein the preliminary layer enhances the adhesion of the metal layer and contains a polymer of acetic acid or methacrylic acid, which contains up to 35 mol% of at least one free carboxyl group Mission of monomers. 6. The composite material according to item 1 or 2 of the patent application scope, wherein there is an additional heat-sealable layer on the outer surface of at least one side. 7. The composite material according to item 7 of the scope of patent application, wherein the heat-sealable layer comprises polyethylene. 8. The composite material according to item 1 or 2 of the scope of patent application, wherein the matrix layer is a polymer film. 9. · A method for manufacturing a composite material, comprising forming a matrix layer, applying a coating layer containing a layered ore, and applying a metal layer, wherein the matrix layer forms a film polymer material, and the layer ore includes a film forming 2: 1 leaf The small pieces of silicate and the metal layer have a thickness ranging from 0 to 005 to 15 microns. -25- This paper size applies to China National Standards (CNS) Ya 4 threats (210X297 public holiday) (Please read the precautions on the back before filling this page)