CN111703165A - Coating type multilayer composite high-barrier film, preparation method and application thereof - Google Patents

Coating type multilayer composite high-barrier film, preparation method and application thereof Download PDF

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Publication number
CN111703165A
CN111703165A CN202010539831.1A CN202010539831A CN111703165A CN 111703165 A CN111703165 A CN 111703165A CN 202010539831 A CN202010539831 A CN 202010539831A CN 111703165 A CN111703165 A CN 111703165A
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pva
barrier
evoh
multilayer composite
barrier film
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Inventor
东为富
李婷
张胜文
马丕明
杨伟军
汪洋
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Jiangnan University
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Jiangnan University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Physics & Mathematics (AREA)
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  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Laminated Bodies (AREA)

Abstract

A coating type multilayer composite high-barrier film, a preparation method and application thereof are disclosed, the coating type multilayer composite high-barrier film is formed by compounding multilayer polymers through a coating composite forming method, and the structural expression is as follows: A/(adh/C)n/B/(adh/C)n(ii)/adh/A, wherein: n is an integer of 0 or more; a denotes a skin layer, B denotes a barrier layer, adh denotes a tie layer, and C denotes an additional layer. The barrier layer B is a PVA-EVOH composition, and the composition comprises the following raw materials in parts by weight: 40-80 parts of PVA, 15-30 parts of EVOH, 5-30 parts of plasticizer, 0.5-10 parts of heat stabilizer and 0.1-2 parts of metal salt. Skin layer A, C is a thermoplastic high molecular polymer. The film has excellent strength and barrier performance of oxygen resistance and water resistance, and can be used in the field of packaging of various foods, medicines and the like.

Description

Coating type multilayer composite high-barrier film, preparation method and application thereof
Technical Field
The invention relates to the field of material processing, in particular to a coating type multilayer composite high-barrier film and a preparation method thereof.
Background
It is reported that about 40 million tons of food are produced annually in the world, with 30% to 50% uneaten due to losses and waste. The medicine waste is also serious, and the medicine waste value caused by overdue in China is billions of yuan each year. How to reduce the loss and waste of food and medicine is a key concern all over the world. The whole process of researching and analyzing the production, processing, storage and circulation of food and medicine till the hands of consumers shows that the high-barrier composite packaging film can block oxygen and water vapor, prolong the shelf life and reduce the loss and waste of food and medicine, however, the following problems exist in the whole development process of the composite film industry: the price of the commonly used high-barrier composite film is too high; the traditional composite technology has the problems of air pollution, sanitation, safety and the like due to the use of solvent-based adhesives.
The development of the high-barrier composite packaging film industry faces the following problems: (1) EVOH (ethylene-vinyl alcohol) as a barrier layer in a common high-barrier composite packaging film is too high in price (4-5 ten thousand/ton), although PVA is low in price (1 ten thousand/ton) and excellent in barrier property, PVA cannot be subjected to melt processing, is easy to absorb water, and is reduced in barrier property after absorbing water; (2) in the traditional composite film preparation process, a solvent type adhesive is used, the volatilization of the solvent can pollute the atmospheric environment, and related residues can influence the sanitation and safety of food and medicines; (3) it is now stipulated that all plastic packaging needs to be recycled by 2030 years ago, in order to meet the requirement, the material of the composite packaging film is simplified as much as possible, and the proportion of non-single material is not more than 5%, which is a challenge for the high-barrier composite packaging film.
Ethylene/vinyl alcohol copolymer (EVOH) has excellent barrier property, the thermal decomposition temperature is 158-189 ℃, but the cost is high, so that the product cost is high. The patent CN 102602123 a discloses a method for preparing high barrier EVOH material, in which EVOH is used as the barrier layer, but the product cost is high. Polyvinyl alcohol (PVA) is a lower cost, superior polymeric material for barrier properties, and has been approved by the food and drug administration for intimate contact with food. However, at present, a large amount of intramolecular and intermolecular hydrogen bonds are easily formed between adjacent hydroxyl groups of a PVA polymer chain, so that the thermal decomposition temperature (200-250 ℃) is close to the melting point (226 ℃), thermal decomposition is generated during melting, thus the thermoplastic processing into a film is difficult, a PVA film is easy to absorb water, and the barrier property is reduced after absorbing water; meanwhile, the PVA processing is easy to generate gel phenomenon to block the mouth mold. The patent of CN 105777949A discloses a polyvinyl alcohol coating film-forming solution for coating a composite film and a preparation method and application thereof, but the PVA is complex to be treated in the early stage and is not suitable for industrial production. Direct blending is generally not possible due to the large difference in melting points between EVOH resin and PVA resin. The patent of CN107163465A discloses a high-barrier coating material and a preparation method thereof, the material comprises a modified EVOH film, the inner surface of the modified EVOH film is coated with PVA nano TiO2Sol and complex process. Therefore, it is important to develop a low-cost coating type multilayer composite high-barrier film package with simple process and environmental protection.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides a coating type multilayer composite high-barrier thin film and a method for preparing the same. The invention takes PVA-EVOH combined resin as a barrier layer, mixes the PVA-EVOH combined resin with inorganic clay, bonds the PVA-EVOH combined resin with other resin through water-based polyurethane containing clay, and carries out coating forming, the forming process of the prepared high-barrier film is simple, and the following technologies are integrated on the traditional composite process for the first time: the PVA-EVOH/clay coating liquid, the waterborne polyurethane/clay adhesive and the electron beam crosslinking technology are adopted to prepare the high-barrier PVA composite packaging film meeting the single material requirement, organic pollution emission and solvent residue are avoided, and a green, environment-friendly, safe and sanitary composite film preparation technology system is formed; and the barrier layer has low cost, good oxygen and water blocking effect and excellent mechanical property, and can be used in the field of packaging of various foods, medicines and the like.
The technical scheme of the invention is as follows:
a coating type multilayer composite high-barrier film is formed by compounding a plurality of layers of polymers through a coating method, wherein the plurality of layers of polymers comprise a resin layer and a bonding layer, the resin layer comprises a surface layer and a barrier layer, and the structural expression of the coating type multilayer composite high-barrier film is as follows:
A/(adh/C)n/B/(adh/C)n/adh/A
in the formula: n is an integer of 0 or more; a represents a surface layer, B represents a barrier layer, adh represents a bonding layer, C represents an additional layer, the materials of A and C are the same or different, and the materials of the surface layers A on both sides are the same or different; A. the material C is a thermoplastic high-molecular polymer, the material B of the barrier layer is a mixture of a PVA-EVOH high-barrier composition and inorganic clay, and the content of the inorganic clay is 0.5-8% of the weight of the PVA-EVOH high-barrier composition.
The PVA-EVOH high-barrier composition comprises the following raw materials in parts by weight:
Figure BDA0002536605320000031
further, in the above-mentioned case,
Figure BDA0002536605320000032
the processing melting point of the PVA-EVOH high-barrier composition is 160-190 ℃.
The PVA is one group or the combination of more than two of PVA0599, PVA1099 and PVA1799 with the polymerization degree of 500-2400 and the alcoholysis degree of 85-100%.
The ethylene content (mole fraction) in the EVOH is 20-45%, and the vinyl alcohol content (mole fraction) is 55-80%.
The plasticizer is one or more of diglycerol, triglycerol, pentaglycerol, decaglycerol, sorbitol, ethylene glycol, propylene glycol, glycerol, glycidol and polyethylene glycol.
The heat stabilizer is one or more of tannic acid, hydroxytyrosol, ellagic acid, chlorogenic acid, caffeic acid, and 6, 7-dihydroxy-4-methylcoumarin.
The metal salt is one or more of magnesium chloride, calcium chloride, zinc chloride, calcium nitrate, calcium sulfate and aluminum chloride.
The preparation method of the PVA-EVOH high-barrier composition comprises the following specific steps:
(1) respectively weighing the PVA, the plasticizer, the heat stabilizer and the metal salt according to the weight parts, adding the weighed PVA, the plasticizer, the heat stabilizer and the metal salt into a mixer, fully and uniformly mixing to prepare a premix, and plasticizing for a period of time at normal temperature or at elevated temperature;
(2) and finally, mixing the plasticized premix with EVOH, putting the mixture into an extruder, and directly extruding and granulating to obtain the PVA-EVOH high-barrier composition.
The adh bonding layer is a waterborne polyurethane adhesive containing inorganic clay, wherein the content of the inorganic clay is 1-10% of the weight of the waterborne polyurethane.
The inorganic clay is one or the combination of more than two of sodium montmorillonite, modified montmorillonite, kaolin, graphene and laponite. The modified montmorillonite is ion exchange modified by using sulfamate, alkyl quaternary ammonium salt and the like and montmorillonite.
The preparation process of the coating type multilayer composite high-barrier film comprises the following steps:
a. introducing inorganic clay into a PVA-EVOH high-barrier composition solution to prepare a modified PVA-EVOH/clay coating solution;
b. directly coating the modified PVA-EVOH/clay coating liquid on the surface of a surface layer base material film subjected to corona or plasma surface treatment, drying and then performing electron beam crosslinking treatment;
c. coating the water polyurethane adhesive of inorganic clay and another surface resin layer, drying and compounding with the film after electron beam crosslinking treatment.
The coating type multilayer composite high-barrier film can be used in the field of packaging of various foods, medicines and the like.
The beneficial technical effects of the invention are as follows:
(1) the plasticizer, the heat stabilizer and the metal salt used in the barrier layer PVA-EVOH resin are environment-friendly and nontoxic, and can be used in the fields of food, medical barrier packaging materials and the like.
(2) A PVA-EVOH/clay aqueous solution coating liquid is developed, and the problem that high barrier cannot be achieved due to the fact that a coating barrier layer is too thin is solved. The technology introduces clay into PVA water solution to prepare modified coating liquid to improve the barrier property, and the clay is directionally arranged in PVA by controlling the viscosity of the coating liquid and the coating process to improve the gas barrier property and the water resistance.
(3) The modified PVA-EVOH/clay coating liquid is directly coated on the surface of a film of base materials such as PE, PET, PP and the like which are subjected to surface treatment, the water absorption of the film is further reduced through electron beam crosslinking treatment, and finally, a water-based polyurethane adhesive is adopted, so that the film is safe, non-toxic and pollution-free.
(4) The electron beam irradiation crosslinking technology does not need to add any compound, which overcomes the problems of adding a chemical crosslinking agent in the traditional chemical crosslinking technology: no chemical auxiliary agent migration and no solvent volatilization. After radiation crosslinking, the barrier layer and the adjacent layer can generate co-crosslinking, so that the interlayer strength and compatibility of the adjacent layer and the barrier layer are improved, the mechanical property of the composite film is improved, and the composite film is favorable for recycling.
(5) The coating type multilayer composite high-barrier film barrier layer has the advantages of low cost, environment-friendly production process, capability of meeting the requirement of single material, good oxygen and water blocking effects and excellent mechanical properties, and can be used in the field of packaging of various foods, medicines and the like.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Weighing 45 parts by weight of polyvinyl alcohol (Zhongpetrochemical great wall energy chemical industry Ningxia Co., Ltd., trade name 1799), 5 parts by weight of polyvinyl alcohol (Zhongpetrochemical great wall energy chemical industry Ningxia Co., Ltd., trade name 1099), 5 parts by weight of polyvinyl alcohol (Zhongpetrochemical great wall energy chemical industry Ningxia Co., Ltd., trade name 1799), 15 parts by weight of sorbitol, 10 parts by weight of diglycerol, 5 parts by weight of tannic acid and 1 part by weight of calcium chloride, adding the materials into a stirrer, and fully and uniformly mixing to prepare a premix; then plasticizing the premix in an oven at 60 ℃ for 3 hours; finally, the plasticized premix was mixed with 20 parts by weight of an ethylene/vinyl alcohol copolymer (Changchun petrochemical Co., Ltd., No. EV4405, ethylene content 44 mol%) and pelletized in a single screw extruder to obtain a pelletPVA-EVOH Barrier layer resin 1。
Example 2
Weighing 45 parts by weight of polyvinyl alcohol (Zhongpetrochemical great wall energy chemical industry Ningxia Co., Ltd., trade name 1799), 5 parts by weight of polyvinyl alcohol (Zhongpetrochemical great wall energy chemical industry Ningxia Co., Ltd., trade name 1099), 5 parts by weight of polyvinyl alcohol (Zhongpetrochemical great wall energy chemical industry Ningxia Co., Ltd., trade name 1799), 15 parts by weight of sorbitol, 10 parts by weight of diglycerol, 5 parts by weight of tannic acid and 1 part by weight of calcium chloride, adding the materials into a stirrer, and fully and uniformly mixing to prepare a premix; then plasticizing the premix in an oven at 60 ℃ for 3 hours; finally, the plasticized premix was mixed with 20 parts by weight of an ethylene/vinyl alcohol copolymer (Changchun petrochemical Co., Ltd., No. EV3801, ethylene content 38 mol%), and the mixture was pelletized in a single-screw extruder to obtain pelletsPVA-EVOH Barrier layer resin 2。
Example 3 the structural formula of the composite film is expressed as follows:
PE/PVA-EVOH/Clay coating solution 1/adh/PE，
3 percent of sodium-based montmorillonite is introducedPVA-EVOH Barrier layer resin 1Preparation of modifications in solutionPVA-EVOH/Clay coating Liquid 1；
Will be modifiedPVA-EVOH/Clay coating solution 1Directly coating the film on the surface of a PE base material subjected to corona (2000W) surface treatment, drying, and then performing electron beam crosslinking (electron beam energy 800 Kev);
and (3) coating the waterborne polyurethane adhesive containing 7% of modified montmorillonite on one side of the PE substrate on the surface layer, drying and compounding with the film subjected to electron beam crosslinking treatment.
Example 4 the structural formula of the composite film is expressed as follows:
PET/PVA-EVOH/Clay coating solution 2/adh/PP，
Introducing 5% of sodium-based montmorillonitePVA-EVOH Barrier layer resin 2Preparation of modifications in solutionPVA-EVOH/Clay coating Liquid 2；
Will be modifiedPVA-EVOH/Clay coating solution 2Directly coating the film on the surface of a PET substrate subjected to corona (2000W) surface treatment, drying, and then performing electron beam crosslinking (electron beam energy 800Kev) treatment;
and (3) coating the waterborne polyurethane adhesive containing 5% of graphene on one side of the PP substrate on the surface layer, drying and compounding with the film subjected to electron beam crosslinking treatment.
Comparative example 1
Is a PET film.
Comparative example 2
30 parts by weight of ethylene/vinyl alcohol copolymer (Changchun petrochemical company, Inc., No. EV4405, ethylene content 44 mol%), 10 parts by weight of sorbitol and 0.5 part by weight of calcium chloride are added into a stirrer and are fully and uniformly mixed to prepare a premix; then plasticizing the premix in an oven at 60 ℃ for 3 hours; finally, the plasticized premix is put into a single-screw extruder for granulation to prepare the composite materialEVOH barrier layer resin 1。
Comparative example 3
The structural formula of the composite film is expressed as follows:
PE/EVOH/Clay coating liquid 1/adh/PE，
3 percent of sodium-based montmorillonite is introducedEVOH barrier layer resin 1Preparation of modifications in solutionEVOH/Clay coating liquid 1；
Will be modifiedEVOH/Clay coating liquid 1Directly coating the film on the surface of a PE base material subjected to corona (2000W) surface treatment, and then performing electron beam crosslinking (electron beam energy 800Kev) treatment;
and coating a common waterborne polyurethane adhesive on one side of the PE base material on the surface layer, drying and compounding with the film subjected to electron beam crosslinking treatment.
Comparative example 4
30 parts by weight of ethylene/vinyl alcohol copolymer (Changchun petrochemical company, Inc., brand EV3801, ethylene content 38 mol%), 10 parts by weight of sorbitol and 0.5 part by weight of calcium chloride are added into a stirrer and are fully and uniformly mixed to prepare a premix; then plasticizing the premix in an oven at 60 ℃ for 3 hours; finally, the plasticized premix is put into a single-screw extruder for granulation to prepare the composite materialEVOH barrier layer resin 2。
Comparative example 5
The structural formula of the composite film is expressed as follows:
PET/EVOH/Clay coating liquid 2/adh/PP，
Introducing 5% of sodium-based montmorilloniteEVOH barrier layer resin 2Preparation of modifications in solutionEVOH/Clay coating liquid 2；
Will be modifiedEVOH/Clay coating liquid 2Directly coating the film on the surface of a PET (polyethylene terephthalate) base material subjected to corona (2000W) surface treatment, and then performing electron beam crosslinking (electron beam energy 800Kev) treatment;
and coating a common waterborne polyurethane adhesive on one side of the PP substrate of the surface layer, drying and compounding with the film subjected to electron beam crosslinking treatment.
And (3) testing:
the products obtained in the examples and comparative examples of the present invention were hot-pressed or directly cut to prepare standard sample bars, and the tensile property test was carried out according to GB/T13022-1991 standard, the peel strength test was carried out according to GB/T8808-1988 standard, and the heat loss test was adoptedThe thermal decomposition temperature and the melting point of the material are tested by a re-analyzer and a differential scanning calorimeter, and the oxygen transmission capacity is tested according to the GB/T19789-3/(m224h 0.1MPa)), the test results are shown in Table 1.
TABLE 1
Figure BDA0002536605320000091
As can be seen from the data in Table 1, the modification was used in example 3 as compared with comparative example 3PVA-EVOH/Clay coating Liquid 1The composite film which is a barrier layer and uses the water-based polyurethane adhesive containing inorganic clay has better oxygen and water resistance performance and excellent mechanical property; similarly, in example 4, modification was used as compared with comparative examples 1 and 5PVA-EVOH/ Clay coating liquid 2The composite film which is used as a barrier layer and uses the water-based polyurethane adhesive containing inorganic clay has better oxygen and water resistance and excellent mechanical property. The coating type multilayer composite high-barrier film barrier layer has the advantages of low cost, environment-friendly production process, capability of meeting the requirement of single material, good oxygen and water blocking effects and excellent mechanical properties, and can be used in the field of packaging of various foods, medicines and the like.
Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.

Claims (10)

1. A coating type multilayer composite high-barrier film is characterized in that the coating type multilayer composite high-barrier film is formed by compounding a plurality of layers of polymers through a coating method, wherein the plurality of layers of polymers comprise a resin layer and a bonding layer, the resin layer comprises a surface layer and a barrier layer, and the structural expression of the coating type multilayer composite high-barrier film is as follows:
A/(adh/C)n/B/(adh/C)n/adh/A
in the formula: n is an integer of 0 or more; a represents a surface layer, B represents a barrier layer, adh represents a bonding layer, C represents an additional layer, the materials of A and C are the same or different, and the materials of the surface layers A on both sides are the same or different; A. the material C is a thermoplastic high-molecular polymer, the material B of the barrier layer is a mixture of a PVA-EVOH high-barrier composition and inorganic clay, and the content of the inorganic clay is 0.5-8% of the weight of the PVA-EVOH high-barrier composition.
2. The coating type multilayer composite high-barrier film as claimed in claim 1, wherein the PVA-EVOH high-barrier composition comprises the following raw materials in parts by weight:
Figure FDA0002536605310000011
3. the coating type multilayer composite high-barrier film as claimed in claim 2, wherein the PVA-EVOH high-barrier composition comprises the following raw materials in parts by weight: PVA55-75 parts
Figure FDA0002536605310000012
4. A coated multilayer composite high barrier film according to claim 2 or 3, wherein the PVA-EVOH high barrier composition is prepared by the following steps:
(1) respectively weighing the PVA, the plasticizer, the heat stabilizer and the metal salt according to the weight parts, adding the weighed PVA, the plasticizer, the heat stabilizer and the metal salt into a mixer, fully and uniformly mixing to prepare a premix, and plasticizing for a period of time at normal temperature or at elevated temperature;
(2) and finally, mixing the plasticized premix with EVOH, putting the mixture into an extruder, and directly extruding and granulating to obtain the PVA-EVOH high-barrier composition.
5. The coating type multilayer composite high-barrier film as claimed in claim 1, 2 or 3, wherein the adh bonding layer is an aqueous polyurethane adhesive containing inorganic clay, wherein the content of the inorganic clay is 1-10% of the weight of the aqueous polyurethane; the thermoplastic high molecular polymer is one or the combination of more than two of PE, PP, PET, PVC, PS, PC, ABS, PA-6, PA-66 and PU.
6. The coated multilayer composite high-barrier film as claimed in claim 4, wherein the adh bonding layer is an aqueous polyurethane adhesive containing inorganic clay, wherein the content of the inorganic clay is 1-10% of the weight of the aqueous polyurethane; the thermoplastic high molecular polymer is one or the combination of more than two of PE, PP, PET, PVC, PS, PC, ABS, PA-6, PA-66 and PU.
7. The coated multilayer composite high-barrier film as claimed in claim 5, wherein the inorganic clay is one or more of sodium montmorillonite, modified montmorillonite, kaolin, graphene and laponite.
8. The coated multilayer composite high-barrier film as claimed in claim 6, wherein the inorganic clay is one or more of sodium montmorillonite, modified montmorillonite, kaolin, graphene and laponite.
9. A preparation method of a coating type multilayer composite high-barrier film is characterized in that the preparation process comprises the following steps:
a. introducing inorganic clay into a PVA-EVOH high-barrier composition solution to prepare a modified PVA-EVOH/clay coating solution;
b. directly coating the modified PVA-EVOH/clay coating liquid on the surface of a surface layer subjected to corona or plasma surface treatment, drying and then performing electron beam crosslinking treatment;
c. coating the water polyurethane adhesive of inorganic clay and another surface resin layer, drying and compounding with the film after electron beam crosslinking treatment.
10. The application of the coating type multilayer composite high-barrier film as claimed in any one of claims 1 to 8, wherein the film is used in the field of packaging of various foods and medicines.
CN202010539831.1A 2020-06-12 2020-06-12 Coating type multilayer composite high-barrier film, preparation method and application thereof Pending CN111703165A (en)

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CN112280087A (en) * 2020-09-30 2021-01-29 浙江大学衢州研究院 High-gas-barrier-property oriented composite film
CN113308013A (en) * 2021-06-10 2021-08-27 广东美士达药包材料股份有限公司 High-barrier composite film for packaging sensitive medicinal materials and preparation method thereof
CN114368208A (en) * 2022-01-28 2022-04-19 佛山市南海利达印刷包装有限公司 Matte film and production method thereof
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CN112280087A (en) * 2020-09-30 2021-01-29 浙江大学衢州研究院 High-gas-barrier-property oriented composite film
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WO2024142049A1 (en) * 2022-12-27 2024-07-04 Solutum Technologies Ltd. Biodegradable and barrier pvoh-based materials and products made therefrom

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