CN112721372B - Modified polyolefin composite membrane composition, modified polyolefin composite membrane, and preparation method and application thereof - Google Patents

Modified polyolefin composite membrane composition, modified polyolefin composite membrane, and preparation method and application thereof Download PDF

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CN112721372B
CN112721372B CN202011577800.1A CN202011577800A CN112721372B CN 112721372 B CN112721372 B CN 112721372B CN 202011577800 A CN202011577800 A CN 202011577800A CN 112721372 B CN112721372 B CN 112721372B
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layer
film
glue
polyethylene
modified polyolefin
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CN112721372A (en
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韦丽明
黎倬辰
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Shanghai Ruoyi New Material Technology Co ltd
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Shanghai Ruoyi New Material Technology 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • 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
    • 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
    • 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
    • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
    • B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
    • B65D85/72—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for edible or potable liquids, semiliquids, or plastic or pasty materials
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • 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
    • B32B2535/00—Medical equipment, e.g. bandage, prostheses, catheter
    • 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 invention relates to the technical field of composite packaging processing, and discloses a modified polyolefin composite membrane composition, a modified polyolefin composite membrane, and a preparation method and application thereof. The composition comprises a first layer of film material, a middle layer of film material and a third layer of film material, wherein the third layer of film material comprises a PE corona layer material, a barrier layer film material and a PE heat-sealing layer material; the first layer film material and the middle layer film material respectively contain C4‑C8One or more of polyethylene, unitary homo-polypropylene, binary co-polypropylene and ternary co-polypropylene; the barrier layer film material contains ethylene-vinyl alcohol copolymer and/or thermoplastic polyvinyl alcohol. The composite film has excellent barrier property, excellent puncture resistance, excellent pressure resistance and excellent dropping property.

Description

Modified polyolefin composite membrane composition, modified polyolefin composite membrane, and preparation method and application thereof
Technical Field
The invention relates to the technical field of composite packaging processing, in particular to a modified polyolefin composite membrane composition, a modified polyolefin composite membrane, a preparation method and an application thereof.
Background
With the improvement of living standard and the variety of aesthetic, the pursuit of consumers and producers to the packaging, whether quality or perception, is extremely high. Most packages are compounded with multi-material films to meet functional and appearance requirements. The single-product composite packaging structure of liquid milk for example is: BOPA film// glue// PET aluminized film// glue// blown PE film; nut class composite packaging structure: BOPP film// glue// paper// glue// BOPET aluminized film// glue// blown PE film.
The package is used as an indispensable material for commodity protection, the package demand and the yield are increased, but the classification and the recovery of the waste multi-material composite package are not easy, and an effective method for separating and classifying and recovering films of different composite materials is still not available at present. The waste packaging materials buried in the land can cause soil impoverishment and deterioration, and the yield of crops is reduced or is not produced; incineration of waste plastics produces a large amount of CO2Toxic gases such as CO and the like and residual heavy metals in ash content aggravate environmental pollution and greenhouse effect; a great deal of research has found that marine life is being endangered by waste packaging materials. The recycling task is repeated at random.
In addition, consumers do not want the visual perception of consumer product packaging to be poor, and want food and daily chemical products to have a longer shelf life, no taint of odor, and no odor without adding chemicals.
Therefore, it is important to research and develop a modified polyolefin composite film composition and a modified polyolefin composite film which have high barrier property, are easy to recycle after being packaged and discarded, and can be processed and recycled by thermoplastic processing.
Disclosure of Invention
The invention aims to solve the problems that the composite packaging material is not easy to recycle, the composite packaging material has poor puncture resistance, moisture resistance and oxygen resistance, and the composite packaging material has poor pressure resistance and drop resistance, and provides a modified polyolefin composite film composition, a modified polyolefin composite film and a preparation method and application thereof. The composite membrane has the advantages of excellent barrier property, excellent puncture resistance, excellent pressure resistance and excellent falling property, and the composite membrane is mainly made of polyolefin and can be completely recycled.
In order to achieve the above object, a first aspect of the present invention provides a modified polyolefin composite film composition, wherein the composition comprises a first layer film, a middle layer film and a third layer film, and the third layer film comprises a PE corona layer material, a barrier layer film material and a PE heat seal layer material;
wherein the first layer film and the intermediate layer film each comprise C4-C8One or more of polyethylene, unitary homo-polypropylene, binary co-polypropylene and ternary co-polypropylene; and the barrier layer film material contains ethylene-vinyl alcohol copolymer and/or thermoplastic polyvinyl alcohol.
In a second aspect, the invention provides a barrier polyolefin composite film prepared from the composition, wherein the composite film comprises a first film 810, an intermediate film 830 and a third film 850 which are sequentially stacked, and the first film 810 is obtained by extruding a first material containing a first film material; the intermediate layer film 830 is extruded from a second material containing an intermediate layer film material;
wherein, the third film 850 comprises a PE corona layer 610, a thermoplastic barrier layer 950 and a PE heat-sealing layer 611 which are sequentially superposed; the PE corona layer 610 is obtained by extruding a third material containing a PE corona layer material; the thermoplastic barrier layer 950 is extruded from a fourth material comprising a thermoplastic ethylene-vinyl alcohol copolymer and/or a thermoplastic polyvinyl alcohol; the PE heat seal layer 611 is obtained by extruding a fifth material containing a PE heat seal layer material.
In a third aspect, the present invention provides a method for preparing the aforementioned composite film, where the method for preparing the composite film includes:
(1) preparing a first layer of film 810 using a first material;
(2) preparing an intermediate layer film 830 using a second material;
(3) preparing a PE corona layer 610 by adopting a third material, preparing a thermoplastic barrier layer 950 by adopting a fourth material, preparing a PE heat-sealing layer 611 by adopting a fifth material, and sequentially bonding the PE corona layer 610, the thermoplastic barrier layer 950 and the PE heat-sealing layer 611 through a first polymer adhesive layer 210 and a second polymer adhesive layer 220 to prepare a third layer of film 850;
(4) the first layer film 810, the intermediate layer film 830, and the third layer film 850 are sequentially bonded to each other by the first glue layer 821 and the second glue layer 822, thereby preparing a modified polyolefin composite film.
The invention provides an application of the composite film in one or more of food packaging, industrial products, daily chemical product packaging and medical appliances.
Through the technical scheme, the modified polyolefin composite membrane has excellent barrier property, excellent puncture resistance, excellent pressure resistance and excellent falling property; in addition, the environment-friendly composite material meets the environment protection trend, and the function and the appearance of the composite material meet the market demand, so that the composite material has great social significance.
Drawings
FIG. 1 is a schematic structural view of a modified polyolefin composite film according to the present invention;
FIG. 2 is a schematic structural view of a third film 850 of the modified polyolefin composite film of the present invention;
FIG. 3 is a schematic flow chart of a process for preparing a finished product using the modified polyolefin composite film of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, there is provided a modified polyolefin composite film composition, wherein the composition comprises a first layer film material, a middle layer film material and a third layer film material, and the third layer film material comprises a PE corona layer material, a barrier layer film material and a PE heat seal layer material;
wherein the first layer film material and the middle layer film material each comprise C4-C8One or more of polyethylene, unitary homo-polypropylene, binary co-polypropylene and ternary co-polypropylene; and the barrier layer film material contains ethylene-vinyl alcohol copolymer and/or thermoplastic polyvinyl alcohol.
According to the invention, the inventor of the invention finds out through a large number of scientific experiments that: the barrier layer film material containing the ethylene-vinyl alcohol copolymer and/or the thermoplastic polyvinyl alcohol is used in the production process of the multilayer co-extrusion polyolefin composite film, the barrier layer film material has high barrier property and degradable property, and under the conditions of proper proportion and extrusion process, the formed high barrier layer has excellent gas barrier and oxygen barrier properties, and meanwhile, the polyolefin composite film can keep good transparency and has good moisture barrier and water resistance.
According to the present invention, the unitary homo-polypropylene, also commonly referred to as homo-polypropylene, is in the present invention homo-polypropylene with an isotacticity of more than 95%.
The binary copolymerized polypropylene is ethylene propylene copolymerized polypropylene and/or ethylene butylene copolymerized polypropylene.
The ternary copolymerized polypropylene is ethylene propylene butene copolymerized polypropylene and/or ethylene propylene hexene copolymerized polypropylene.
According to the invention, the barrier layer film material preferably contains thermoplastic polyvinyl alcohol (TPVA), wherein the thermoplastic polyvinyl alcohol has a melt flow rate of 2.0-5.0g/10min at 210 ℃ under a 2.16kg load and a density of 0.92-1.30g/cm3(ii) a Preferably, the thermoplastic polyvinyl alcohol has a melt flow rate of 2.5 to 4.0g/10min at 210 ℃ under a 2.16kg load and a density of 1.0 to 1.28g/cm3(ii) a More preferably, the thermoplastic polyvinyl alcohol has a melt flow rate of 2.7 to 2.9g/10min at 210 ℃ under a 2.16kg load and a density of 1.05 to 1.15g/cm3。
In the present invention, both the thermoplastic polyvinyl alcohol and the ethylene-vinyl alcohol copolymer are commercially available, for example, from China petrochemical under the respective models TPVA-1 and EVOH-1.
According to the invention, the PE corona layer contains a first medium density linear polyethylene (MLDPE) and a first antiblocking masterbatch; preferably, the content of the first medium-density linear polyethylene is 80.0-99.5 wt% and the content of the first anti-blocking master batch is 0.5-20 wt% based on the total weight of the PE corona layer material; more preferably, the content of the first medium density linear polyethylene is 90-98 wt% and the content of the first anti-blocking master batch is 2-10 wt% based on the total weight of the PE corona layer material; still more preferably, the content of the first medium density linear polyethylene is 95 to 97 wt% and the content of the first anti-blocking master batch is 3 to 5 wt% based on the total weight of the PE corona layer material.
According to the invention, the PE heat-sealing layer material contains one or more of second medium-density linear polyethylene (MLDPE), metallocene catalyzed polyethylene (m-LLDPE), high-pressure polyethylene (LDPE), second anti-blocking master batch and high-molecular smooth master batch; preferably, based on the total weight of the PE heat-seal layer material, the content of the second medium-density linear polyethylene is 10.0-58.5 wt%, the content of the metallocene-catalyzed polyethylene is 20-30 wt%, the content of the high-pressure polyethylene is 20-40 wt%, the content of the second anti-blocking master batch is 0.5-10 wt%, and the content of the high-molecular smooth master batch is 1.0-10 wt%. More preferably, based on the total weight of the PE heat seal layer, the content of the second medium density linear polyethylene is 25 to 40 wt%, the content of the metallocene-catalyzed polyethylene is 25 to 29 wt%, the content of the high pressure polyethylene is 25 to 30 wt%, the content of the second anti-blocking master batch is 5 to 8 wt%, and the content of the high molecular smooth master batch is 5 to 8 wt%.
According to the invention, the metallocene-catalyzed polyethylene is C6-C8Metallocene-catalyzed polyethylene, preferably having a melt flow rate of 0.5 to 4.0g/10min at 190 ℃ under a 2.16kg load and a density of 0.86 to 0.930g/cm3(ii) a Preferably, the metallocene-catalyzed polyethylene has a melt flow rate of from 0.5 to 3.0 at 190 ℃ under a load of 2.16kgg/10min, density of 0.86-0.89g/cm3。
According to the invention, the high-pressure polyethylene has a melt flow rate of 1.5 to 4.0g/10min at 190 ℃ under a load of 2.16kg and a density of 0.89 to 0.935g/cm3(ii) a Preferably, the high pressure polyethylene has a melt flow rate of 1.5 to 3.0g/10min at 190 ℃ under a load of 2.16kg and a density of 0.89 to 0.92g/cm3。
According to the invention, the high-molecular smooth master batch is prepared by blending and modifying a blend E, wherein the blend E contains optional silicone, erucamide and third medium-density linear polyethylene. Preferably, the silicone is present in an amount of from 0 to 20 weight percent, based on the total weight of the blend E; the erucamide content is 0.5-10 wt%, and the third medium density linear polyethylene content is 70-99.5 wt%.
According to the invention, the first, second and third medium-density linear polyethylenes are identical or different, each having a melt flow rate of 1.5 to 4.5g/10min at 190 ℃ under a load of 2.16kg and a density of 0.87 to 0.940g/cm3(ii) a Preferably, the melt flow rate is 1.5 to 3.5g/10min and the density is 0.89 to 0.92g/cm, each at 190 ℃ under a load of 2.16kg3。
According to the invention, the first anti-blocking masterbatch and the second anti-blocking masterbatch are identical or different and each consist of Silica (SiO) and medium density polyethylene, wherein the Silica (SiO) is present in the first anti-blocking masterbatch or the second anti-blocking masterbatch, based on the total weight of the masterbatch2) Is 0.5-1 wt%, and the medium density polyethylene is 99-99.5 wt%.
According to a second aspect of the present invention, there is provided a barrier polyolefin composite film prepared from the composition, wherein the composite film comprises a first film 810, an intermediate film 830 and a third film 850 which are sequentially stacked, and the first film 810 is extruded from a first material containing a first film material; the intermediate layer film 830 is obtained by extruding a second material containing an intermediate layer film material;
wherein, the third film 850 comprises a PE corona layer 610, a thermoplastic barrier layer 950 and a PE heat-sealing layer 611 which are sequentially superposed; the PE corona layer 610 is obtained by extruding a third material containing a PE corona layer material; the thermoplastic barrier layer 950 is extruded from a fourth material comprising a thermoplastic ethylene-vinyl alcohol copolymer and/or a thermoplastic polyvinyl alcohol; the PE heat seal layer 611 is obtained by extruding a fifth material containing a PE heat seal layer material.
According to the present invention, the surface of the interlayer film 830 is further plated with an aluminum film, preferably, the aluminum film includes a vaporized aluminum film and/or an aluminum oxide film.
According to the invention, the inventor of the invention finds out through a large number of scientific experiments that: the surface of the intermediate layer film 830 is also plated with an aluminum film, and the aluminum film can form a compact barrier layer on the surface of the intermediate layer film 830, so that excellent moisture and water resistance, air and oxygen resistance can be obtained; further, the inventors of the present invention have found that the aluminum film has high brittleness, and if it is used alone, it is easily cracked during film winding or post-processing, and the barrier property is deteriorated, but in the present invention, the aluminum film is vapor-deposited on the surface of the intermediate layer film 830, and the above-mentioned defects can be overcome; meanwhile, the transparency of the polyolefin composite membrane can be ensured.
According to the invention, the first layer of film 810 has a thickness of 5-80 μm; the thickness of the second layer of film 830 is 5-150 μm; the thickness of the third layer of film 850 is 5-200 μm; preferably, the first layer of film 810 has a thickness of 9-60 μm; the thickness of the second layer of film 830 is 10-50 μm; the thickness of the third layer of film 850 is 40-100 μm; more preferably, the first layer of film 810 has a thickness of 20-30 μm; the thickness of the second layer of film 830 is 20-30 μm; the third layer 850 is 70-90 μm thick.
According to the invention, the total thickness of the composite membrane is 15-430 μm, preferably 59-150 μm, more preferably 110-130 μm.
According to the present invention, the composite film further includes a first layer film 810, a first glue layer 821, an intermediate layer film 830, a second glue layer 822, and a third layer film 850, which are sequentially stacked.
According to the present invention, the first glue layer 821 and the second glue layer 822 are the same or different and are each one or more of a polyvinyl alcohol compound glue, a polyurethane two-component glue and a modified polyolefin adhesive, and preferably are polyvinyl alcohol compound glues.
According to the invention, the polyvinyl alcohol compound glue comprises a polyvinyl alcohol main agent and a curing agent, and the solid content of the polyvinyl alcohol main agent is 15-32 wt% and the solid content of the curing agent is 10-25 wt% based on the total weight of the polyvinyl alcohol compound glue.
According to the invention, the ratio of the polyvinyl alcohol main agent to the curing agent is 10 (0.5-1.5).
According to the present invention, the respective sizing amounts of the first glue layer 821 and the second glue layer 822 are 1.0-10.0g/m2Preferably 2.5 to 5.0g/m2。
According to the present invention, the third film 850 further includes a PE corona layer 610, a first polymeric adhesive layer 210, a thermoplastic barrier layer 950, a second polymeric adhesive layer 220, and a PE heat seal layer 611, which are sequentially stacked.
According to the invention, the first polymer adhesive layer 210 and the second polymer adhesive layer 220 are the same or different and are each a maleic anhydride graft copolymer, the melt flow rate at a melting temperature of 119-125 ℃ and 190 ℃ under a 2.16kg load is 2.8-3.5g/10min, and the density is 0.935-0.942g/cm3。
According to the invention, the weight ratio of the PE corona layer 610, the first polymer adhesive layer 210, the thermoplastic barrier layer 950, the second polymer adhesive layer 220 and the PE heat-sealing layer 611 is 1 (0.02-0.95) to (0.02-0.95): (0.02-0.95): (0.5-2); preferably 1 (0.1-0.6) to 0.1-0.6): (0.1-0.6): (1.0-1.8).
According to a third aspect of the present invention, there is provided a method for preparing the composite film, wherein the method comprises:
(1) preparing a first layer of film 810 using a first material;
(2) preparing an intermediate layer film 830 using a second material;
(3) preparing a PE corona layer 610 by adopting a third material, preparing a thermoplastic barrier layer 950 by adopting a fourth material, preparing a PE heat-sealing layer 611 by adopting a fifth material, and sequentially bonding the PE corona layer 610, the thermoplastic barrier layer 950 and the PE heat-sealing layer 611 through a first polymer adhesive layer 210 and a second polymer adhesive layer 220 to prepare a third layer of film 850;
(4) the first layer film 810, the intermediate layer film 830, and the third layer film 850 are sequentially bonded to each other by the first glue layer 821 and the second glue layer 822, thereby preparing a modified polyolefin composite film.
According to the invention, the preparation method further comprises: the first layer film 810, the intermediate layer film 830, and the third layer film 850 are made by coextrusion as well as by stretching, blown bubble, or casting.
According to the present invention, the first film 810 is selected from one or more of a multilayer coextruded stretched polyolefin film, a multilayer coextruded cast polyolefin film, and a multilayer coextruded blown polyolefin film.
The multilayer co-extruded and stretched film is selected from any one of a multilayer co-extruded and unidirectional stretched polypropylene (MOPP) film, a multilayer co-extruded and bidirectional stretched polypropylene (BOPP) film, a multilayer co-extruded and unidirectional stretched polyethylene (MOPE) film and a multilayer co-extruded and bidirectional stretched polyethylene (BOPE) film.
The multilayer co-extrusion casting polyolefin film is a multilayer co-extrusion casting polypropylene (CPP) film and/or a multilayer co-extrusion Casting Polyethylene (CPE) film.
Wherein the multilayer co-extrusion blow-molded polyolefin film is a multilayer co-extrusion blow-molded polypropylene (IPP) film and/or a multilayer co-extrusion blow-molded polyethylene (IPE) film.
According to the present invention, preferably, the functional polyethylene film 810 is a multilayer co-extruded Biaxially Oriented Polyethylene (BOPE) film.
According to the present invention, an aluminum film is plated on the surface of the intermediate layer film 830 by using an evaporation method.
According to the present invention, the intermediate layer film 830 is prepared by co-extrusion and unidirectional stretching, bidirectional stretching or casting, preferably, the intermediate layer film 830 is selected from one of a multi-layer co-extrusion and stretching polyolefin evaporation aluminum film, a multi-layer co-extrusion and stretching polyolefin evaporation aluminum oxide film, a multi-layer co-extrusion and casting polyolefin evaporation aluminum film, and a multi-layer co-extrusion and casting polyolefin evaporation aluminum oxide film;
the multilayer co-extruded and stretched polyolefin film is any one of a multilayer co-extruded and unidirectional stretched polypropylene (MOPP) film, a multilayer co-extruded and bidirectional stretched polypropylene (BOPP) film, a multilayer co-extruded and unidirectional stretched polyethylene (MOPE) film and a multilayer co-extruded and bidirectional stretched polyethylene (BOPE) film;
wherein the multilayer co-extrusion casting polyolefin is any one of a multilayer co-extrusion casting polypropylene (CPP) film and a multilayer co-extrusion Casting Polyethylene (CPE) film;
preferably, the functional polyethylene film 830 is a multilayer co-extrusion biaxially oriented polyethylene vapor deposited aluminum oxide film.
According to the present invention, the third film 850 is made by coextrusion as well as by stretching, blown tube or casting.
Preferably, the third film 850 is a multilayer coextruded cast barrier film; preferably, a five layer coextruded cast film; preferably, the five-layer co-extrusion casting barrier film layer structure is a film formed by melting and co-extruding the PE corona layer 610, the first polymer adhesive layer 210, the thermoplastic barrier layer 950, the second polymer adhesive layer 220 and the PE heat-sealing layer 611 in sequence through an extruder.
According to a third aspect of the present invention, there is provided a use of the composite film described above in one or more of food packaging, industrial goods, consumer goods packaging and medical devices.
According to a preferred embodiment of the present invention, the preparation of the modified polyolefin composite film using the modified polyolefin composite film composition of the present invention and the preparation method of the present invention comprises:
(1) the modified polyolefin composite film composition comprises:
a first layer of film material: multilayer coextruded Biaxially Oriented Polyethylene (BOPE) films.
Middle layer film material: the multilayer co-extrusion biaxial tension polyethylene evaporation coating alumina film.
A third layer of film material:
PE corona layer material: a first medium density linear polyethylene (MLDPE) and a first antiblock masterbatch; based on the total weight of the PE corona layer material, the content of the first medium-density linear polyethylene is 95.5-96.5 wt%, and the content of the first anti-blocking master batch is 3.5-4.5 wt%.
And (3) barrier layer film material: a thermoplastic polyvinyl alcohol having a melt flow rate of 2.7 to 2.8g/10min at 210 ℃ under a load of 2.16kg and a density of 1.05 to 1.15g/cm3。
PE heat-sealing layer material: second medium density linear polyethylene (MLDPE), metallocene catalyzed polyethylene (m-LLDPE), high pressure polyethylene (LDPE), second anti-blocking masterbatch and high molecular smooth masterbatch; based on the total weight of the PE heat-seal layer material, the content of the second medium-density linear polyethylene is 29-40 wt%, the content of the metallocene catalyzed polyethylene is 25-27 wt%, the content of the high-pressure polyethylene is 25-30 wt%, the content of the second anti-blocking master batch is 5-7 wt%, and the content of the high-molecular smooth master batch is 5-7 wt%.
The metallocene-catalyzed polyethylene has a melt flow rate of 0.5 to 3.0g/10min and a density of 0.86 to 0.89g/cm at 190 ℃ under a load of 2.16kg3The melt flow rate of the high-pressure polyethylene is 1.5-3.0g/10min, and the density is 0.89-0.92g/cm3The first medium density linear polyethylene and the second medium density linear polyethylene are the same, the melt flow rate is 1.5-3.0g/10min, and the density is 0.89-0.92g/cm3。
The first polymer adhesive layer 210 is composed of maleic anhydride graft copolymer;
the second polymer adhesive layer 220 comprises maleic anhydride graft copolymer;
the first glue layer 821 is composed of polyvinyl alcohol;
the composition of the second glue layer 822 is polyvinyl alcohol.
(2) Preparation method of modified polyolefin composite membrane
(2-1) preparing a first film 810 from the first mass of the first film by extrusion and biaxial stretching;
preparing a film from the intermediate layer film material by an extrusion and biaxial stretching method, and preparing an intermediate layer film 830 by an aluminum oxide evaporation method;
preparing a PE corona layer 610 from the PE corona layer material by an extrusion casting method;
preparing the barrier layer 950 from thermoplastic polyvinyl alcohol by extrusion casting;
preparing a PE heat-sealing layer 611 from the PE heat-sealing layer material by an extrusion casting method;
(2-2) as shown in fig. 2, sequentially adhering the PE corona layer 610, the thermoplastic barrier layer 950 and the PE heat-seal layer 611 through the first polymer adhesive layer 210 and the second polymer adhesive layer 220 to prepare a third film 850;
(4) as shown in fig. 1, the first layer film 810, the intermediate layer film 830, and the third layer film 850 are bonded to each other sequentially by the first glue layer 821 and the second glue layer 822;
wherein, the extrusion ratio of the PE corona layer 610, the polymer adhesive layer 210, the thermoplastic barrier layer 950, the polymer adhesive layer 210 and the PE heat-sealing layer 611 is 1 (0.1-0.6) to (0.1-0.6): (0.1-0.6): (1.0-1.8);
in addition, according to the flow chart shown in fig. 3, gluing, compounding, drying, curing and bag making are carried out: the composite sizing amount is 2.8g/m2Glue 821 and glue 822, the composite structure is 810/glue/830/glue/850, drying after compounding through a drying oven, and then standing for 2 days for curing under the environment that the temperature is 48 +/-5 ℃ and the humidity is below 50% RH; taking out, slitting and making bags; the dummy frame is a process that can be selected not to be performed.
The modified polyolefin composite membrane is obtained by the preparation method, and is marked as S1; wherein the first layer 810 has a thickness of 20-30 μm; the thickness of the interlayer film 830 is 20-30 μm; the thickness of the third film 850 is 70-90 μm, and the total thickness of the modified polyolefin composite film is 110-130 μm.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
(1) and (3) puncture resistance strength test: the standard environment of sample state regulation and test is carried out according to the regulation of GB/T2918, the test environment condition is that the temperature is 23 ℃ plus or minus 2 ℃, the relative humidity is 50 percent plus or minus 1 percent, and the test is carried out according to GB/T37841-2019 'test method for puncture resistance of plastic films and slices'.
(2) Oxygen transmission capacity test: the standard environment for sample state regulation and test is specified in GB/T2918, and the test environment conditions are 23 ℃ +/-2 ℃ and 50% +/-1% relative humidity, and the test is carried out according to GB/T1038-.
(3) Water vapor transmission test: the standard environment for sample state regulation and test is specified in GB/T2918, and the test environment conditions are 23 ℃ +/-2 ℃ and 50% +/-1% relative humidity, and the test is carried out according to GB/T1037-.
(4) Pressure resistance of the bag: the standard environment of sample state regulation and test is carried out according to the regulation of GB/T2918, and the test environment conditions are that the temperature is 23 ℃ plus or minus 2 ℃, the relative humidity is 50 percent plus or minus 1 percent, and the test is carried out according to GB/T10004-. Making into three-side sealed bag, wherein the weight of the bag and the inner packing material is 1000 g.
(5) Drop performance of the bag: the standard environment of sample state regulation and test is carried out according to the regulation of GB/T2918, and the test environment conditions are that the temperature is 23 ℃ plus or minus 2 ℃, the relative humidity is 50 percent plus or minus 1 percent, and the test is carried out according to GB/T10004-2008 'plastic composite film for packaging, bag dry method composite and extrusion composite'. The weight of the bag and the inner package is 1000g, and the falling height is 500 mm.
Example 1
This example illustrates the preparation of a modified polyolefin composite film using the modified polyolefin composite film composition of the present invention and the preparation method of the present invention.
(1) The modified polyolefin composite film composition comprises:
a first layer of film material: multilayer coextruded Biaxially Oriented Polyethylene (BOPE) films.
Middle layer film material: the multilayer co-extrusion biaxial tension polyethylene evaporation coating alumina film.
A third layer of film material:
PE corona layer material: a first medium density linear polyethylene (MLDPE) and a first antiblock masterbatch; the content of the first medium-density linear polyethylene is 96.5 wt% and the content of the first anti-blocking master batch is 3.5 wt% based on the total weight of the PE corona layer material.
And (3) barrier layer film material: thermoplastic polyvinyl alcohol having a melt flow rate of 2.8g/10min at 210 ℃ under a load of 2.16kg and a density of 1.05g/cm3。
PE heat-sealing layer material: second medium density linear polyethylene (MLDPE), metallocene catalyzed polyethylene (m-LLDPE), high pressure polyethylene (LDPE), second anti-blocking masterbatch and high molecular smooth masterbatch; based on the total weight of the PE heat-seal layer material, the content of the second medium-density linear polyethylene is 35 wt%, the content of the metallocene catalyzed polyethylene is 25 wt%, the content of the high-pressure polyethylene is 30 wt%, the content of the second anti-blocking master batch is 5 wt%, and the content of the high-molecular smooth master batch is 5 wt%.
The metallocene-catalyzed polyethylene had a melt flow rate of 3.0g/10min and a density of 0.89g/cm at 190 ℃ under a load of 2.16kg3The melt flow rate of the high-pressure polyethylene is 3.0g/10min, and the density is 0.92g/cm3The first medium density linear polyethylene and the second medium density linear polyethylene are the same, the melt flow rate is 3.0g/10min, and the density is 0.92g/cm3。
The first polymer adhesive layer 210 is composed of maleic anhydride graft copolymer;
the second polymer adhesive layer 220 comprises maleic anhydride graft copolymer;
the first glue layer 821 is composed of polyvinyl alcohol;
the composition of the second glue layer 822 is polyvinyl alcohol.
(2) Preparation method of modified polyolefin composite membrane
(2-1) preparing a first film 810 from the first mass of the first film by extrusion and biaxial stretching;
preparing a film from the intermediate layer film material by an extrusion and biaxial stretching method, and preparing an intermediate layer film 830 by an aluminum oxide evaporation method;
preparing a PE corona layer 610 from the PE corona layer material by an extrusion casting method;
preparing a barrier layer film 950 from polyvinyl alcohol by an extrusion casting method;
preparing a PE heat-sealing layer 611 from the PE heat-sealing layer material by an extrusion casting method;
(2-2) as shown in fig. 2, sequentially adhering the PE corona layer 610, the thermoplastic barrier layer 950 and the PE heat-seal layer 611 through the first polymer adhesive layer 210 and the second polymer adhesive layer 220 to prepare a third film 850;
(4) as shown in fig. 1, the first layer film 810, the intermediate layer film 830, and the third layer film 850 are bonded to each other sequentially by the first glue layer 821 and the second glue layer 822;
wherein, PE corona layer 610, polymer adhesive layer 210, thermoplasticity barrier layer 950, polymer adhesive layer 210, PE heat-seal layer 611, the extrusion capacity proportion is 1: 0.6: 0.6: 0.6: 1.8;
in addition, according to the flow chart shown in fig. 3, gluing, compounding, drying, curing and bag making are carried out: the composite sizing amount is 2.8g/m2Glue 821 and glue 822, the composite structure is 810/glue/830/glue/850, drying after compounding through a drying oven, and then standing for 2 days for curing under the environment that the temperature is 48 +/-5 ℃ and the humidity is below 50% RH; taking out, slitting and making bags; the dummy frame is a process that can be selected not to be performed.
The modified polyolefin composite membrane is obtained by the preparation method, and is marked as S1; wherein the first layer 810 has a thickness of 20 μm; the thickness of the interlayer film 830 is 20 μm; the thickness of the third film 850 is 80 μm, and the total thickness of the modified polyolefin composite film is 122 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Example 2
This example illustrates the preparation of a modified polyolefin composite film using the modified polyolefin composite film composition of the present invention and the preparation method of the present invention.
(1) The modified polyolefin composite film composition comprises:
a first layer of film material: multilayer coextruded Biaxially Oriented Polyethylene (BOPE) films.
Middle layer film material: the multilayer co-extrusion biaxial tension polyethylene evaporation coating alumina film.
A third layer of film material:
PE corona layer material: a first medium density linear polyethylene (MLDPE) and a first antiblock masterbatch; the content of the first medium-density linear polyethylene is 80 weight percent and the content of the first anti-blocking master batch is 20 weight percent based on the total weight of the PE corona layer material.
And (3) barrier layer film material: a thermoplastic polyvinyl alcohol having a melt flow rate of 2.0g/10min at 210 ℃ under a load of 2.16kg and a density of 0.92g/cm3。
PE heat-sealing layer material: second medium density linear polyethylene (MLDPE), metallocene catalyzed polyethylene (m-LLDPE), high pressure polyethylene (LDPE), second anti-blocking masterbatch and high molecular smooth masterbatch; based on the total weight of the PE heat-seal layer material, the content of the second medium-density linear polyethylene is 10 wt%, the content of the metallocene catalyzed polyethylene is 30 wt%, the content of the high-pressure polyethylene is 40 wt%, the content of the second anti-blocking master batch is 10 wt%, and the content of the high-molecular smooth master batch is 10 wt%.
The metallocene-catalyzed polyethylene had a melt flow rate of 0.5g/10min and a density of 0.86g/cm at 190 ℃ under a load of 2.16kg3The melt flow rate of the high-pressure polyethylene is 1.5g/10min, and the density is 0.89g/cm3The first medium density linear polyethylene and the second medium density linear polyethylene are the same, the melt flow rate is 1.5g/10min, and the density is 0.89g/cm3。
The first polymer adhesive layer 210 is composed of maleic anhydride graft copolymer;
the second polymer adhesive layer 220 comprises maleic anhydride graft copolymer;
the first glue layer 821 is composed of polyvinyl alcohol;
the composition of the second glue layer 822 is polyvinyl alcohol.
(2) Preparation method of modified polyolefin composite membrane
(2-1) preparing a first film 810 from the first mass of the first film by extrusion and biaxial stretching;
preparing a film from the intermediate layer film material by an extrusion and biaxial stretching method, and preparing an intermediate layer film 830 by an aluminum oxide evaporation method;
preparing a PE corona layer 610 from the PE corona layer material by an extrusion casting method;
preparing a barrier layer film 950 from polyvinyl alcohol by an extrusion casting method;
preparing a PE heat-sealing layer 611 from the PE heat-sealing layer material by an extrusion casting method;
(2-2) as shown in fig. 2, sequentially adhering the PE corona layer 610, the thermoplastic barrier layer 950 and the PE heat-seal layer 611 through the first polymer adhesive layer 210 and the second polymer adhesive layer 220 to prepare a third film 850;
(4) as shown in fig. 1, the first layer film 810, the intermediate layer film 830, and the third layer film 850 are bonded to each other sequentially by the first glue layer 821 and the second glue layer 822;
wherein, PE corona layer 610, polymer adhesive layer 210, thermoplasticity barrier layer 950, polymer adhesive layer 210, PE heat-seal layer 611, the extrusion capacity proportion is 1: 0.6: 0.6: 0.6: 1.8;
in addition, according to the flow chart shown in fig. 3, gluing, compounding, drying, curing and bag making are carried out: the composite sizing amount is 10g/m2Glue 821 and glue 822, the composite structure is 810/glue/830/glue/850, drying after compounding through a drying oven, and then standing for 2 days for curing under the environment that the temperature is 48 +/-5 ℃ and the humidity is below 50% RH; taking out, slitting and making bags; the dummy frame is a process that can be selected not to be performed.
The modified polyolefin composite membrane is obtained by the preparation method, and is marked as S2; wherein the first layer 810 has a thickness of 20 μm; the thickness of the interlayer film 830 is 20 μm; the thickness of the third film 850 is 80 μm, and the total thickness of the modified polyolefin composite film is 128 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Example 3
This example illustrates the preparation of a modified polyolefin composite film using the modified polyolefin composite film composition of the present invention and the preparation method of the present invention.
(1) The modified polyolefin composite film composition comprises:
a first layer of film material: multilayer coextruded Biaxially Oriented Polyethylene (BOPE) films.
Middle layer film material: the multilayer co-extrusion biaxial tension polyethylene evaporation coating alumina film.
A third layer of film material:
PE corona layer material: a first medium density linear polyethylene (MLDPE) and a first antiblock masterbatch; based on the total weight of the PE corona layer material, the content of the first medium-density linear polyethylene is 99.5 wt%, and the content of the first anti-blocking master batch is 0.5 wt%.
And (3) barrier layer film material: thermoplastic polyvinyl alcohol having a melt flow rate of 5g/10min at 210 ℃ under a load of 2.16kg and a density of 1.3g/cm3。
PE heat-sealing layer material: second medium density linear polyethylene (MLDPE), metallocene catalyzed polyethylene (m-LLDPE), high pressure polyethylene (LDPE), second anti-blocking masterbatch and high molecular smooth masterbatch; based on the total weight of the PE heat-seal layer material, the content of the second medium-density linear polyethylene is 58.5 wt%, the content of the metallocene catalyzed polyethylene is 20 wt%, the content of the high-pressure polyethylene is 20 wt%, the content of the second anti-blocking master batch is 0.5 wt%, and the content of the high-molecular smooth master batch is 1 wt%.
The metallocene-catalyzed polyethylene had a melt flow rate of 4.0g/10min and a density of 0.93g/cm at 190 ℃ under a load of 2.16kg3SaidThe high pressure polyethylene had a melt flow rate of 4.0g/10min and a density of 0.935g/cm3The first medium density linear polyethylene and the second medium density linear polyethylene are the same, the melt flow rate is 4.5g/10min, and the density is 0.94g/cm3。
The first polymer adhesive layer 210 is composed of maleic anhydride graft copolymer;
the second polymer adhesive layer 220 comprises maleic anhydride graft copolymer;
the first glue layer 821 is composed of polyvinyl alcohol;
the composition of the second glue layer 822 is polyvinyl alcohol.
(2) Preparation method of modified polyolefin composite membrane
(2-1) preparing a first film 810 from the first mass of the first film by extrusion and biaxial stretching;
preparing a film from the intermediate layer film material by an extrusion and biaxial stretching method, and preparing an intermediate layer film 830 by an aluminum oxide evaporation method;
preparing a PE corona layer 610 from the PE corona layer material by an extrusion casting method;
preparing a barrier layer film 950 from polyvinyl alcohol by an extrusion casting method;
preparing a PE heat-sealing layer 611 from the PE heat-sealing layer material by an extrusion casting method;
(2-2) as shown in fig. 2, sequentially adhering the PE corona layer 610, the thermoplastic barrier layer 950 and the PE heat-seal layer 611 through the first polymer adhesive layer 210 and the second polymer adhesive layer 220 to prepare a third film 850;
(4) as shown in fig. 1, the first layer film 810, the intermediate layer film 830, and the third layer film 850 are bonded to each other sequentially by the first glue layer 821 and the second glue layer 822;
wherein, PE corona layer 610, polymer adhesive layer 210, thermoplasticity barrier layer 950, polymer adhesive layer 210, PE heat-seal layer 611, the extrusion capacity proportion is 1: 0.02: 0.02: 0.02: 1.8;
in addition, according to the flow chart shown in fig. 3, gluing, compounding, drying, curing and bag making are carried out: the composite sizing amount is 1g/m2Glue 821 and 822, composite junctionThe structure is 810/glue/830/glue/850, the composite is dried after passing through a drying oven, and then the mixture is kept stand for 2 days for curing under the environment that the temperature is 48 +/-5 ℃ and the humidity is below 50% RH; taking out, slitting and making bags; the dummy frame is a process that can be selected not to be performed.
The modified polyolefin composite membrane is obtained by the preparation method, and is marked as S3; wherein the first layer 810 has a thickness of 20 μm; the thickness of the interlayer film 830 is 20 μm; the thickness of the third film 850 is 80 μm, and the total thickness of the modified polyolefin composite film is 120 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Example 4
This example illustrates the preparation of a modified polyolefin composite film using the modified polyolefin composite film composition of the present invention and the preparation method of the present invention.
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
(1) after the intermediate layer film material is prepared into a film by an extrusion and biaxial stretching method, the intermediate layer film 830 is prepared without evaporating aluminum oxide;
the modified polyolefin composite membrane is obtained by the preparation method, and is marked as S4; wherein the first layer 810 has a thickness of 20 μm; the thickness of the interlayer film 830 is 20 μm; the thickness of the third film 850 is 80 μm, and the total thickness of the modified polyolefin composite film is 122 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Example 5
This example illustrates the preparation of a modified polyolefin composite film using the modified polyolefin composite film composition of the present invention and the preparation method of the present invention.
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
(1)810 and 850 are different thicknesses.
The modified polyolefin composite membrane is obtained by the preparation method, and is marked as S5; wherein the first layer 810 has a thickness of 60 μm; the thickness of the interlayer film 830 is 50 μm; the thickness of the third film 850 is 100 μm, and the total thickness of the modified polyolefin composite film is 212 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Example 6
This example illustrates the preparation of a modified polyolefin composite film using the modified polyolefin composite film composition of the present invention and the preparation method of the present invention.
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
(1)810, 830, 850 are different in thickness.
The modified polyolefin composite membrane is obtained by the preparation method, and is marked as S6; wherein the first layer 810 has a thickness of 10 μm; the thickness of the interlayer film 830 is 10 μm; the thickness of the third film 850 is 10 μm, and the total thickness of the modified polyolefin composite film is 32 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Example 7
This example illustrates the preparation of a modified polyolefin composite film using the modified polyolefin composite film composition of the present invention and the preparation method of the present invention.
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
(1) the first glue layer 821 and the second glue layer 822 are polyurethane two-component glue;
(2) after the intermediate layer film material is prepared into a film by an extrusion and biaxial stretching method, the intermediate layer film 830 is prepared without evaporating aluminum oxide;
the modified polyolefin composite membrane is obtained by the preparation method, and is marked as S7; wherein the first layer 810 has a thickness of 20 μm; the thickness of the interlayer film 830 is 20 μm; the thickness of the third film 850 is 80 μm, and the total thickness of the modified polyolefin composite film is 122 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Comparative example 1
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
(1) the modified polyolefin composite film composition does not comprise a barrier layer film material;
(2) after the intermediate layer film material is prepared into a film by an extrusion and biaxial stretching method, the intermediate layer film 830 is prepared without evaporating aluminum oxide;
the modified polyolefin composite membrane is prepared as a result and is marked as D1; wherein the first layer 810 has a thickness of 20 μm; the thickness of the interlayer film 830 is 20 μm; the thickness of the third film 850 is 80 μm, and the thickness of the modified polyolefin composite film is 122 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Comparative example 2
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
(1) PE corona layer (610), polymer bonding layer (210), thermoplasticity barrier layer (950), polymer bonding layer (210), PE heat-seal layer (611), the extrusion capacity proportion is 1: 1.0: 1.0: 1.0: 1.8.
(2) the first glue layer 821 and the second glue layer 822 are modified polyolefin adhesives;
(3) after the intermediate layer film material is prepared into a film by an extrusion and biaxial stretching method, the intermediate layer film 830 is prepared without evaporating aluminum oxide;
the modified polyolefin composite membrane is prepared as a result and is marked as D2; wherein the first layer 810 has a thickness of 20 μm; the thickness of the interlayer film 830 is 20 μm; the thickness of the third film 850 is 80 μm, and the thickness of the modified polyolefin composite film is 128 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Comparative example 3
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
only polyolefin facing film 810: multilayer co-extrusion biaxially oriented polyethylene film.
The modified polyolefin composite membrane is prepared as a result and is marked as D3; wherein the first layer 810 has a thickness of 30 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Comparative example 4
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
only polyolefin facing film 810: multilayer co-extrusion biaxially oriented polypropylene film.
The modified polyolefin composite membrane is prepared as a result and is marked as D4; wherein the first layer 810 has a thickness of 30 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Comparative example 5
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
only polyolefin facing film 810: multilayer coextrusion casting polyethylene film.
The modified polyolefin composite membrane is prepared as a result and is marked as D5; wherein the first layer 810 has a thickness of 30 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Comparative example 6
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
only polyolefin facing film 810: multilayer coextrusion casting polypropylene film.
The modified polyolefin composite membrane is prepared as a result and is marked as D6; wherein the first layer 810 has a thickness of 30 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Comparative example 7
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
(1) the modified polyolefin composite film composition does not comprise an intermediate layer film material;
(2) preparation method of modified polyolefin composite membrane
Bonding the first layer film 810 and the third layer film 850 sequentially through the first glue layer 821 and the second glue layer 822;
the modified polyolefin composite membrane is prepared as a result and is marked as D7; wherein the first layer 810 has a thickness of 20 μm; the thickness of the interlayer film 830 is 0 μm; the thickness of the third film 850 is 80 μm, and the thickness of the modified polyolefin composite film is 101 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Comparative example 8
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
(1) the modified polyolefin composite film composition does not comprise a first layer film material;
(2) preparation method of modified polyolefin composite membrane
The intermediate layer film 830 and the third layer film 850 are bonded to each other sequentially by the first glue layer 821 and the second glue layer 822;
the modified polyolefin composite membrane is prepared as a result and is marked as D8; wherein the first layer 810 has a thickness of 0 μm; the thickness of the interlayer film 830 is 20 μm; the thickness of the third film 850 is 80 μm, and the thickness of the modified polyolefin composite film is 101 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
Comparative example 9
A modified polyolefin composite film was prepared in the same manner as in example 1, except that:
(1) the modified polyolefin composite film composition does not comprise a PE corona layer material, a barrier layer film material and a PE heat sealing layer material;
(2) preparation method of modified polyolefin composite membrane
Bonding the first layer film 810 and the intermediate layer film 830 sequentially by the first glue layer 821 and the second glue layer 822;
the modified polyolefin composite membrane is prepared as a result and is marked as D9; wherein the first layer 810 has a thickness of 20 μm; the thickness of the interlayer film 830 is 20 μm; the thickness of the third film 850 is 0 μm, and the thickness of the modified polyolefin composite film is 41 μm.
In addition, the modified polyolefin composite membrane is subjected to performance tests of maximum puncture force, oxygen transmission capacity and water vapor transmission capacity, and the results are shown in table 1;
in addition, the results of the pressure resistance and the drop property tests of the bag product made of the modified polyolefin composite film are shown in table 2.
TABLE 1
Figure BDA0002864475930000261
As can be seen from the results in table 1, the results of the barrier property and puncture resistance tests of the examples and comparative examples using the technical solution of the present invention show that: the larger the thickness proportion of the multilayer co-extrusion biaxially oriented polyethylene film is, the larger the maximum puncture force is; under the same condition, the solid content proportion of the glue is large, the composite package tends to become hard and brittle, and the maximum puncture force is reduced; the maximum puncture force of polyethylene is greater than that of polypropylene film.
(2) Oxygen transmission amount:
the test result shows that:
the film is evaporated with an alumina layer to obtain excellent oxygen barrier properties.
The thicker the barrier layer of the multilayer coextrusion casting polyethylene barrier film is, the better the barrier property is.
The oxygen resistance of the polyvinyl alcohol glue is higher than that of the common glue sold in the market; the larger the glue coating amount of the polyvinyl alcohol glue, the better the oxygen resistance.
The polypropylene has large steric hindrance due to the side methyl, and the oxygen barrier property of the polypropylene is better than that of the polyethylene under the same film manufacturing process condition.
(3) Water vapor transmission amount:
the test result shows that:
the film is evaporated with an alumina layer to obtain excellent water vapor barrier property.
The polyolefin film and the polyolefin vapor-deposited alumina film have good water vapor resistance. The barrier property of the thermoplastic polyvinyl alcohol barrier layer plays a role in positive superposition, and the water vapor resistance is the best. The larger the ratio of the thicknesses of the biaxially oriented polyethylene films is, the better the water vapor barrier property is.
The polypropylene has side methyl groups and large steric hindrance, and the water vapor barrier property of the polypropylene is superior to that of the polyethylene under the same film manufacturing process conditions.
TABLE 2
Figure BDA0002864475930000271
Figure BDA0002864475930000281
As can be seen from table 2:
the multilayer coextrusion casting barrier film 850 has high heat seal strength, high interlayer peeling strength, good pressure resistance of the bag and strong falling resistance under the conditions that the layer thickness ratio of a non-corona layer (heat seal layer) is high and the glue 820 is appropriate in glue coating amount. The bag is free from leakage and breakage.
The multilayer coextrusion casting barrier film 850 has low or no layer thickness ratio of a non-corona layer (heat-seal layer), and has low heat-seal strength, low interlayer peeling strength, poor pressure resistance of the bag and poor anti-falling performance under the condition of little or no glue 820 gluing amount. The bag leaks and ruptures.
In the polyolefin surface layer film 810, the multi-layer co-extrusion biaxially oriented polyethylene and the multi-layer co-extrusion biaxially oriented polypropylene film are stretched, molecular chains are arranged orderly, the crystallinity is high, and heat sealing is avoided, so that the pressure resistance and the falling resistance of the bag are poor. Bag leakage, rupture; the multilayer co-extrusion casting polyethylene film is not stretched, the molecular chain is smooth, and the thermal bonding strength is slightly higher than that of the multilayer co-extrusion casting polypropylene film. Therefore, the pressure resistance of the bag is slightly better, and the falling resistance is slightly stronger. The bag is free from leakage and breakage.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (24)

1. A modified polyolefin composite film composition is characterized by comprising a first layer film material, a middle layer film material and a third layer film material, wherein the third layer film material comprises a PE corona layer material, a barrier layer film material and a PE heat sealing layer material;
wherein the first layer film and the intermediate layer film each comprise C4-C8One or more of polyethylene, unitary homo-polypropylene, binary co-polypropylene and ternary co-polypropylene;
and the barrier layer film material is thermoplastic polyvinyl alcohol, the melt flow rate of the thermoplastic polyvinyl alcohol at 210 ℃ under the load of 2.16kg is 2-5g/10min, and the density is 0.92-1.3g/cm3；
The PE corona layer material contains first medium-density linear polyethylene and first anti-blocking master batch; based on the total weight of the PE corona layer material, the content of the first medium-density linear polyethylene is 80-99.5 wt%, and the content of the first anti-blocking master batch is 0.5-20 wt%;
the PE heat-sealing layer material contains one or more of second medium-density linear polyethylene, metallocene catalytic polyethylene, high-pressure polyethylene, second anti-adhesion master batch and high-molecular smooth master batch; based on the total weight of the PE heat-seal layer material, the content of the second medium-density linear polyethylene is 10-58.5 wt%, the content of the metallocene-catalyzed polyethylene is 20-30 wt%, the content of the high-pressure polyethylene is 20-40 wt%, the content of the second anti-blocking master batch is 0.5-10 wt%, and the content of the high-molecular smooth master batch is 1-10 wt%;
the first anti-blocking master batch and the second anti-blocking master batch are the same or different and respectively consist of silicon dioxide and medium-density polyethylene, wherein the content of the silicon dioxide is 0.5-1 wt% and the content of the medium-density polyethylene is 99-99.5 wt% based on the total weight of the first anti-blocking master batch or the second anti-blocking master batch;
the metallocene catalyzed polyethylene is C6-C8Metallocene-catalyzed polyethylene; the metallocene catalyzed polyethylene has a melt flow rate of 0.5-4.0g/10min at 190 ℃ under a load of 2.16kg and a density of 0.86-0.930g/cm3；
The high-pressure polyethylene has a melt flow rate of 1.5-4.0g/10min at 190 deg.C under a load of 2.16kg, and a density of 0.89-0.935g/cm3；
The high-molecular smooth master batch is prepared by blending and modifying a blend E, wherein the blend E contains optional silicone, erucamide and third medium-density linear polyethylene; based on the total weight of the blend E, the content of the silicone is 0 to 20 weight percent; the erucamide content is 0.5-10 wt%, and the third medium density linear polyethylene content is 70-99.5 wt%;
the first, second and third medium density linear polyethylenes are the same or different, each having a melt temperature at 190 ℃ under a 2.16kg loadThe volume flow rate is 1.5-4.5g/10min, and the density is 0.87-0.940g/cm3。
2. The composition of claim 1, wherein the thermoplastic polyvinyl alcohol has a melt flow rate of 2.5 to 4g/10min at 210 ℃ under a 2.16kg load and a density of 1 to 1.28g/cm3。
3. The composition of claim 1, wherein the first, second, and third medium density linear polyethylenes are the same or different and each have a melt flow rate of 1.5 to 3.5g/10min at 190 ℃ under a 2.16kg load and a density of 0.89 to 0.92g/cm3。
4. A barrier polyolefin composite film made from the composition according to any of claims 1 to 3, wherein the composite film comprises a first film (810), an intermediate film (830) and a third film (850) stacked in that order, and wherein the first film (810) is extruded from a first material comprising a first film material; the intermediate layer film (830) is obtained by extruding a second material containing an intermediate layer film material;
wherein the third film (850) comprises a PE corona layer (610), a thermoplastic barrier layer (950) and a PE heat-seal layer (611) which are sequentially superposed; and the PE corona layer (610) is obtained by extruding a third material containing the PE corona layer material; the thermoplastic barrier layer (950) is obtained by extruding a fourth material of thermoplastic polyvinyl alcohol; the PE heat-sealing layer (611) is obtained by extruding a fifth material containing the PE heat-sealing layer material.
5. A composite film according to claim 4 wherein the surface of the interlayer film (830) is further coated with an aluminium film.
6. The composite film of claim 5, wherein the aluminum film comprises a vaporized aluminum film and/or an aluminum oxide film.
7. The composite film according to claim 4 wherein the first film (810) has a thickness of 5-80 μm; the thickness of the second layer of film (830) is 5-150 μm; the third layer of film (850) has a thickness of 5-200 μm.
8. A composite film according to claim 7 wherein the first film (810) has a thickness of 9-60 μm; the thickness of the second layer of film (830) is 10-50 μm; the third layer of film (850) has a thickness of 40-100 μm.
9. A composite film according to claim 4 wherein the total thickness of the composite film is from 15 to 430 μm.
10. The composite film of claim 9, wherein the total thickness of the composite film is 59-150 μ ι η.
11. A composite film according to claim 4 wherein the composite film further comprises a first layer of film (810), a first glue layer (821), an intermediate layer of film (830), a second glue layer (822) and a third layer of film (850) stacked in that order.
12. The composite film of claim 11, wherein the first glue layer (821) and the second glue layer (822) are the same or different and are each one or more of a polyvinyl alcohol built glue, a polyurethane two-component glue, and a modified polyolefin adhesive.
13. The composite film of claim 12, wherein the first glue layer (821) and the second glue layer (822) are the same or different and are each a polyvinyl alcohol built glue.
14. The composite film according to claim 12 or 13, wherein the polyvinyl alcohol compound glue comprises a polyvinyl alcohol main agent and a curing agent, and the solid content of the polyvinyl alcohol main agent is 15-32 wt% and the solid content of the curing agent is 10-25 wt% based on the total weight of the polyvinyl alcohol compound glue.
15. The composite film of claim 14, wherein the ratio of the polyvinyl alcohol main agent to the curing agent is 10 (0.5-1.5).
16. A composite film according to claim 11 or 12, wherein the first and second glue layers (821, 822) each have a glue amount of 1-10g/m2。
17. A composite film according to claim 16, wherein the first glue layer (821) and the second glue layer (822) each have a glue amount of 2.5-5g/m2。
18. A composite film according to claim 4 or 11 wherein the third film (850) further comprises a PE corona layer (610), a first polymeric adhesive layer (210), a thermoplastic barrier layer (950), a second polymeric adhesive layer (220) and a PE heat seal layer (611) superimposed in that order.
19. A composite film according to claim 18 wherein the PE corona layer (610), the first polymeric adhesive layer (210), the thermoplastic barrier layer (950), the second polymeric adhesive layer (220), the PE heat seal layer (611) are present in a weight ratio of 1 (0.02-0.95) to (0.02-0.95): (0.02-0.95): (0.5-2).
20. A composite film according to claim 19 wherein the PE corona layer (610), the first polymeric adhesive layer (210), the thermoplastic barrier layer (950), the second polymeric adhesive layer (220), the PE heat seal layer (611) are present in a weight ratio of 1 (0.1-0.6) to (0.1-0.6): (0.1-0.6): (1.0-1.8).
21. A method of making a composite membrane according to any one of claims 4 to 20, said method comprising:
(1) preparing a first layer of film (810) using a first material;
(2) preparing an intermediate layer film (830) using a second material;
(3) preparing a PE corona layer (610) by adopting a third material, preparing a thermoplastic barrier layer (950) by adopting a fourth material, preparing a PE heat-sealing layer (611) by adopting a fifth material, and sequentially bonding the PE corona layer (610), the thermoplastic barrier layer (950) and the PE heat-sealing layer (611) through a first polymer bonding layer (210) and a second polymer bonding layer (220) to prepare a third layer of film (850);
(4) the first film (810), the intermediate film (830) and the third film (850) are sequentially bonded by a first glue layer (821) and a second glue layer (822) to prepare the modified polyolefin composite film.
22. The method of claim 21, wherein the method further comprises: the first layer film (810), the intermediate layer film (830), and the third layer film (850) are made by coextrusion in combination with a stretching process, a blown-tube process, or a casting process.
23. A method according to claim 21 or 22, wherein the surface of the intermediate layer film (830) is aluminized by means of evaporation.
24. Use of a composite film according to any one of claims 4 to 20 in one or more of food packaging, industrial, consumer chemical packaging and medical devices.
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