CN117601529A - High-barrier degradable polyethylene composite film, bag and preparation method - Google Patents
High-barrier degradable polyethylene composite film, bag and preparation method Download PDFInfo
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- CN117601529A CN117601529A CN202311368105.8A CN202311368105A CN117601529A CN 117601529 A CN117601529 A CN 117601529A CN 202311368105 A CN202311368105 A CN 202311368105A CN 117601529 A CN117601529 A CN 117601529A
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- polyethylene
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- 239000004698 Polyethylene Substances 0.000 title claims abstract description 310
- -1 polyethylene Polymers 0.000 title claims abstract description 308
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 306
- 238000002360 preparation method Methods 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000007789 sealing Methods 0.000 claims abstract description 127
- 238000007639 printing Methods 0.000 claims abstract description 118
- 238000013329 compounding Methods 0.000 claims abstract description 17
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 100
- 239000002994 raw material Substances 0.000 claims description 89
- 239000000155 melt Substances 0.000 claims description 74
- 230000015556 catabolic process Effects 0.000 claims description 61
- 238000006731 degradation reaction Methods 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 55
- 229920001684 low density polyethylene Polymers 0.000 claims description 48
- 239000004702 low-density polyethylene Substances 0.000 claims description 48
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 42
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 38
- 230000004888 barrier function Effects 0.000 claims description 24
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 24
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 24
- 229920001179 medium density polyethylene Polymers 0.000 claims description 16
- 239000004701 medium-density polyethylene Substances 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 13
- 229920001903 high density polyethylene Polymers 0.000 claims description 12
- 239000004700 high-density polyethylene Substances 0.000 claims description 12
- 238000010096 film blowing Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 9
- 238000009264 composting Methods 0.000 abstract description 7
- 238000004806 packaging method and process Methods 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 235000013305 food Nutrition 0.000 abstract description 5
- 229920000426 Microplastic Polymers 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 282
- 238000001125 extrusion Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000003292 glue Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012793 heat-sealing layer Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000012940 solvent-free polyurethane adhesive Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
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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
- 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
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- 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
- B65D31/00—Bags or like containers made of paper and having structural provision for thickness of contents
-
- 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
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- 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
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- 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
- B32B2307/716—Degradable
-
- 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
- B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D2565/38—Packaging materials of special type or form
- B65D2565/381—Details of packaging materials of special type or form
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of polyethylene composite films, and provides a high-barrier degradable polyethylene composite film, a high-barrier degradable polyethylene composite bag and a preparation method of the high-barrier degradable polyethylene composite film. The high-barrier degradable polyethylene composite film provided by the invention is obtained by compounding a degradable polyethylene printing film and a high-barrier polyethylene heat-sealing film. The high-barrier degradable polyethylene composite film provided by the invention has the advantages of excellent mechanical property, high transparency, good printability, high oxygen resistance and high water resistance, can be effectively degraded under the conditions of light, hot oxygen and composting, can be completely degraded into carbon dioxide and water, and can not generate microplastic, so that the high-barrier degradable polyethylene composite film provided by the invention has wide application prospect and can be used as packaging bags of foods, daily chemicals and the like.
Description
Technical Field
The invention relates to the technical field of polyethylene films, in particular to a high-barrier degradable polyethylene composite film, a high-barrier degradable polyethylene composite bag and a preparation method of the high-barrier degradable polyethylene composite film.
Background
Polyethylene films are widely used in various industries, and can be used as shrink films, optical protective films, shopping bags, food packaging bags and the like. When the polyethylene film is used as a packaging bag, the polyethylene film is required to have certain strength, is not easy to damage in the transportation process, and cannot cause leakage of packaging contents; when the polyethylene film is used as a food packaging bag, the polyethylene film is also required to have higher barrier properties, such as oxygen resistance, water resistance and the like, so that the deterioration of the packaging content is avoided. However, the polyethylene film has good stability, is not easy to decompose, and the discarded PE film is difficult to be subjected to innocent treatment. With the rising of the global plastic usage, the pressure generated by plastic garbage is heavier, the environmental pollution problem generated by waste plastic is more and more concerned by people, and the environmental protection and social responsibility are required to be changed into sustainable development worldwide.
Degradable films refer to films that can be completely degraded into harmless substances under certain conditions. At present, the degradable film is generally prepared from degradable materials, but the existing degradable film has the defects of low strength, poor barrier property, poor transparency, printing ink dropping and the like, can only be used in the fields with low requirements such as shopping bags, garbage bags and the like, and cannot be used in the fields with high requirements such as foods, daily chemicals and the like.
Disclosure of Invention
In view of this, the present invention provides a high barrier degradable polyethylene composite film, bag and method of making. The high-barrier degradable polyethylene composite film provided by the invention has the advantages of good mechanical property, good barrier property, high transparency, no ink drop during printing and excellent degradability.
In order to achieve the above object, the present invention provides the following technical solutions:
a high-barrier degradable polyethylene composite film is obtained by compounding a degradable polyethylene printing film and a high-barrier polyethylene heat-sealing film;
the degradable polyethylene printing film comprises an outer layer, a middle layer and an inner layer;
the preparation raw materials of the outer layer and the inner layer of the degradable polyethylene printing film comprise the following components in parts by weight: 10-30 parts of medium density polyethylene, 30-70 parts of high density polyethylene, 15-40 parts of medium density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
The preparation raw materials of the middle layer of the degradable polyethylene printing film comprise the following components in parts by mass: 10-40 parts of first medium-density metallocene polyethylene, 10-30 parts of second medium-density metallocene polyethylene, 30-85 parts of high-strength low-density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
the high-barrier polyethylene heat-sealing film comprises an outer layer, a middle layer and an inner layer;
the preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10-30 parts of low-density polyethylene, 15-40 parts of low-density metallocene polyethylene, 20-75 parts of linear low-density polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
the preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10-30 parts of low-density polyethylene, 10-50 parts of linear low-density polyethylene, 30-80 parts of low-density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
the preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10 to 25 parts of low-density polyethylene, 30 to 80 parts of low-density metallocene polyethylene, 20 to 60 parts of ultra-low-density metallocene polyethylene, 1.5 to 2.5 parts of degradation master batch and 0.5 to 1 part of processing aid.
Preferably, the degradable polyethylene printing film outer layer and the degradable polyethylene printing film inner layer are prepared from the following raw materials: the melt index of the medium density polyethylene is 2.5-3.5 g/10min, and the density is 0.925-0.940 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the high-density polyethylene is 0.3-1.5 g/10min, and the density is 0.955-0.970 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the medium density metallocene polyethylene is 0.2-1.0 g/10min, and the density is 0.925-0.940 g/cm 3 ；
The preparation raw materials of the middle layer of the degradable polyethylene printing film comprise: the melt index of the first medium density metallocene polyethylene is 0.2-1.0 g/10min, and the density is 0.935-0.945 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the second medium density metallocene polyethylene is 2.0-3.0 g/10min, and the density is 0.930-0.940 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the high-strength low-density metallocene polyethylene is 0.2-1.0 g/10min, and the density is 0.910-0.920 g/cm 3 。
Preferably, the preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise: the melt index of the low density polyethylene is 1.5-2.5 g/10min, and the density is 0.920-0.930 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the low-density metallocene polyethylene is 1.5-2.5 g/10min, and the density is 0.908-0.920 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the linear low density polyethylene is 1.5-2.5 g/10min, and the density is 0.910-0.925 g/cm 3 ；
The preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise: the melt index of the low density polyethylene is 1.5-2.5 g/10min, and the density is 0.920-0.930 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the linear low density polyethylene is 1.5-2.5 g/10min, and the density is 0.910-0.925 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the low-density metallocene polyethylene is 0.5-2.0 g/10min, and the density is 0.910-0.925 g/cm 3 ；
The preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise: the melt index of the low density polyethylene is 1.5-2.5 g/10min, and the density is 0.920-0.930 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the low-density metallocene polyethylene is 0.3-1.5 g/10min, and the density is 0.900-0.915 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the ultra-low density metallocene polyethylene is 0.5-1.8 g/10min, and the density is 0.890-0.915 g/cm 3 。
PreferablyThe degradable master batches used for the outer layer, the middle layer and the inner layer of the degradable polyethylene printing film and the outer layer, the middle layer and the inner layer of the high-barrier polyethylene heat-sealing film have the melt fingers of 46-55 g/10min and the density of 0.920-0.940 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the processing aid is 1.5.0-2.8 g/10min, and the density is 0.910-0.920 g/cm 3 。
Preferably, the degradable polyethylene printing film outer layer and the degradable polyethylene printing film inner layer are prepared from the following raw materials: the brand of the medium density polyethylene is 151BW, the brand of the high density polyethylene is 8300, and the brand of the medium density metallocene polyethylene is 3505MA;
the preparation raw materials of the middle layer of the degradable polyethylene printing film comprise: the brand of the first medium-density metallocene polyethylene is 4009, the brand of the second medium-density metallocene polyethylene is 2036P, and the brand of the high-strength low-density metallocene polyethylene is XP6056ML;
The preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise: the brand of the low-density polyethylene is 2420H, the brand of the low-density metallocene polyethylene is 1520, and the brand of the linear low-density polyethylene is 7042;
the preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise: the brand of the low-density polyethylene is 2420H, the brand of the linear low-density polyethylene is 201XV, and the brand of the low-density metallocene polyethylene is 1018BN;
the preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise: the brand of the low-density polyethylene is 2426H, the brand of the low-density metallocene polyethylene is AT6202, and the brand of the ultra-low-density metallocene polyethylene is SP0510H;
the outer layer, the middle layer and the inner layer of the degradable polyethylene printing film are made of high-barrier polyethylene heat-sealing film, the brand of degradation master batch used by the outer layer, the middle layer and the inner layer is TRF-57, and the brand of processing aid is PA0895LD.
Preferably, the thickness of the degradable polyethylene printing film is 30-80 mu m, and the thickness of the high-barrier degradable polyethylene heat-sealing film is 40-100 mu m;
the degradable polyethylene printing film comprises the following components: the mass fraction of the outer layer is 20-30%, the mass fraction of the middle layer is 40-60%, and the mass fraction of the inner layer is 20-30%;
The high-barrier degradable polyethylene heat-sealing film comprises the following components: the mass fraction of the outer layer is 25-30%, the mass fraction of the middle layer is 40-50%, and the mass fraction of the inner layer is 25-30%.
The invention also provides a preparation method of the high-barrier degradable polyethylene composite film, which comprises the following steps:
carrying out three-layer coextrusion film blowing on preparation raw materials of an outer layer, a middle layer and an inner layer of the degradable polyethylene printing film to obtain the degradable polyethylene printing film;
performing three-layer coextrusion film blowing on the preparation raw materials of the outer layer, the middle layer and the inner layer of the high-barrier degradable polyethylene heat-sealing film to obtain the high-barrier degradable polyethylene heat-sealing film;
and compounding the degradable polyethylene printing film and the high-barrier degradable polyethylene heat-sealing film by adopting an adhesive, and curing to obtain the high-barrier degradable polyethylene composite film.
Preferably, before the degradable polyethylene printing film and the high-barrier degradable polyethylene heat-sealing film are compounded, printing is further carried out on the surface of the degradable polyethylene printing film.
Preferably, the curing temperature is 35-45 ℃ and the curing time is 24-48 h.
The invention also provides a high-barrier degradable polyethylene composite bag which is prepared from the high-barrier degradable polyethylene composite film, wherein the high-barrier degradable polyethylene composite film is the high-barrier degradable polyethylene composite film according to the scheme or the high-barrier degradable polyethylene composite film prepared by the preparation method according to the scheme.
The invention provides a high-barrier degradable polyethylene composite film, which is obtained by compounding a degradable polyethylene printing film and a high-barrier polyethylene heat-sealing film; the degradable polyethylene printing film comprises an outer layer, a middle layer and an inner layer; the preparation raw materials of the outer layer and the inner layer of the degradable polyethylene printing film comprise the following components in parts by weight: 10-30 parts of medium density polyethylene, 30-70 parts of high density polyethylene, 15-40 parts of medium density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid; the preparation raw materials of the middle layer of the degradable polyethylene printing film comprise the following components in parts by mass: 10-40 parts of first medium-density metallocene polyethylene, 10-30 parts of second medium-density metallocene polyethylene, 30-85 parts of high-strength low-density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid; the high-barrier polyethylene heat-sealing film comprises an outer layer, a middle layer and an inner layer; the preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10-30 parts of low-density polyethylene, 15-40 parts of low-density metallocene polyethylene, 20-75 parts of linear low-density polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid; the preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10-30 parts of low-density polyethylene, 10-50 parts of linear low-density polyethylene, 30-80 parts of low-density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid; the preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10 to 25 parts of low-density polyethylene, 30 to 80 parts of low-density metallocene polyethylene, 20 to 60 parts of ultra-low-density metallocene polyethylene, 1.5 to 2.5 parts of degradation master batch and 0.5 to 1 part of processing aid. The preparation raw materials of three layers in the degradable polyethylene printing film and the high-barrier polyethylene heat-sealing film are strictly controlled, so that the degradable polyethylene printing film and the high-barrier polyethylene heat-sealing film are ensured to have higher mechanical property and transparency, meanwhile, the degradable polyethylene printing film has excellent printing property, the ink layer has high bonding fastness, the high-barrier polyethylene heat-sealing film has excellent barrier property, and the water vapor transmittance and the oxygen transmittance are lower; meanwhile, the invention also adds degradation master batch into three layers of the degradable polyethylene printing film and the high-barrier polyethylene heat-sealing film, so that the film has degradability. In conclusion, the high-barrier degradable polyethylene composite film is compounded with the high-barrier polyethylene heat-sealing film, has excellent mechanical property, high transparency, good printability and high oxygen and water resistance, can be effectively degraded under the conditions of light, thermal oxygen and composting, can be completely degraded into carbon dioxide and water, and does not generate microplastic, so that the high-barrier degradable polyethylene composite film provided by the invention has wide application prospect and can be used as packaging bags of foods, daily chemicals and the like.
Detailed Description
The invention provides a high-barrier degradable polyethylene composite film, which is obtained by compounding a degradable polyethylene printing film and a high-barrier polyethylene heat-sealing film;
the degradable polyethylene printing film comprises an outer layer, a middle layer and an inner layer;
the preparation raw materials of the outer layer and the inner layer of the degradable polyethylene printing film comprise the following components in parts by weight: 10-30 parts of medium density polyethylene, 30-70 parts of high density polyethylene, 15-40 parts of medium density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
the preparation raw materials of the middle layer of the degradable polyethylene printing film comprise the following components in parts by mass: 10-40 parts of first medium-density metallocene polyethylene, 10-30 parts of second medium-density metallocene polyethylene, 30-85 parts of high-strength low-density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
the high-barrier polyethylene heat-sealing film comprises an outer layer, a middle layer and an inner layer;
the preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10-30 parts of low-density polyethylene, 15-40 parts of low-density metallocene polyethylene, 20-75 parts of linear low-density polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
The preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10-30 parts of low-density polyethylene, 10-50 parts of linear low-density polyethylene, 30-80 parts of low-density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
the preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10 to 25 parts of low-density polyethylene, 30 to 80 parts of low-density metallocene polyethylene, 20 to 60 parts of ultra-low-density metallocene polyethylene, 1.5 to 2.5 parts of degradation master batch and 0.5 to 1 part of processing aid.
The high barrier degradable polyethylene composite film of the present invention is described in detail below.
The components of the degradable polyethylene print film will be described first.
The preparation raw materials of the outer layer of the degradable polyethylene printing film comprise 10-30 parts by mass, preferably 15-25 parts by mass of medium density polyethylene; the melt index of the medium density polyethylene is preferably 2.5-3.5 g/10min, and the density is preferably 0.925-0.940 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the specific embodiment of the invention, the medium density polyethylene is preferably 151BW, the melt index is preferably 3g/10min, and the density is preferably 0.933g/cm 3 The manufacturer is Ikson; the medium density polyethylene adopted by the invention has the characteristics of high temperature resistance, good transparency, high easy-to-add compound fastness, easy processing and the like.
Based on the weight parts of the medium-density polyethylene adopted by the outer layer of the degradable polyethylene printing film, the preparation raw materials of the outer layer of the degradable polyethylene printing film comprise 30-70 parts of high-density polyethylene, preferably 40-60 parts; the melt index of the high-density polyethylene is preferably 0.3-1.5 g/10min, and the density is preferably 0.955-0.970 g/cm 3 In the specific embodiment of the invention, the high-density polyethylene has the brand 8300, the melt index of which is preferably 0.7g/10min, and the density of which is preferably 0.963g/cm 3 The manufacturer is SK chemistry; the high-density polyethylene adopted by the invention has the properties of high temperature resistance, high strength, few crystal points and good transparency.
Based on the weight parts of the medium density polyethylene adopted by the outer layer of the degradable polyethylene printing film, the preparation raw materials of the outer layer of the degradable polyethylene printing film comprise 15-40 parts of medium density metallocene polyethylene, preferably 20-30 parts; the melt index of the medium density metallocene polyethylene is preferably 0.2-1.0 g/10min, and the density is preferably 0.925-0.940 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In a specific embodiment of the present invention, the medium density metallocene polyethylene has a trade name of 3505MA, preferably 0.5g/10min in melt index, and a density of 0.935g/cm 3 The manufacturer is Exxon. The medium density metallocene polyethylene adopted by the invention has the characteristics of high temperature resistance, good transparency, good toughness, easy processing and the like.
Based on the weight parts of the medium-density polyethylene adopted by the outer layer of the degradable polyethylene printing film, the preparation raw materials of the outer layer of the degradable polyethylene printing film comprise 1.5-2.5 parts of degradation master batch, preferably 2 parts; the melt index of the degradation master batch is preferably 46-55 g/10min, more preferably 50-52 g/10min, and the density is preferably 0.920-0.940 g/cm 3 More preferably 0.925 to 0.935g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the specific embodiment of the invention, the brand of the degradation master batch is preferably TRF-57, the melt index is preferably 51g/10min, and the density is preferably 0.93g/cm 3 The manufacturer is Polymaterial in England; the degradation master batch adopted by the invention can convert polyethylene into the bio-usable wax, does not need specific environmental degradation, does not leave micro plastics or toxic substances after degradation, and is harmless to the nature; in addition, after the degradation master batch is added, the physical properties of the film are not changed, and compared with other degradation films, the film has wider application range and lower cost; the original process equipment is not required to be changed when the degradation master batch is added, and the degradation master batch can be recycled and granulated together with common plastics without influencing physical properties. Specifically, under the catalytic action of the degradation master batch, the polyethylene can undergo the following three chemical reactions: 1. when the polyethylene is subjected to the action of light, heat and other energy, the chain of the polyethylene molecular bond carbon structure is triggered to break so as to generate high-activity free radicals; 2. the free radical grows, and the high-activity free radical reacts rapidly under the aerobic condition to generate intermediate products such as peroxy free radical or hydroperoxy free radical; 3. chain termination, molecular bond rupture and a series of chemical reactions of the compound containing unstable peroxy free radicals or hydroperoxy free radicals are carried out to generate hydrocarbon oxygen structure micromolecular compound which is finally changed into carbon dioxide, water and wax, the compound is nontoxic and harmless to nature, and the wax is subjected to bioconversion under the condition of open environment temperature through bacteria and fungi naturally existing in soil; the finally obtained degradable polyethylene printing film meets the degradation requirements of ASTM6954, GB/T20197 and BSI PAS 9017.
Based on the weight parts of the medium-density polyethylene adopted by the outer layer of the degradable polyethylene printing film, the preparation raw materials of the outer layer of the degradable polyethylene printing film comprise 0.5-1 part of processing aid, preferably 0.8-1 part; the melt index of the processing aid is preferably 1.5% to the extent2.8g/min, more preferably 1.8-2.5 g/min, and the density is preferably 0.910-0.920 g/cm 3 More preferably 0.912 to 0.915g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The processing aid is preferably a functional master batch prepared from a fluoropolymer and a polyolefin resin; in a specific embodiment of the present invention, the processing aid is preferably of the type PA0895LD, the melt index of which is preferably 2.1g/min, and the density of which is preferably 0.915g/cm 3 The manufacturer is Suzhou Kang Sitan engineering plastics Co., ltd, and the processing aid adopted by the invention can effectively reduce die orifice accumulated materials, reduce crystal points, reduce extrusion pressure and improve production efficiency.
The preparation raw materials of the middle layer of the degradable polyethylene printing film comprise 10-40 parts by mass, preferably 20-30 parts by mass, of first medium-density metallocene polyethylene; the melt index of the first medium density metallocene polyethylene is preferably 0.2-1.0 g/10min, and the density is preferably 0.935-0.945 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In a specific embodiment of the present invention, the first medium density metallocene polyethylene has a brand 4009, preferably a melt index of 0.5g/10min, and a density of 0.94g/cm 3 The manufacturer is Ikson; the first medium density metallocene polyethylene adopted by the invention has the characteristics of high temperature resistance, good transparency and good toughness.
Based on the weight parts of the first medium density metallocene polyethylene adopted in the middle layer of the degradable polyethylene printing film, the preparation raw materials of the middle layer of the degradable polyethylene printing film comprise 10-30 parts, preferably 15-25 parts, of the second medium density metallocene polyethylene; the melt index of the second medium density metallocene polyethylene is preferably 2.0-3.0 g/10min, and the density is preferably 0.930-0.940 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In a specific embodiment of the present invention, the second medium density metallocene polyethylene has a brand 2036P, a melt index of preferably 2.5g/10min, and a density of preferably 0.935g/cm 3 The manufacturer is the Dow chemical. The second medium density metallocene polyethylene adopted by the invention has the characteristics of high transparency, good toughness and easy processing.
Taking the weight part of the first medium-density metallocene polyethylene adopted in the middle layer of the degradable polyethylene printing film as a reference, the preparation raw material package of the middle layer of the degradable polyethylene printing film30 to 85 parts, preferably 40 to 70 parts, of high-strength low-density metallocene polyethylene; the melt index of the high-strength low-density metallocene polyethylene is preferably 0.2-1.0 g/10min, and the density is preferably 0.910-0.920 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In a specific embodiment of the present invention, the high strength low density metallocene polyethylene has a brand XP6056ML, preferably 0.5g/10min melt index and 0.916g/cm density 3 The manufacturer is Ikson; the high-strength low-density metallocene polyethylene adopted by the invention has the characteristics of good transparency, good toughness and high puncture strength.
Based on the weight parts of the first medium-density metallocene polyethylene adopted in the middle layer of the degradable polyethylene printing film, the preparation raw materials of the middle layer of the degradable polyethylene printing film comprise 1.5-2.5 parts of degradation master batches, preferably 2 parts of degradation master batches, and the melt fingers, density and specific marks of the degradation master batches adopted in the middle layer of the degradable polyethylene printing film are preferably consistent with those of the degradation master batches used in the outer layer, and are not repeated here.
Based on the weight parts of the first medium-density metallocene polyethylene adopted in the middle layer of the degradable polyethylene printing film, the preparation raw materials of the middle layer of the degradable polyethylene printing film comprise 0.5-1 part of processing aid, preferably 0.5-0.6 part; the melt fingers and density of the processing aid adopted in the middle layer of the degradable polyethylene printing film are preferably consistent with those of the processing aid used in the outer layer, and are not repeated here.
In the invention, the preparation raw materials of the inner layer and the outer layer of the degradable polyethylene printing film are consistent, and are not repeated here.
The components of the high barrier polyethylene heat seal film are described below.
The preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise 10-30 parts by mass, preferably 15-25 parts by mass of low-density polyethylene; the melt index of the low-density polyethylene is preferably 1.5-2.5 g/10min, and the density is preferably 0.920-0.930 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the specific embodiment of the invention, the low-density polyethylene has the brand of 2420H, the melt index of which is preferably 2g/10min, and the density of which is preferably 0.924g/cm 3 The manufacturer is Yangzi basf; the inventionThe low-density polyethylene adopted obviously has the characteristics of good transparency, compound fastness and easy processing.
Based on the weight parts of the low-density polyethylene adopted by the outer layer of the high-barrier polyethylene heat-sealing film, the preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise 15-40 parts of low-density metallocene polyethylene, and preferably 20-30 parts; the melt index of the low-density metallocene polyethylene is preferably 1.5-2.5 g/10min, and the density is preferably 0.908-0.920 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In a specific embodiment of the present invention, the low density metallocene polyethylene has a brand 1520, preferably a melt index of 1.9g/10min, and a density of 0.913g/cm 3 The manufacturer was Sanjingchu chemical Co. The low-density metallocene polyethylene adopted by the invention has the properties of good coating adhesion, high transparency, high toughness and few crystal points.
Based on the weight parts of the low-density polyethylene adopted by the outer layer of the high-barrier polyethylene heat-sealing film, the preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise 20-75 parts of linear low-density polyethylene, preferably 30-60 parts; the melt index of the linear low density polyethylene is preferably 1.5-2.5 g/10min, and the density is preferably 0.910-0.925 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the specific embodiment of the invention, the linear low density polyethylene is preferably 7042, the melt index is preferably 2g/10min, and the density is preferably 0.918g/cm 3 The manufacturer is the Zhonghai shell; the linear low-density polyethylene adopted by the invention has the characteristics of good compound fastness, good toughness and easy processing.
The preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise 1.5-2.5 parts, preferably 2 parts, of degradation master batch based on the weight parts of the low-density polyethylene adopted by the outer layer of the high-barrier polyethylene heat-sealing film, and the melt fingers, density and specific brands of the degradation master batch adopted by the outer layer of the high-barrier polyethylene heat-sealing film are preferably consistent with those of the degradation master batch used by the outer layer of the degradable polyethylene printing film, and are not repeated herein.
The preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise 0.5-1 part of processing aid, preferably 0.5-0.6 part of processing aid based on the weight parts of low-density polyethylene adopted by the outer layer of the high-barrier polyethylene heat-sealing film; the melt fingers and density of the processing aid adopted by the outer layer of the high-barrier polyethylene heat-sealing film are preferably consistent with those of the processing aid used by the outer layer of the degradable polyethylene printing film, and are not repeated here.
The preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise 10-30 parts by mass, preferably 15-25 parts by mass of low-density polyethylene; the melt index of the low-density polyethylene is preferably 1.5-2.5 g/10min, and the density is preferably 0.920-0.930 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the specific embodiment of the invention, the low-density polyethylene is preferably 2420H, the melt index is preferably 2g/10min, and the density is preferably 0.924g/cm 3 The manufacturer is Yangzi basf; the low-density polyethylene adopted by the invention has the characteristics of good transparency, good compound fastness, easy processing and the like.
Based on the weight parts of the low-density polyethylene adopted in the middle layer of the high-barrier polyethylene heat-sealing film, the preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise 10-50 parts of linear low-density polyethylene, preferably 20-40 parts; the melt index of the linear low density polyethylene is preferably 1.5-2.5 g/10min, and the density is preferably 0.910-0.925 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In a specific embodiment of the present invention, the linear low density polyethylene is preferably 201XV, the melt index is preferably 2g/10min, and the density is preferably 0.918g/cm 3 The manufacturer is Ikson; the linear low-density polyethylene adopted by the invention has the characteristics of good transparency, good toughness and easy processing.
Based on the weight parts of the low-density polyethylene adopted in the middle layer of the high-barrier polyethylene heat-sealing film, the preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise 30-80 parts of low-density metallocene polyethylene, preferably 40-70 parts; the melt index of the low-density metallocene polyethylene is preferably 0.5-2.0 g/10min, and the density is preferably 0.910-0.925 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In a specific embodiment of the present invention, the low density metallocene polyethylene is preferably 1018BN, the melt index is preferably 1g/10min, and the density is preferably 0.918g/cm 3 The manufacturer is LG chemistry; the low-density metallocene polyethylene used in the invention hasHas the properties of high transparency, high toughness and few crystal points.
Based on the weight parts of the low-density polyethylene adopted in the middle layer of the high-barrier polyethylene heat-sealing film, the preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise 1.5-2.5 parts, preferably 2 parts of degradation master batches, and the melt fingers, the density and the specific brands of the degradation master batches adopted in the middle layer of the high-barrier polyethylene heat-sealing film are preferably consistent with those of the degradation master batches used in the outer layer of the degradable polyethylene printing film, and are not repeated herein.
Based on the weight parts of the low-density polyethylene adopted in the middle layer of the high-barrier polyethylene heat-sealing film, the preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise 0.5-1 part of processing aid, preferably 0.5-0.6 part; the melt fingers and density of the processing aid adopted in the middle layer of the high-barrier polyethylene heat-sealing film are preferably consistent with those of the processing aid used in the outer layer of the degradable polyethylene printing film, and are not repeated here.
The preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise 10-25 parts by mass, preferably 15-20 parts by mass of low-density polyethylene; the melt index of the low-density polyethylene is preferably 1.5-2.5 g/10min, and the density is preferably 0.920-0.930 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the specific embodiment of the invention, the low-density polyethylene is preferably 2426H, the melt index is preferably 2g/10min, and the density is preferably 0.924g/cm 3 The manufacturer is the Ming division of China petrochemical company, and the low-density polyethylene has the characteristics of good transparency, good heat sealing property, good opening property, easy processing and the like.
Based on the weight parts of the low-density polyethylene adopted by the inner layer of the high-barrier polyethylene heat-sealing film, the preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise 30-80 parts, preferably 40-70 parts, of low-density metallocene polyethylene, the melt index of the low-density metallocene polyethylene is preferably 0.3-1.5 g/10min, and the density is preferably 0.900-0.915 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In a specific embodiment of the present invention, the low density metallocene polyethylene is preferably of the type AT6202, the melt index of which is preferably 0.85g/10min, and the density of which is preferably 0.908g/cm 3 The manufacturer is the Dow chemical, theThe low-density metallocene polyethylene has excellent pollution-resistant heat sealing property, low sealing temperature, high toughness and few crystal points.
Based on the weight parts of the low-density polyethylene adopted by the inner layer of the high-barrier polyethylene heat-sealing film, the preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise 20-60 parts of ultra-low-density metallocene polyethylene, and preferably 30-50 parts; the melt index of the ultra-low density metallocene polyethylene is preferably 0.5-1.8 g/10min, and the density is preferably 0.890-0.915 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the specific embodiment of the invention, the brand of the ultra-low density metallocene polyethylene is preferably 0510H, the melt index is preferably 1.2g/10min, and the density is preferably 0.904g/cm 3 The manufacturer is Sanjing chemical Co., ltd, and the ultra-low density metallocene polyethylene has excellent pollution-resistant heat sealing property, ultra-low sealing temperature, high heat sealing strength and few crystal points.
Based on the weight parts of the low-density polyethylene adopted by the inner layer of the high-barrier polyethylene heat-sealing film, the preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise 1.5 to 2.5 parts, preferably 2 parts of degradation master batches, and the melt fingers, the density and the specific brands of the degradation master batches adopted by the inner layer of the high-barrier polyethylene heat-sealing film are preferably consistent with those of the degradation master batches used by the outer layer of the degradable polyethylene printing film, and are not repeated herein.
The preparation raw materials of the high-barrier polyethylene heat-sealing film inner layer comprise 0.5-1 part of processing aid, preferably 0.5-0.6 part, based on the weight parts of low-density polyethylene adopted by the high-barrier polyethylene heat-sealing film inner layer; the melt fingers and density of the processing aid adopted by the inner layer of the high-barrier polyethylene heat-sealing film are preferably consistent with those of the processing aid used by the outer layer of the degradable polyethylene printing film, and are not repeated here.
In the present invention, in the degradable polyethylene print film: the mass fraction of the outer layer is preferably 20-30%, the mass fraction of the middle layer is preferably 40-60%, and the mass fraction of the inner layer is preferably 20-30%; the high-barrier degradable polyethylene heat-sealing film comprises the following components: the mass fraction of the outer layer is 25-30%, the mass fraction of the middle layer is 40-50%, and the mass fraction of the inner layer is 25-30%.
In the present invention, the thickness of the degradable polyethylene print film is preferably 30 to 80 μm, more preferably 40 μm, and the thickness of the high barrier degradable polyethylene heat seal film is preferably 40 to 100 μm, more preferably 60 μm; the thickness of the high-barrier degradable polyethylene composite film is preferably 70-180 μm, more preferably 100 μm.
In the invention, the longitudinal tensile strength of the degradable polyethylene printing film is preferably 44-46 MPa, the transverse tensile strength is preferably 42-43 MPa, the longitudinal elongation at break is preferably 590-620%, the transverse elongation at break is preferably 710-720%, the haze is preferably 10.5% or less, more preferably 10.1% or less, and the wetting tension is preferably 40-45 mN/15mm.
In the invention, the longitudinal tensile strength of the high-barrier degradable polyethylene heat-sealing film is preferably 32-34 MPa, the transverse tensile strength is preferably 29-31 MPa, the longitudinal elongation at break is preferably 540-560%, the transverse elongation at break is preferably 730-740%, the haze is preferably less than or equal to 10.5%, more preferably less than or equal to 10.3%, the wetting tension is preferably 40-45 mN/15mm, the water vapor permeability is preferably less than or equal to 4.5%, more preferably less than or equal to 4.1%, and the oxygen permeability is preferably less than or equal to 3.5%.
In the invention, the high-barrier degradable polyethylene composite film is obtained by compounding a degradable polyethylene printing film and a high-barrier polyethylene heat-sealing film, and specifically, the outer layer (namely a corona layer) of the degradable polyethylene printing film and the outer layer (namely a corona layer) of the high-barrier polyethylene heat-sealing film are bonded during compounding; the outer layer of the degradable polyethylene printing film is a printing layer, and specifically, the printing layer is compounded after the printing is finished.
In the invention, the longitudinal tensile strength of the high-barrier degradable polyethylene composite film is preferably 38-39 MPa, the transverse tensile strength is preferably 35-37 MPa, the longitudinal elongation at break is preferably 450-460%, the transverse elongation at break is preferably 710-720%, the haze is preferably less than or equal to 12.5%, more preferably less than or equal to 12.3%, the wetting tension is preferably 40-45 mN/15mm, the water vapor transmittance is preferably less than or equal to 4.0%, more preferably less than or equal to 3.7%, and the oxygen transmittance is preferably less than or equal to 3.5%; the high-barrier degradable polyethylene composite film can realize effective degradation under the conditions of natural environment, photodegradation, thermal oxygen degradation and composting.
The invention also provides a preparation method of the high-barrier degradable polyethylene composite film, which comprises the following steps:
carrying out three-layer coextrusion film blowing on preparation raw materials of an outer layer, a middle layer and an inner layer of the degradable polyethylene printing film to obtain the degradable polyethylene printing film;
performing three-layer coextrusion film blowing on the preparation raw materials of the outer layer, the middle layer and the inner layer of the high-barrier degradable polyethylene heat-sealing film to obtain the high-barrier degradable polyethylene heat-sealing film;
and compounding the degradable polyethylene printing film and the high-barrier degradable polyethylene heat-sealing film by adopting an adhesive, and curing to obtain the high-barrier degradable polyethylene composite film.
The preparation raw materials of the outer layer, the middle layer and the inner layer of the degradable polyethylene printing film are subjected to three-layer coextrusion film blowing (marked as a first coextrusion film blowing) to obtain the degradable polyethylene printing film. In the invention, the process of the first coextrusion blown film specifically comprises the following steps: and respectively feeding the preparation raw materials of the outer layer, the middle layer and the inner layer into an outer layer extruder, a middle layer extruder and an inner layer extruder for melting and plasticizing, conveying the obtained glue solution to a die head, extruding and blowing a film to obtain a film bubble, and sequentially carrying out bubble stabilizing, upper traction, corona treatment, trimming, lower traction and rolling after cooling the film bubble to obtain the degradable polyethylene printing film.
In the invention, the outer layer extruder, the middle layer extruder and the inner layer extruder adopted by the first co-extrusion film blowing are all preferably provided with 5 heating areas, and are sequentially marked as 1 area to 5 areas according to the passing sequence of raw materials; the die head is provided with 4 heating areas, which are sequentially marked as 1 area to 4 areas according to the passing sequence of raw materials.
In the present invention, the extrusion temperatures of the outer layer extruder, the middle layer extruder, the inner layer extruder and the respective zones of the die head used for the first co-extrusion blown film are shown in table 1:
TABLE 1 extrusion temperatures of the outer, middle and inner layer extruders and die head regions of the first co-extrusion blown film
In the invention, the extrusion pressure of the first extrusion blown film outer layer extruder is preferably 225-315 bar, the extrusion pressure of the middle layer extruder is preferably 215-355 bar, and the extrusion pressure of the inner layer extruder is preferably 205-285 bar.
The preparation raw materials of the outer layer, the middle layer and the inner layer of the high-barrier degradable polyethylene heat-seal film are subjected to three-layer coextrusion film blowing (marked as a second coextrusion film blowing), so that the high-barrier degradable polyethylene heat-seal film is obtained. In the present invention, the specific operation process of the second co-extrusion blown film is consistent with that of the first co-extrusion blown film, and will not be described herein again; the outer layer extruder, the middle layer extruder and the inner layer extruder adopted by the second coextrusion blown film are all preferably provided with 5 heating areas, and are sequentially marked as 1 area to 5 areas according to the passing sequence of raw materials; the die head is provided with 4 heating areas, which are sequentially marked as 1 area to 4 areas according to the passing sequence of raw materials.
In the present invention, the extrusion temperatures of the outer layer extruder, the middle layer extruder, the inner layer extruder and the respective zones of the die head used for the second co-extrusion blown film are shown in table 2:
TABLE 2 extrusion temperatures of the second coextrusion blown film outer, middle, inner layer extruders and die zones
| Temperature (temperature) | Zone 1 | Zone 2 | Zone 3 | Zone 4 | Zone 5 |
| An outer layer | 162±5℃ | 168±5℃ | 170±5℃ | 165±5℃ | 160±5℃ |
| Middle layer | 165±5℃ | 170±5℃ | 172±5℃ | 168±5℃ | 165±5℃ |
| Inner layer | 170±5℃ | 175±5℃ | 178±5℃ | 172±5℃ | 168±5℃ |
| Die head | 180±5℃ | 186±5℃ | 182±5℃ | 180±5℃ |
The extrusion pressure of the second extrusion blown film outer layer extruder is preferably 235-318 bar, the extrusion pressure of the middle layer extruder is preferably 205-335 bar, and the extrusion pressure of the inner layer extruder is preferably 225-310 bar.
After the degradable polyethylene printing film and the high-barrier degradable polyethylene heat-sealing film are obtained, the degradable polyethylene printing film and the high-barrier degradable polyethylene heat-sealing film are compounded by adopting an adhesive, and the high-barrier degradable polyethylene composite film is obtained after curing. In the present invention, printing is further included on the surface of the outer layer (i.e., corona layer) of the degradable polyethylene printing film before compounding, and the printing method is preferably gravure printing; the adhesive is preferably a solvent-free adhesive, and the solvent-free adhesive is preferably a two-component solvent-free polyurethane adhesive of Wanhua chemical (Beijing) limited company, and the model is 6039A/739B; the invention preferably firstly coats PVA solution on the surface of the outer layer (namely corona layer) of the high-barrier degradable polyethylene heat-sealing film, and then adopts a solvent-free process to compound the printing surface of the degradable polyethylene printing film and the outer layer of the high-barrier degradable polyethylene heat-sealing film; the thickness of the PVA solution is preferably 0.5-1 mu m, the concentration of the PVA solution is preferably 12-15 wt%, and the solvent of the PVA solution is preferably water; according to the invention, the PVA solution is coated on the surface of the high-barrier degradable polyethylene heat-sealing film, so that the oxygen barrier property of the film can be improved, and the quality guarantee period of a product can be prolonged; the conditions of the compounding preferably include: glue mixing temperature: the components A and B are set at 38 ℃; coating temperature: the temperature of each steel roller of the coating and sizing system is set to be 45 ℃; the mass ratio of the glue ratios 6039A and 739B is 100/60; the sizing amount is 1.5-2.2 g/m 2 . The invention has no special requirements on the operation process of the compounding, and can be realized by adopting a solvent-free process which is well known to a person skilled in the art.
In the present invention, the curing temperature is preferably 35 to 45 ℃, more preferably 40 ℃, and the curing time is preferably 24 to 48 hours, more preferably 48 hours.
The invention also provides a high-barrier degradable polyethylene composite bag which is prepared from the high-barrier degradable polyethylene composite film, wherein the high-barrier degradable polyethylene composite film is the high-barrier degradable polyethylene composite film according to the scheme or the high-barrier degradable polyethylene composite film prepared by the preparation method according to the scheme; the method of the present invention for making the bag is not particularly limited, and methods well known to those skilled in the art may be employed, and in the specific embodiment of the present invention, the heat-sealing layer of the high barrier degradable polyethylene composite film is preferably heat-sealed in contact with the required bag type, and the heat-sealing conditions preferably include: the edge sealing temperature is 150-160 ℃, the bottom sealing temperature is 160-170 ℃, and the heat sealing pressure is 4-6 kg.
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, but should not be construed as limiting the scope of the present invention.
The sources of the raw materials and the performance parameters used in the examples are shown in tables 3 to 4.
Table 3 raw material sources and performance parameters used for preparing degradable polyethylene print films in examples
Table 4 raw material sources and performance parameters used to prepare high barrier degradable polyethylene heat seal films in examples
Example 1
The degradable polyethylene printing film has a three-layer structure, and the materials of the outer layer, the middle layer and the inner layer are respectively as follows in percentage by weight: 25% of the outer layer, 50% of the middle layer and 25% of the inner layer.
The preparation method of the degradable polyethylene printing film comprises the following steps: raw materials of the outer layer, the middle layer and the inner layer are mixed in proportion through an automatic batching system and then are sent into an outer layer extruder, the middle layer extruder and the inner layer extruder, the raw materials of the outer layer, the middle layer extruder and the inner layer extruder are melted and plasticized and then are sent into a die head, blown film is extruded, the film is cooled by air cooling, a cylinder is flattened by a stabilizing ring and a herringbone row to be driven and rotated by an upper traction roller and then enter a corona treatment device for corona treatment through a guide roller, and then trimming is carried out by a lower traction roller and then enters a front-back rolling device for front-back rolling, so that the degradable polyethylene printing film with the thickness of 40 mu m can be obtained. The raw material proportions of the outer layer, the middle layer and the inner layer of the degradable polyethylene printing film are shown in Table 5; the temperatures and pressures of the outer, middle and inner extruders and dies are shown in Table 6.
The high-barrier degradable polyethylene heat-sealing film has a three-layer structure, and the materials of the outer layer, the middle layer and the inner layer are respectively as follows in percentage by weight: 30% of the outer layer, 40% of the middle layer and 30% of the inner layer; the preparation method of the high-barrier degradable polyethylene heat-sealing film is consistent with that of the degradable polyethylene printing film, and the raw material proportions of the outer layer, the middle layer and the inner layer are shown in Table 7; the temperature and pressure of the outer layer, middle layer and inner layer extruders and dies are shown in Table 8, and the thickness of the high barrier degradable polyethylene heat sealing film is 60 μm.
Printing the prepared degradable polyethylene printing film according to a conventional gravure process; coating PVA solution on the surface of the high-barrier degradable polyethylene heat-sealing film, wherein the thickness of the coating is 0.5 mu m; the printed degradable polyethylene printing film and the high-barrier degradable polyethylene heat-sealing film are compounded by a solvent-free adhesive, the adopted solvent-free adhesive is a two-component solvent-free polyurethane adhesive of Wanhua chemical (Beijing) limited company, and the compounding conditions comprise: glue mixing temperature: the components A and B are set at 38 ℃; coating temperature: the temperature of each steel roller of the coating and sizing system is set to be 45 ℃; glue ratio a/b=100/60; the sizing amount is 2.1g/m 2 。
And (3) placing the composite film in a curing room at 40+/-5 ℃ for curing for 48 hours, taking out, placing at room temperature for 12 hours to obtain the high-barrier degradable polyethylene composite film, and then making bags according to the required bag-type conventional process to obtain the high-barrier degradable polyethylene composite bag.
TABLE 5 amount of three raw materials for degradable polyethylene printing film (in parts by mass)
TABLE 6 extruder temperature and pressure for preparing degradable polyethylene printed films
| Temperature (temperature) | Zone 1 | Zone 2 | Zone 3 | Zone 4 | Zone 5 | Pressure (bar) |
| An outer layer | 172℃ | 178℃ | 175℃ | 170℃ | 165℃ | 225～315 |
| Middle layer | 175℃ | 182℃ | 178℃ | 175℃ | 172℃ | 215～355 |
| Inner layer | 172℃ | 178℃ | 175℃ | 170℃ | 165℃ | 205～285 |
| Die head | 185℃ | 190℃ | 185℃ | 180℃ |
Table 7 high barrier degradable polyethylene heat sealing film three layer raw material usage (in mass parts)
Table 8 extruder temperature and pressure for preparing high barrier degradable polyethylene heat seal film
| Temperature (temperature) | Zone 1 | Zone 2 | Zone 3 | Zone 4 | Zone 5 | Pressure (bar) |
| An outer layer | 162℃ | 168℃ | 170℃ | 165℃ | 160℃ | 225～318 |
| Middle layer | 165℃ | 170℃ | 172℃ | 168℃ | 165℃ | 205～335 |
| Inner layer | 170℃ | 175℃ | 178℃ | 172℃ | 168℃ | 225～310 |
| Die head | 180℃ | 186℃ | 182℃ | 180℃ |
Example 2
The degradable polyethylene printing film comprises the following three layers in percentage by weight: 30% of the outer layer, 40% of the middle layer and 30% of the inner layer, and the thickness of the degradable polyethylene printing film is 40 mu m. The high-barrier degradable polyethylene heat-sealing film comprises the following three layers in percentage by weight: 25% of the outer layer, 45% of the middle layer and 30% of the inner layer, and the thickness of the high-barrier degradable polyethylene heat-sealing film is 60 mu m. The amounts of the materials used for the respective layers are shown in tables 5 and 7.
The preparation method is the same as that of the example 1, and the high-barrier degradable polyethylene composite film and the high-barrier degradable polyethylene composite bag are obtained.
Example 3
The degradable polyethylene printing film comprises the following three layers in percentage by weight: 20% of the outer layer, 60% of the middle layer and 20% of the inner layer, and the thickness of the degradable polyethylene printing film is 40 mu m. The high-barrier degradable polyethylene heat-sealing film comprises the following three layers in percentage by weight: 25% of the outer layer, 50% of the middle layer and 25% of the inner layer, and the thickness of the high-barrier degradable polyethylene heat-sealing film is 60 mu m. The amounts of the materials used for the respective layers are shown in tables 5 and 7.
The preparation method is the same as that of the example 1, and the high-barrier degradable polyethylene composite film and the high-barrier degradable polyethylene composite bag are obtained.
Comparative example 1
The composite film of comparative example 1 is a composite structure of a PET printing layer and a PE heat sealing layer, wherein the PET layer is a printing layer, the thickness is 12 μm, and the composite film is a commercial product; the PE heat-sealing layer is a high-barrier EVOH co-extrusion heat-sealing film, the thickness is 60 mu m, and the PE heat-sealing layer is a commercial product.
Printing the purchased PET printing film by using a conventional gravure process according to the requirements of customers;
compounding the printed PET film and the purchased high-barrier EVOH co-extrusion heat-sealing film through a solvent-free adhesive, wherein the adopted adhesive is a double-component solvent-free adhesive of Wanhua chemical (Beijing) limited companyPolyurethane adhesive, model 6039A/739B, and the compounding conditions are as follows: glue mixing temperature: the temperature of the components A and B is set to 40 ℃; coating temperature: the temperature of each steel roller of the coating and sizing system is set to be 45 ℃; glue ratio a/b=100/60 (mass ratio); the sizing amount is 2.1g/m 2 ；
And (3) placing the composite film in a curing room at the temperature of 48+/-5 ℃ for curing for 48 hours, cooling for 12 hours, and then making bags according to the required conventional bag-type process to obtain the composite bag.
Comparative example 2
The polyethylene printing film comprises the following three layers in percentage by weight: 20% of the outer layer, 60% of the middle layer and 20% of the inner layer, and the thickness of the polyethylene printing film is 40 mu m. The weight percentage of the three layers of the high-barrier polyethylene heat-sealing film is as follows: 25% of the outer layer, 50% of the middle layer and 25% of the inner layer, and the thickness of the high-barrier polyethylene heat-sealing film is 60 mu m. The amounts of the materials used for the respective layers are shown in tables 5 and 7.
The preparation method was the same as in example 1 to obtain a polyethylene composite film and a bag.
Performance test:
the degradable polyethylene printed films prepared in examples 1 to 3 and comparative example 2, and the PET film in comparative example 1 were tested for mechanical properties, wetting tension, haze, ink layer bonding fastness, and degradation properties, and the results are shown in table 9.
TABLE 9 results of Performance test of degradable polyethylene printed films
As can be seen from the data in Table 9, the degradable polyethylene printing film prepared by the invention has good mechanical properties, low haze and high ink layer bonding fastness, and can be effectively degraded under the conditions of light, thermal oxygen and composting, while the PET film in comparative example 1 has unqualified degradation performance, and the polyethylene printing film in comparative example 2 has no degradation master batch added to the outer layer, the middle layer and the inner layer, and has unqualified degradation performance under the conditions of light, thermal oxygen and composting.
The high barrier degradable polyethylene heat sealing films prepared in examples 1 to 3 and comparative example 2, and the high barrier EVOH coextrusion heat sealing film in comparative example 1 were tested for mechanical properties, wetting tension, haze, barrier properties, heat sealing strength, and degradation properties, and the results are shown in table 10.
Table 10 high barrier degradable polyethylene heat seal film performance test results
As can be seen from the data in Table 10, the high-barrier degradable polyethylene heat-sealing film prepared by the invention has good mechanical properties, low haze, good water vapor and oxygen barrier property and good heat-sealing strength, and can be effectively degraded under the conditions of light, thermal oxygen and composting, while the PET film in comparative example 1 has unqualified degradation performance, and the high-barrier polyethylene heat-sealing film in comparative example 2 has no degradation master batch added in the outer layer, the middle layer and the inner layer, and has unqualified degradation performance under the conditions of light, thermal oxygen and composting.
The composite films prepared in examples 1 to 3 and comparative examples 1 to 2 were tested for mechanical properties, wetting tension, haze, barrier properties, ink layer bonding fastness, heat seal strength, and degradation properties, and the results are shown in table 11.
Table 11 results of the composite performance test
As can be seen from the detection data in Table 11, the high-barrier degradable polyethylene composite film prepared by the invention has good mechanical property, low haze, good barrier property, high structural fastness of the ink layer and excellent degradation property; the degradation performance of the composite films in comparative examples 1 to 2 is not qualified.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The high-barrier degradable polyethylene composite film is characterized by being obtained by compounding a degradable polyethylene printing film and a high-barrier polyethylene heat-sealing film;
the degradable polyethylene printing film comprises an outer layer, a middle layer and an inner layer;
the preparation raw materials of the outer layer and the inner layer of the degradable polyethylene printing film comprise the following components in parts by weight: 10-30 parts of medium density polyethylene, 30-70 parts of high density polyethylene, 15-40 parts of medium density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
the preparation raw materials of the middle layer of the degradable polyethylene printing film comprise the following components in parts by mass: 10-40 parts of first medium-density metallocene polyethylene, 10-30 parts of second medium-density metallocene polyethylene, 30-85 parts of high-strength low-density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
the high-barrier polyethylene heat-sealing film comprises an outer layer, a middle layer and an inner layer;
the preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10-30 parts of low-density polyethylene, 15-40 parts of low-density metallocene polyethylene, 20-75 parts of linear low-density polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
The preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10-30 parts of low-density polyethylene, 10-50 parts of linear low-density polyethylene, 30-80 parts of low-density metallocene polyethylene, 1.5-2.5 parts of degradation master batch and 0.5-1 part of processing aid;
the preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise the following components in parts by weight: 10 to 25 parts of low-density polyethylene, 30 to 80 parts of low-density metallocene polyethylene, 20 to 60 parts of ultra-low-density metallocene polyethylene, 1.5 to 2.5 parts of degradation master batch and 0.5 to 1 part of processing aid.
2. The high barrier degradable polyethylene composite film according to claim 1, wherein the degradable polyethylene printed film outer layer and inner layer are prepared from the following raw materials: the melt index of the medium density polyethylene is 2.5-3.5 g/10min, and the density is 0.925-0.940 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the high-density polyethylene is 0.3-1.5 g/10min, and the density is 0.955-0.970 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the medium density metallocene polyethylene is 0.2-1.0 g/10min, and the density is 0.925-0.940 g/cm 3 ；
The preparation raw materials of the middle layer of the degradable polyethylene printing film comprise: the melt index of the first medium density metallocene polyethylene is 0.2-1.0 g/10min, and the density is 0.935-0.945 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the second medium density metallocene polyethylene is 2.0-3.0 g/10min, and the density is 0.930-0.940 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the high-strength low-density metallocene polyethylene is 0.2-1.0 g/10min, and the density is 0.910-0.920 g/cm 3 。
3. The high-barrier degradable polyethylene composite film according to claim 1, wherein the high-barrier polyethylene heat-sealing film outer layer is prepared from the following raw materials: the melt index of the low density polyethylene is 1.5-2.5 g/10min, and the density is 0.920-0.930 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the low-density metallocene polyethylene is 1.5-2.5 g/10min, and the density is 0.908-0.920 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the linear low density polyethylene is 1.5-2.5 g/10min, and the density is 0.910-0.925 g/cm 3 ；
The preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise: the melt index of the low density polyethylene is 1.5-2.5 g/10min, and the density is 0.920-0.930 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the linear low density polyethylene is 1.5-2.5 g/10min, and the density is 0.910-0.925 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the low-density metallocene polyethylene is 0.5-2.0 g/10min, and the density is 0.910-0.925 g/cm 3 ；
The height is as followsThe preparation raw materials of the inner layer of the barrier polyethylene heat-sealing film comprise: the melt index of the low density polyethylene is 1.5-2.5 g/10min, and the density is 0.920-0.930 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the low-density metallocene polyethylene is 0.3-1.5 g/10min, and the density is 0.900-0.915 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the ultra-low density metallocene polyethylene is 0.5-1.8 g/10min, and the density is 0.890-0.915 g/cm 3 。
4. The high-barrier degradable polyethylene composite film according to claim 1, wherein the degradable polyethylene printing film has an outer layer, a middle layer and an inner layer, and the high-barrier polyethylene heat-sealing film has a density of 0.920 to 0.940g/cm and a melt index of the degradable master batch of 46 to 55g/10min 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index of the processing aid is 1.5.0-2.8 g/10min, and the density is 0.910-0.920 g/cm 3 。
5. The high-barrier degradable polyethylene composite film according to any one of claims 1 to 4, wherein the degradable polyethylene printed film outer layer and inner layer are prepared from the following raw materials: the brand of the medium density polyethylene is 151BW, the brand of the high density polyethylene is 8300, and the brand of the medium density metallocene polyethylene is 3505MA;
the preparation raw materials of the middle layer of the degradable polyethylene printing film comprise: the brand of the first medium-density metallocene polyethylene is 4009, the brand of the second medium-density metallocene polyethylene is 2036P, and the brand of the high-strength low-density metallocene polyethylene is XP6056ML;
The preparation raw materials of the outer layer of the high-barrier polyethylene heat-sealing film comprise: the brand of the low-density polyethylene is 2420H, the brand of the low-density metallocene polyethylene is 1520, and the brand of the linear low-density polyethylene is 7042;
the preparation raw materials of the middle layer of the high-barrier polyethylene heat-sealing film comprise: the brand of the low-density polyethylene is 2420H, the brand of the linear low-density polyethylene is 201XV, and the brand of the low-density metallocene polyethylene is 1018BN;
the preparation raw materials of the inner layer of the high-barrier polyethylene heat-sealing film comprise: the brand of the low-density polyethylene is 2426H, the brand of the low-density metallocene polyethylene is AT6202, and the brand of the ultra-low-density metallocene polyethylene is SP0510H;
the outer layer, the middle layer and the inner layer of the degradable polyethylene printing film are made of high-barrier polyethylene heat-sealing film, the brand of degradation master batch used by the outer layer, the middle layer and the inner layer is TRF-57, and the brand of processing aid is PA0895LD.
6. The high-barrier degradable polyethylene composite film according to any one of claims 1 to 4, wherein the thickness of the degradable polyethylene printed film is 30 to 80 μm, and the thickness of the high-barrier degradable polyethylene heat-seal film is 40 to 100 μm;
the degradable polyethylene printing film comprises the following components: the mass fraction of the outer layer is 20-30%, the mass fraction of the middle layer is 40-60%, and the mass fraction of the inner layer is 20-30%;
The high-barrier degradable polyethylene heat-sealing film comprises the following components: the mass fraction of the outer layer is 25-30%, the mass fraction of the middle layer is 40-50%, and the mass fraction of the inner layer is 25-30%.
7. The method for preparing the high-barrier degradable polyethylene composite film according to any one of claims 1 to 6, which is characterized by comprising the following steps:
carrying out three-layer coextrusion film blowing on preparation raw materials of an outer layer, a middle layer and an inner layer of the degradable polyethylene printing film to obtain the degradable polyethylene printing film;
performing three-layer coextrusion film blowing on the preparation raw materials of the outer layer, the middle layer and the inner layer of the high-barrier degradable polyethylene heat-sealing film to obtain the high-barrier degradable polyethylene heat-sealing film;
and compounding the degradable polyethylene printing film and the high-barrier degradable polyethylene heat-sealing film by adopting an adhesive, and curing to obtain the high-barrier degradable polyethylene composite film.
8. The method of claim 7, wherein the step of printing on the surface of the degradable polyethylene print film before compounding the degradable polyethylene print film and the high barrier degradable polyethylene heat seal film.
9. The method according to claim 7, wherein the curing is carried out at a temperature of 35 to 45 ℃ for 24 to 48 hours.
10. A high-barrier degradable polyethylene composite bag, which is characterized by being prepared from a high-barrier degradable polyethylene composite film, wherein the high-barrier degradable polyethylene composite film is prepared by the high-barrier degradable polyethylene composite film according to any one of claims 1 to 6 or the preparation method according to any one of claims 7 to 9.
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