CN114193879B - High-barrier aluminized composite film and preparation method thereof - Google Patents

High-barrier aluminized composite film and preparation method thereof Download PDF

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CN114193879B
CN114193879B CN202111407172.7A CN202111407172A CN114193879B CN 114193879 B CN114193879 B CN 114193879B CN 202111407172 A CN202111407172 A CN 202111407172A CN 114193879 B CN114193879 B CN 114193879B
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aluminized
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CN114193879A (en
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黄义军
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Chengdu Zhongheng Printing Co ltd
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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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Abstract

The application relates to the field of packaging materials, and particularly discloses a high-barrier aluminum-plated composite film and a preparation method thereof. The high-barrier aluminized composite film comprises a BOPP printed film, an aluminized PET film and a PE film, wherein the PE film comprises an outer layer, a middle layer and an inner layer; the aluminized surface of the aluminized PET film is compounded with the outer layer of the PE film through a second adhesive; the second adhesive is a solvent-free polyurethane adhesive; the outer layer raw materials of the PE film comprise thermoplastic elastomer, POE, ethylene-methyl methacrylate copolymerization and poly alpha-methyl styrene resin; the middle layer raw material comprises copolymer PP, LDPE, LLDPE, m-PE, ethylene-methyl acrylate copolymer and slipping agent; the inner layer raw material comprises LDPE and m-PE. The high-barrier aluminized composite film can be used for food packaging, and has the advantages of good barrier property, high mechanical strength, difficult stripping and layering and good heat sealing performance.

Description

High-barrier aluminized composite film and preparation method thereof
Technical Field
The application relates to the field of packaging materials, in particular to a high-barrier aluminized composite film and a preparation method thereof.
Background
The aluminizer is a film formed by depositing aluminum vapor on a base film in a vacuum state; the more commonly used aluminizers at present mainly comprise a polyester aluminizer (VMPET) and a CPP aluminizer (VMCPP). Since aluminized films have good barrier properties and metallic luster, they have been rapidly developed in the field of flexible packaging in recent years. In order to obtain better packaging heat sealing performance, barrier performance and mechanical strength, the aluminized film can be compounded with other films to prepare an aluminized composite film.
In the three-layer structure aluminized composite film, a BOPP/VMPET/PE composite film is commonly used, and the preparation method generally comprises the following steps: printing ink on one side of the BOPP film to form a BOPP printing film; then coating an adhesive on the printing surface of the BOPP printing film to form a first adhesive layer, and then coating an aluminized film on the BOPP printing film so that the aluminized surface of the aluminized film and the printing surface of the BOPP printing film are respectively positioned on two sides of the first adhesive layer; finally, coating an adhesive on one side of the aluminized film far away from the printing surface to form a second adhesive layer, and coating the PE film on the second adhesive layer; the layer structure of the composite film is BOPP layer/printing layer/first adhesive layer/aluminized layer/PET layer/second adhesive layer/PE layer.
The traditional adhesive is an adhesive material of polyurethane adhesive, and is used after being mixed according to a certain proportion by taking organic solvents such as ethyl ester and the like as diluents; in recent years, due to the enhancement of environmental awareness, the aqueous adhesive slowly replaces the organic solvent type adhesive. After the BOPP printing film is coated with the aqueous adhesive, the BOPP printing film is heated by an oven to remove excessive moisture, and then the aluminizer is coated on the adhesive layer by a pressure roller. However, compared with an organic solvent type adhesive, the aqueous adhesive has the problems of slow water volatilization and low peeling strength of an aluminized film, in actual production, a drying process needs to be strictly controlled, a plurality of drying processes are not thorough, an aluminized surface can be contacted with water molecules, an aluminized layer transferring phenomenon occurs, namely, most of the aluminized layer is transferred to other films when the composite film is peeled from the layers, so that peeling strength is reduced, barrier performance is reduced, and quality of a product is affected.
In order to reduce the transfer of the aluminized layer caused by the penetration of the solvent-based adhesive into the aluminized layer, a solvent-free polyurethane adhesive can be used to alleviate the transfer of the aluminized layer caused by the diffusion of the adhesive. However, except for the influence of the adhesive, the composite film is formed by compositing a BOPP film, a PET film and a PE film, and the molecular chain structures and the performances of the films have larger differences, so that internal stress is generated between the layers due to inconsistent stretching rates, and the transfer of an aluminized layer is aggravated. Therefore, how to reduce the transfer of the aluminized layer, improve the interlayer peeling strength of the composite film and improve the barrier property of the composite film is a problem to be solved.
Disclosure of Invention
In order to improve the interlayer peeling strength of the composite film and the barrier property of the composite film, the application provides a high-barrier aluminized composite film and a preparation method thereof.
In a first aspect, the present application provides a high-barrier aluminized composite film, which adopts the following technical scheme:
the high-barrier aluminized composite film comprises a BOPP printed film, an aluminized PET film and a PE film, wherein the PE film comprises an outer layer, a middle layer and an inner layer;
the printing surface of the BOPP printing film and one side of the aluminized PET film, which is far away from the aluminized surface of the aluminized PET film, are compounded through a first adhesive;
the aluminized surface of the aluminized PET film is compounded with the outer layer of the PE film through a second adhesive;
the second adhesive is a solvent-free polyurethane adhesive;
the PE film comprises, by weight, 40-60 parts of a thermoplastic elastomer, 25-35 parts of POE, 10-20 parts of an ethylene-methyl methacrylate copolymer and 4-6 parts of poly alpha-methylstyrene resin;
the middle layer raw material comprises 50-70 parts of copolymerized PP, 10-15 parts of LDPE, 10-15 parts of LLDPE, 5-10 parts of m-PE, 5-10 parts of ethylene-methyl acrylate copolymer and 0.5-3 parts of slipping agent;
the inner layer raw material comprises 80-90 parts of LDPE and 10-20 parts of m-PE.
Through adopting above-mentioned technical scheme, this application changes the aluminizing face of traditional aluminizing PET membrane and printing membrane complex into aluminizing face and PE membrane complex, will plate simultaneously between aluminizing face and the PE membrane and compound through solvent-free polyurethane adhesive, can reduce the solvent of adhesive and to the transfer phenomenon of aluminizing the layer that the infiltration of aluminizing the layer led to. Meanwhile, as the ink layer of the BOPP film is in direct contact with the PET base film, the phenomenon that the ink is transferred to the aluminized layer can be reduced, and the peeling strength between the BOPP printed film and the aluminized PET film is improved. At this time, the type of the first adhesive between the BOPP printing film and the aluminized PET film is not particularly required, and the first adhesive can be a solvent type adhesive or a solvent-free adhesive; and the BOPP printing film and the aluminized PET film are compounded, and after being heated and stretched, the internal stress of the BOPP printing film and the aluminized PET film can be balanced within a certain time, so that the interlayer layering phenomenon between the BOPP printing film and the aluminized PET film is reduced.
Researches show that the heat shrinkage of the PE film after compounding is a main cause for transferring an aluminized layer, so that the PE film is modified, the formula of each layer is adjusted by utilizing a three-layer coextrusion structure of the PE film, the inner layer of the PE film provides good heat sealing strength, the middle layer of the PE film provides certain rigidity and barrier property, the corrosiveness of package contents on the aluminized layer can be reduced, the heat shrinkage of the PE film can be restrained, and the internal stress difference between the PE film and a BOPP printing film/aluminized PET film is reduced; the elasticity of the outer layer is matched with the solvent-free polyurethane adhesive, so that partial internal stress generated by the PE film can be absorbed, and the transfer of the aluminized layer is relieved, thereby reducing the transfer phenomenon of the aluminized layer caused by the internal stress generated by inconsistent stretching ratios of all layers and improving the capability of the composite film for blocking oxygen and water vapor.
For the adhesive, the molecular weight is smaller, the molecular activity is strong, the permeability and the destructiveness to an aluminized layer are stronger, and the molecular weight is larger, the molecular weight distribution is uneven in the production process, and the aluminized layer is damaged. In order to reduce the influence of the adhesive on the aluminized layer, the outer layer of the PE film has certain self-adhesion, so that the peeling strength between the PE film and the aluminized PET film can be improved, the dosage of the second adhesive can be reduced, the curing time can be shortened, and the damage of the adhesive to the aluminized layer can be reduced.
The thermoplastic elastomer can be styrene-butadiene-styrene block copolymer (SBS) and styrene-isoprene-styrene block copolymer (SIS), SBS and SIS have good elasticity and bonding property, and after the SBS and SIS are mixed with a certain amount of ethylene-methyl methacrylate copolymer, POE and poly alpha-methyl styrene resin, the mixture is used as an outer layer of the PE film, so that good flexibility and bonding strength can be provided for the outer layer of the PE film, thereby relieving the thermal shrinkage of the PE film, reducing the internal stress of the PE film, reducing the transfer of an aluminized layer, improving the interlayer bonding force and improving the barrier property of the composite film.
Preferably, the thickness ratio of the outer layer, the middle layer and the inner layer of the PE film is 2-3:4-6:2-3.
By adopting the technical scheme, the thickness ratio of the outer layer, the middle layer and the inner layer of the PE film is controlled to be 2-3:4-6:2-3, the middle layer is taken as a framework material, and the rigidity of the PE film can be utilized to limit the thermal retraction of the PE film; and in this ratio, each layer has better compatibility, and interlayer separation phenomenon can be reduced.
Preferably, the density of the LDPE of the middle layer is from 0.920 to 0.925g/cm 3 The melt index is 1.8-2.2g/10min; LLDPE has a density of 0.925 to 0.930g/cm 3 The melt index is 1.5-2.0g/10min; the density of m-PE is g/cm 3 The melt index is g/10min.
Preferably, the LDPE of the inner layer has a density of 0.920 to 0.930g/cm 3 The melt index is 1.5-2.0g/10min; the density of m-PE is 0.910-0.915g/cm 3 The melt index is 0.5-1.0g/10min.
Preferably, the PE film is prepared by the following method:
mixing: respectively mixing the outer layer raw material, the middle layer raw material and the inner layer raw material, and then putting the mixture into a three-layer coextrusion casting machine;
melting: heating the three-layer coextrusion casting machine in sections, wherein the temperature of the first section is 160-170 ℃, the temperature of the second section is 180-200 ℃, the temperature of the third section is 210-230 ℃, and the temperature of the die head is 220-230 ℃; the raw materials in the molten state of each layer are extruded through a die lip after being converged by a die head; casting: the temperature of the casting roll was set to 25-30℃and the extrudate was quenched to form a PE film under vacuum pressure of 0.6-1 mbar.
Through adopting above-mentioned technical scheme, adopt multilayer coextrusion casting processing's mode to prepare PE membrane can have good heat-seal nature simultaneously, stiffness and self-adhesion concurrently, and the film has better homogeneity. The adoption of the sectional heating mode can enable the raw materials such as PP and the like to be plasticized more fully, and is beneficial to improving the mechanical strength of the film.
Preferably, the thickness of the BOPP printing film is 15-20 mu m, the thickness of the aluminized PET is 10-15 mu m, and the thickness of the PE film is 65-85 mu m.
By adopting the technical scheme, the composite film is formed by compounding a plurality of layers of films, so that the composite film has the advantages of all layers and has better comprehensive performance; the thickness of the PE film is thicker than that of BOPP printed film and aluminized PET, better heat seal strength and mechanical strength can be provided, transfer of an aluminized layer can be reduced, and barrier performance of the composite film is effectively improved.
Preferably, the second adhesive has a sizing amount of 1-1.5g/m 2 。
By adopting the technical scheme, the sizing amount of the traditional adhesive is generally 2.8-3.5g/m 2 The usage amount of the adhesive is far smaller than that of the traditional adhesive, and the influence of the adhesive on the aluminized layer can be reduced as much as possible.
In a second aspect, the present application provides a method for preparing a high-barrier aluminized composite film, which adopts the following technical scheme: the preparation method of the high-barrier aluminized composite film comprises the following steps:
s1, coating a first adhesive on a printing surface of a BOPP printing film, coating an aluminized PET film, enabling one side of the PET film far away from the aluminized surface to be in contact with the first adhesive, and curing to obtain the BOPP printing film/aluminized PET film;
s2, coating a second adhesive on the aluminum plating surface of the BOPP printing film/the aluminum plating PET film, coating a PE film, enabling the outer layer of the PE film to be in contact with the second adhesive, and curing to obtain the BOPP printing film/the aluminum plating PET film/the PE film.
Preferably, the composite pressure of the PE film and the BOPP printing film/aluminized PET film in the S2 is 0.1-0.3MPa.
By adopting the technical scheme, the composite film is compounded under the pressure of 0.1-0.3MPa, so that the damage and the damage of the pressure to the film can be reduced, the interlayer binding force between the films can be improved, and the layering phenomenon of the composite film can be reduced.
Preferably, the curing temperature in the step S2 is 45-55 ℃ and the curing time is 16-30h.
By adopting the technical scheme, the curing is carried out at the temperature of 45-55 ℃, so that the composite fastness can be improved, and the interlayer separation phenomenon can be reduced.
In summary, the present application has the following beneficial effects:
the aluminized surface of the aluminized PET film and the outer layer of the PE film in the composite film are compounded through the solvent-free polyurethane adhesive, so that the penetration of a solvent to the aluminized layer can be reduced, and the mutual transfer of printing ink and the aluminized layer can be avoided; in addition, the PE film obtained by adjusting the raw materials of the outer layer, the middle layer and the inner layer and the interlayer proportion of the PE film has good heat sealing performance and mechanical strength, and the heat retraction of the PE film can be reduced through the rigidity and the stiffness of the middle layer, so that the transfer of an aluminized layer is limited; internal stress can be absorbed through the elasticity of the outer layer, and the transfer of the aluminized layer is relieved; the outer layer also has certain self-adhesion, so that the dosage of the second adhesive can be reduced, and the negative influence of the adhesive on the aluminized layer is reduced; but also can improve the interlayer peeling strength, thereby further improving the barrier property, the mechanical strength and the heat sealing performance of the composite film.
Drawings
FIG. 1 is a schematic cross-sectional view of a layer structure of embodiment 1 of the present application;
fig. 2 is a schematic cross-sectional view of the layer structure of comparative example 1 of the present application.
In the figure, 1, BOPP printing film layer; 11. a BOPP base film layer; 12. printing a layer; 2. plating an aluminum PET film layer; 21. a PET base film layer; 22. plating an aluminum layer; 3. a PE film layer; 4. a first adhesive layer; 5. and a second adhesive layer.
Detailed Description
The present application is described in further detail below with reference to examples.
Preparation example of PE film
The raw materials in the preparation examples are commercially available, except for the specific descriptions. Wherein, the outer layer raw materials: the thermoplastic elastomer is one of styrene-butadiene-styrene segmented copolymer, styrene-isoprene-styrene segmented copolymer or their mixture; the following preparation examples all select styrene-butadiene-styrene block copolymers (SBS); POE is available from dow chemical under model 8411; ethylene-methyl methacrylate copolymer (EMMA) was purchased from japanese alumni chemistry under the model SWA340; poly alpha-methylstyrene resin (PaMS) was purchased from Shandong Kepler Biotechnology Inc. under the model number AMS120. Middle layer raw material: PP was obtained from Nordic chemical under the model BC918CF at a density of 0.905g/cm 3 LDPE with a melt index (230 ℃/2.16 kg) of 3g/10min was purchased from Zhonghai Shell, model 2426H, density of 0.925g/cm 3 A melt index (190 ℃ C./2.16 kg) of 1.9g/10min; LLDPE was purchased from Presman, japanese model SP2520, density 0.925g/cm 3 The melt index is 1.9g/10min; m-PE purchaseFrom Exxon Mobil, model Energy cell 3505HH, density of 0.935g/cm 3 Melt index of 0.5g/10min; ethylene methyl acrylate copolymer (EMA) was purchased from dupont, usa under the model 1218AC; the slipping agent is erucamide. The LDPE of the inner layer was purchased from Zhonghai Shell, model 2426H, density 0.925g/cm 3 The melt index is 1.9g/10min; m-PE was purchased from Exxon Mobil under the model ExcheDe XP8784ML at a density of 0.914g/cm 3 The melt index was 0.8g/10min.
PREPARATION EXAMPLE 1 PREPARATION EXAMPLE 7
The preparation examples 1 to 7 differ in the raw materials, and the raw materials are shown in Table 1, and the following description will be given by taking the preparation example 1 as an example.
The preparation method of the PE film provided in preparation example 1 comprises the following steps:
mixing: respectively mixing the outer layer raw material, the middle layer raw material and the inner layer raw material, and then putting the mixture into a three-layer coextrusion casting machine;
melting: heating the three-layer coextrusion casting machine in sections, wherein the first temperature is 165 ℃, the second temperature is 190 ℃, the third temperature is 220 ℃ and the die head temperature is 225 ℃; the raw materials in the molten state of each layer are extruded through a die lip after being converged by a die head;
casting: the temperature of the casting roll was set to 25℃and the extrudate was quenched to form at a vacuum pressure of 0.8mbar to give PE films having outer, middle and inner layers in a thickness ratio of 3:4:3.
Table 1 raw materials used for PE film in preparation example (unit: kg)
Figure BDA0003372685650000051
Figure BDA0003372685650000061
Preparation example 8
The difference between this preparation example and preparation example 1 is that the thickness ratio of the outer layer, the middle layer and the inner layer of the PE film is 2:6:2.
Preparation example 9
The difference between this preparation example and preparation example 1 is that the thickness ratio of the outer layer, the middle layer and the inner layer of the PE film is 1:6:3.
Preparation example 10
The difference between this preparation example and preparation example 1 is that the thickness ratio of the outer layer, the middle layer and the inner layer of the PE film is 3:6:1.
PREPARATION EXAMPLE 11
The difference between this preparation example and preparation example 1 is that the thickness ratio of the outer layer, the middle layer and the inner layer of the PE film is 4:3:3.
Preparation example 12
The difference between this preparation and preparation 1 is that the outer layer material of the PE film consists of 80kg of LDPE, which is purchased from Zhonghai Shell, model 2426H, and 20kg of LLDPE, the density of which is 0.925g/cm 3 The melt index is 1.9g/10min; LLDPE was purchased from Presman, japanese model SP2520, density 0.925g/cm 3 The melt index was 1.9g/10min.
Examples
The starting materials in the examples are commercially available, except for the specific descriptions. The first adhesive and the second adhesive are prepared from solvent-free polyurethane, and are purchased from Hangao, germany and are UK 2073/2173, and the polyol and the isocyanate are mixed according to the volume ratio of 2:1. The BOPP printing film is prepared by selecting a common BOPP film, carrying out corona treatment on one side of the BOPP film, and printing ink according to the traditional process to form a printing layer. The aluminized PET film is a common PET film, and aluminized on one side of the PET film by adopting a vacuum aluminizing technology to form an aluminized layer with the thickness of 0.2 mu m, so as to obtain the aluminized PET film.
Example 1: referring to fig. 1, a high-barrier aluminized composite film comprises a BOPP printed film layer 1, an aluminized PET film layer 2 and a PE film layer 3; the BOPP printing film layer 1 comprises a BOPP base film layer 11 and a printing layer 12, the aluminized PET film layer 2 comprises a PET base film layer 21 and an aluminized layer 22, and a first bonding layer 4 is arranged between the printing layer 12 and the PET base film layer 21; a second adhesive layer 5 is arranged between the aluminized layer 22 and the outer layer of the PE film layer 3.
The high-barrier aluminized composite film is prepared by the following method:
s1, coating a first adhesive on a printing surface of a BOPP printing film, and coating an aluminized PET film to enable one side of the PET film far away from the aluminized surface to be in contact with the first adhesive, wherein the composite pressure is 0.2MPa; then curing for 24 hours at 50 ℃ to obtain a BOPP printing film/aluminized PET film;
s2, coating a second adhesive on the aluminum plating surface of the BOPP printing film/the aluminum plating PET film, coating a PE film, enabling the outer layer of the PE film to be in contact with the second adhesive under the composite pressure of 0.2MPa, and curing for 24 hours at the temperature of 50 ℃ to obtain the BOPP printing film/the aluminum plating PET film/the PE film.
The BOPP printing film of the high-barrier aluminized composite film has the thickness of 15 mu m, the aluminized PET film has the thickness of 10 mu m, the PE film has the thickness of 65 mu m, and the PE film is prepared by the preparation example 1.
Example 2
This example differs from example 1 in that a PE film was prepared from preparation example 2.
Example 3
This example differs from example 1 in that a PE film was prepared from preparation example 3.
Example 4
This example differs from example 1 in that a PE film was prepared from preparation example 8.
Example 5
This example differs from example 1 in that a PE film was prepared from preparation example 9.
Example 6
This example differs from example 1 in that a PE film was produced from production example 10.
Example 7
This example differs from example 1 in that a PE film was prepared from preparation example 11.
Example 8
This example differs from example 1 in that the PE film has a thickness of 85 μm.
Example 9
This example differs from example 1 in that the PE film thickness is 55 μm.
Comparative example
Comparative example 1
Referring to fig. 2, an aluminized composite film comprises a BOPP printed film layer 1, an aluminized PET film layer 2 and a PE film layer 3; the BOPP printing film layer 1 comprises a BOPP base film layer 11 and a printing layer 12, the aluminized PET film layer 2 comprises a PET base film layer 21 and an aluminized layer 22, and a first bonding layer 4 is arranged between the printing layer 12 and the aluminized layer 22; a second adhesive layer 5 is arranged between the PET base film layer 21 and the outer layer of the PE film layer 3.
An aluminized composite film is prepared by the following steps:
s1, coating a first adhesive on a printing surface of a BOPP printing film, and covering an aluminized PET film to enable the aluminized surface of the PET film to be in contact with the first adhesive, wherein the composite pressure is 0.2MPa; then curing for 24 hours at 50 ℃ to obtain a BOPP printing film/aluminized PET film;
s2, coating a second adhesive on one side of the BOPP printing film/aluminized PET film far away from the aluminized surface, coating a PE film, enabling the outer layer of the PE film to be in contact with the second adhesive under the composite pressure of 0.2MPa, and curing for 24 hours at the temperature of 50 ℃ to obtain the BOPP printing film/aluminized PET film/PE film.
The BOPP printing film of the high-barrier aluminized composite film has the thickness of 15 mu m, the aluminized PET film has the thickness of 10 mu m, the PE film has the thickness of 65 mu m, and the PE film is prepared by the preparation example 1.
Comparative example 2
This comparative example differs from example 1 in that a PE film was produced from production example 12.
Comparative example 3
This comparative example differs from example 1 in that a PE film was produced from production example 4.
Comparative example 4
This comparative example differs from example 1 in that a PE film was produced from production example 5.
Comparative example 5
This comparative example differs from example 1 in that a PE film was produced from production example 6.
Comparative example 6
This comparative example differs from example 1 in that a PE film was prepared from preparation example 7.
Performance test
Composite films were prepared in examples 1 to 9 and comparative examples 1 to 6, and their properties were examined according to T/BZ1331-2020 "multilayer composite Plastic film, bag", and the test results are shown in tables 2, 3 and 4.
Table 2 table of performance tests of composite films of example 1 and comparative examples 1-2
Figure BDA0003372685650000081
Figure BDA0003372685650000091
The composite film of comparative example 1 is a composite film in which an aluminum-plated surface of an aluminum-plated PET film is compounded with an outer layer of a PE film; from the data of table 2, in combination with example 1 and comparative example 1, it can be seen that the interlayer peel strength of the composite film of comparative example 1 is lower than that of example 1, indicating that the composite fastness of the composite film is significantly changed when the interlayer structure of the composite film is changed.
The PE film of the composite film of comparative example 2 was prepared from preparation example 8 of PE film whose outer layer raw material consisted of only LDPE and LLDPE. According to the data in Table 2, in combination with example 1 and comparative example 2, it can be seen that the PE film prepared by the preparation method of the present application can significantly improve the stretch breaking force, interlayer peeling force and impact resistance of the composite film, compared to the conventional PE film.
TABLE 3 Performance test Table of composite films of examples 1-3 and comparative examples 3-6
Figure BDA0003372685650000092
Figure BDA0003372685650000101
Examples 1 to 3 and comparative examples 3 to 6 differ in the amount of raw materials for PE films. Among them, comparative examples 3, 4 are different from the PE film of example 1 in the amount of the outer layer raw material; from the data in Table 3, it can be seen that the composite film has better interlayer peeling force and water-oxygen barrier property when the outer layer raw material SBS of PE film is 40-60 parts, POE is 25-35 parts, EMMA is 10-20 parts in combination with example 1 and comparative examples 3-4.
Comparative example 5, comparative example 6 differ from the PE film of example 1 in the amount of the intermediate layer raw material used; according to the data in Table 3, when the intermediate layer is prepared from 50-70 parts of copolymerized PP, 10-15 parts of LDPE, 10-15 parts of LLDPE, 5-10 parts of m-PE and 5-10 parts of ethylene-methyl acrylate copolymer in combination with the embodiment 1 and the comparative examples 5-6, the composite film has better mechanical strength, interlayer stripping and water-oxygen barrier property.
Table 4 performance test table for composite films of examples 1, 5-9
Figure BDA0003372685650000102
Examples 1 and 5 to 7 differ in that the interlayer thickness ratio of the PE film is different; according to the data in Table 4, when the interlayer ratio of the PE film is different in combination with examples 1 and 5-7, the mechanical strength, heat sealing strength, interlayer peeling force, impact strength and water-oxygen barrier property of the composite film are all changed, and when the thickness ratio of the outer layer, the middle layer and the inner layer of the PE film is 2-3:3-6:2-3, the PE film has better overall performance.
Examples 1 and 8 to 9 differ in the thickness of the PE film; from the data in Table 4, in combination with examples 1 and examples 8 to 9, it can be seen that the tensile force, impact strength and water-oxygen barrier property of the composite film are significantly enhanced, but the interlayer peeling force is not significantly changed as the thickness of the composite film is increased. Therefore, the PE film has better comprehensive strength when the thickness of the PE film is 65-85 mu m from the economic cost.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (10)

1. The high-barrier aluminized composite film is characterized by comprising a BOPP printed film, an aluminized PET film and a PE film, wherein the PE film comprises an outer layer, a middle layer and an inner layer;
the printing surface of the BOPP printing film and one side of the aluminized PET film, which is far away from the aluminized surface of the aluminized PET film, are compounded through a first adhesive;
the aluminized surface of the aluminized PET film is compounded with the outer layer of the PE film through a second adhesive;
the second adhesive is a solvent-free polyurethane adhesive;
the PE film comprises, by weight, 40-60 parts of a thermoplastic elastomer, 25-35 parts of POE, 10-20 parts of an ethylene-methyl methacrylate copolymer and 4-6 parts of poly alpha-methyl styrene resin, wherein the thermoplastic elastomer is one of a styrene-butadiene-styrene block copolymer and a styrene-isoprene-styrene block copolymer or a mixture thereof;
the middle layer raw material comprises 50-70 parts of copolymerized PP, 10-15 parts of LDPE, 10-15 parts of LLDPE, 5-10 parts of m-PE, 5-10 parts of ethylene-methyl acrylate copolymer and 0.5-3 parts of slipping agent;
the inner layer raw material comprises 80-90 parts of LDPE and 10-20 parts of m-PE.
2. The high-barrier aluminum-plated composite film according to claim 1, wherein the thickness ratio of the outer layer, the middle layer and the inner layer of the PE film is 2-3:4-6:2-3.
3. A high barrier aluminized composite film according to claim 1, wherein the density of the LDPE in the middle layer is 0.920-0.925g/cm 3 The melt index is 1.8-2.2g/10min; LLDPE has a density of 0.925 to 0.930g/cm 3 The melt index is 1.5-2.0g/10min; the density of the m-PE is 0.935g/cm 3 The melt index was 0.5g/10min.
4. A high barrier aluminized composite film according to claim 1, wherein the density of the LDPE of the inner layer is 0.920-0.930g/cm 3 The melt index is 1.5-2.0g/10min; the density of m-PE is 0.910-0.915g/cm 3 The melt index is 0.5-1.0g/10min.
5. The high-barrier aluminum-plated composite film according to claim 1, wherein the PE film is prepared by the following method:
mixing: respectively mixing the outer layer raw material, the middle layer raw material and the inner layer raw material, and then putting the mixture into a three-layer coextrusion casting machine;
melting: heating the three-layer coextrusion casting machine in sections, wherein the temperature of the first section is 160-170 ℃, the temperature of the second section is 180-200 ℃, the temperature of the third section is 210-230 ℃, and the temperature of the die head is 220-230 ℃; the raw materials in the molten state of each layer are extruded through a die lip after being converged by a die head;
casting: the temperature of the casting roll was set to 25-30℃and the extrudate was quenched to form a PE film under vacuum pressure of 0.6-1 mbar.
6. The high-barrier aluminum-plated composite film according to claim 1, wherein the BOPP printed film has a thickness of 15-20 μm, the aluminum-plated PET film has a thickness of 10-15 μm, and the PE film has a thickness of 65-85 μm.
7. The high-barrier aluminum-plated composite film according to claim 1, wherein the second adhesive has a sizing amount of 1-1.5g/m 2 。
8. The method for preparing the high-barrier aluminum-plated composite film according to any one of claims 1 to 7, which is characterized by comprising the following steps:
s1, coating a first adhesive on a printing surface of a BOPP printing film, coating an aluminized PET film, enabling one side of the PET film far away from the aluminized surface to be in contact with the first adhesive, and curing to obtain the BOPP printing film/aluminized PET film;
s2, coating a second adhesive on the aluminum plating surface of the BOPP printing film/the aluminum plating PET film, coating a PE film, enabling the outer layer of the PE film to be in contact with the second adhesive, and curing to obtain the BOPP printing film/the aluminum plating PET film/the PE film.
9. The method for producing a high barrier aluminum-plated composite film according to claim 8, wherein the composite pressure of the PE film and BOPP printed film/aluminum-plated PET film in S2 is 0.1 to 0.3MPa.
10. The method for producing a high barrier aluminum-plated composite film according to claim 8, wherein the curing temperature in S2 is 45-55 ℃ and the curing time is 16-30h.
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