CN113211920A - Multilayer co-extrusion full-degradable high-barrier packaging film and preparation method thereof - Google Patents
Multilayer co-extrusion full-degradable high-barrier packaging film and preparation method thereof Download PDFInfo
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- CN113211920A CN113211920A CN202110587994.1A CN202110587994A CN113211920A CN 113211920 A CN113211920 A CN 113211920A CN 202110587994 A CN202110587994 A CN 202110587994A CN 113211920 A CN113211920 A CN 113211920A
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- Prior art keywords
- layer
- packaging film
- multilayer
- blend
- barrier packaging
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- 239000012785 packaging film Substances 0.000 title claims abstract description 37
- 229920006280 packaging film Polymers 0.000 title claims abstract description 37
- 238000001125 extrusion Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000010410 layer Substances 0.000 claims abstract description 53
- 230000004888 barrier function Effects 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000012790 adhesive layer Substances 0.000 claims abstract description 19
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims abstract description 14
- 230000007062 hydrolysis Effects 0.000 claims abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 239000012793 heat-sealing layer Substances 0.000 claims abstract description 9
- 239000011241 protective layer Substances 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 4
- 239000004626 polylactic acid Substances 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 12
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 11
- 229920001610 polycaprolactone Polymers 0.000 claims description 10
- 239000004632 polycaprolactone Substances 0.000 claims description 9
- 229920000954 Polyglycolide Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 5
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 claims description 2
- JYLRDAXYHVFRPW-UHFFFAOYSA-N butane-1,1-diol;terephthalic acid Chemical compound CCCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 JYLRDAXYHVFRPW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims 2
- 230000006750 UV protection Effects 0.000 claims 1
- 239000005022 packaging material Substances 0.000 abstract description 8
- 229920001896 polybutyrate Polymers 0.000 abstract description 7
- 239000002361 compost Substances 0.000 abstract description 3
- 150000001718 carbodiimides Chemical class 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920006238 degradable plastic Polymers 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002643 polyglutamic acid Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/536—Hardness
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- 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
- B32B2307/71—Resistive to light or to UV
-
- 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
- B32B2307/712—Weather resistant
-
- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Abstract
A multilayer coextrusion full-degradable high-barrier packaging film and a preparation method thereof, the packaging film is composed of 5 layers: the first layer is an outer protective layer A, and the components of the first layer are a blend of PLA, PBAT, carbodiimide hydrolysis-resistant agent and ultraviolet-resistant agent; the second layer is an adhesive layer B, and the component of the adhesive layer B is a blend of PLA and a multi-active functional group compatibilizer; the third layer is a high barrier layer C, and the component of the high barrier layer C is PGA; the fourth layer is an adhesive layer D, and the component of the adhesive layer D is a blend of PLA and a multi-active functional group compatibilizer; the fifth layer is a heat sealing layer E, and the component of the heat sealing layer E is a blend of PLA and PCL. Is prepared by adopting a multi-layer co-extrusion method. The multilayer co-extrusion fully-degradable high-barrier packaging film has the advantages of good weather resistance, high barrier property and slow decay of the barrier property; the product is packaged by the packaging material, so that the shelf life of the product can be prolonged; and the compost is fully degradable, and is particularly suitable for the field of packaging film bags which need high barrier property, durability and meet the requirement of full degradation.
Description
Technical Field
The invention relates to a film material for a pre-packaging film bag, in particular to a high-barrier fully-degradable packaging material and a preparation method thereof.
Background
The loss of agricultural and food products globally due to the lack of high barrier packaging material accounts for about one fifth of the total yield. In China, the total yield of fruits and vegetables is about 20% every year, and the loss caused by poor barrier property of a packaging material reaches about 4500 hundred million yuan in the transportation and storage process. Furthermore, precision mechanical parts, electronic parts, medicines, medical instruments and the like are also preferably packaged by high-barrier packaging materials to enhance the quality protection of the products. Therefore, the development of high-barrier packaging materials is of great significance.
When the packaging material used for the packaging film bag achieves multiple barrier or other characteristics to water vapor, oxygen and the like, a multi-layer co-extrusion mode is mostly adopted, and functional layers made of different materials are combined together. The most common at present are coextruded blown films composed of a multilayer combination of PA, EVOH, PVDC with PE, EVA, PP, etc. The used materials are all non-degradable materials, which easily causes white pollution. In recent years, people realize that white pollution has seriously influenced ecological balance, and the trend of adopting degradable plastics to replace non-degradable plastics is a development trend.
In the prior degradable plastic, Polyglycolide (PGA) has good barrier property to oxygen and water vapor, and is an excellent high-barrier material. When the water-based paint is used alone, water vapor in the air easily causes hydrolysis and aging of the water-based paint, the physical properties of the water-based paint are reduced, the normal use of the water-based paint is affected, and the shelf life of the water-based paint is extremely short.
CN105968548A in 2016, 9, 28 discloses a high barrier packaging film, which is prepared from the following components in parts by weight: 40-60 parts of ethylene-vinyl alcohol copolymer, 10-20 parts of high-density polyethylene, 2-4 parts of nano silicon dioxide, 1-2 parts of nano aluminum oxide, 2-5 parts of gamma-mercaptopropyl trimethoxy silane, 1-3 parts of phenyl trimethoxy silane, 1-2 parts of polyvinyl formal, 1-3 parts of erucamide, 1-2 parts of microcrystalline wax, 50-70 parts of N, N-dimethyl formamide, 0.5-1 part of dioctyl phthalate, 1-3 parts of polyethylene glycol, 20-30 parts of isopropanol, 20-40 parts of acetone and 20-40 parts of deionized water. Although the tensile strength can reach 51.7MPa at most; the lowest moisture permeability coefficient is only 608g/(cm s & pa), the lowest oxygen permeability coefficient is only 0.020 multiplied by 10 < -15 >/(cm & s & pa), and the water-gas-oxygen barrier property is good but the water-gas-oxygen barrier property cannot be biodegraded.
CN107556536A discloses a low-cost bio-based fully-degradable film and a preparation method thereof in 2018, 1 month and 9 days, wherein the film comprises the following components in parts by weight: 15-25 parts of polyglycolide, 25-35 parts of corn starch, 35-55 parts of poly (butylene adipate/terephthalate), 5 parts of compatilizer, 3.75-12.25 parts of starch plasticizer, 0.5-0.7 part of citric acid, 0.75-1.25 parts of acetyl tributyl citrate, 0.3-0.5 part of maleic anhydride, 1640.2 parts of antioxidant and 0.2 part of 2- (2 '-hydroxy 5' -methylphenyl) benzotriazole. It contains 35-55 parts of poly (butylene adipate)/terephthalate, and whether the poly (butylene terephthalate) can be completely biodegraded is questionable. The service life is also short.
CN107652641A discloses a low-cost bio-based fully-degradable high-permeability film and a preparation method thereof in 2018, 2.2.8.A film comprises the following components in parts by weight: 30-50 parts of polyglycolide, 40-60 parts of polylactic acid, 0.2-5 parts of compatilizer, 4 parts of plasticizer, 4 parts of PVAc, 2 parts of maleic anhydride, 1640.2 parts of antioxidant and 10100.3 parts of antioxidant. It is claimed that the light transmittance may exceed 91% and the longitudinal tensile strength may reach 59.82MPa, which, although it is claimed to be low in cost, is not necessarily low in cost due to its high polylactic acid content; the proportion of very easily hydrolyzed Polyglycolide (PGA) is also quite high, the attenuation of the barrier property of the product is necessarily quicker, and the service life of the product is shorter.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the existing packaging film and providing a fully-degradable multilayer co-extrusion high-barrier packaging film which has slow decay of barrier property and long service life, can effectively prolong the shelf life of products when being used for packaging the products and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is that the multilayer co-extrusion full-degradation high-barrier packaging film is composed of 5 layers:
the first layer is an outer protective layer A, and the components of the outer protective layer A are polylactic acid (PLA), a copolymer (PBAT) of butanediol adipate and butanediol terephthalate, and a blend of a hydrolysis resisting agent and an ultraviolet resisting agent;
the second layer is an adhesive layer B, and the component of the adhesive layer B is a blend of polylactic acid (PLA) and a multi-active functional group compatibilizer;
the third layer is a high barrier layer C, and the component of the high barrier layer C is Polyglycolide (PGA);
the fourth layer is an adhesive layer D, and the component of the adhesive layer D is a blend of polylactic acid (PLA) and a multi-active functional group compatibilizer;
the fifth layer is a heat sealing layer E, and the component of the heat sealing layer E is a blend of polylactic acid (PLA) and Polycaprolactone (PCL).
Further, in the outer protective layer A, the mass ratio of PBAT is 30-40%, the mass ratio of hydrolysis resistant agent is 0.3-0.5%, and the mass ratio of ultraviolet resistant agent is 0.3-0.5%.
Further, the adhesive layer B and the adhesive layer D are respectively 3-4% of a multi-active functional group compatibilizer, and the balance is PLA.
Furthermore, the mass ratio of the heat sealing layer E to the PCL is 15-25%.
Further, in the outer protective layer A, the melt index of the blend of PLA, PBAT, the hydrolysis resistant agent and the ultraviolet resistant agent is 1-10 g/min.
Further, the ultraviolet light resistant agent is selected from one of ultraviolet light resistant agents UV-531, UV-329, UV-326 and UV-328.
Further, in the adhesive layer B and the adhesive layer D, the melt index of the blend of PLA and the multi-active functional group compatibilizer is 1-10 g/min.
In the barrier layer C, the melt index of PGA is 1-10 g/min.
Further, the multi-active functional group compatibilizer is one selected from diisocyanate, dianhydride, styrene-glycidyl methacrylate copolymer and styrene-maleic anhydride copolymer.
Further, the melt index of the blend of PLA and PCL in the heat sealing layer E is 1-10 g/min.
Furthermore, the film thickness of the multilayer co-extrusion fully-degradable high-barrier packaging film is preferably 20-40 μm, wherein the thickness of the layer A accounts for 15-20% of the total thickness, the thickness of the layer B accounts for 5-10% of the total thickness, the thickness of the layer C accounts for 40-50% of the total thickness, the thickness of the layer D accounts for 5-10% of the total thickness, and the thickness of the layer E accounts for 15-20% of the total thickness.
Further, the preparation method of the multilayer co-extrusion fully-degradable high-barrier packaging film adopts a multilayer co-extrusion method, co-extrusion is carried out at the temperature of 160-230 ℃, and traction and rolling are carried out after cooling.
The beneficial technical effects of the invention are as follows:
in the fully-degradable high-barrier packaging film, the PGA material which is very easy to absorb moisture and hydrolyze is arranged in the middle layer and isolated from the outside, so that the problem of performance attenuation and reduction of the product caused by the very easy hydrolysis of the film material in the early stage is solved; the outer protective layer is made of PLA and PBAT, the material has good toughness and hardness, and good protection to the film, and the durability of the film is further improved by matching with a hydrolysis resistant agent and an anti-ultraviolet light agent; the inner layer adopts the blend of PLA and PCL, and has good heat sealability. The adhesive resin between the functional layers is PLA and polyfunctional compatibilizer, and the adhesive force between the layers is improved through reactive compatibilization. The packaging film has good weather resistance, high barrier property and slow decay of the barrier property; the product is packaged by the packaging material, so that the shelf life of the product can be prolonged; and the compost can be fully degraded, which is beneficial to preventing white pollution.
The fully-degradable high-barrier packaging film is particularly suitable for the field of packaging film bags which need high barrier and durability and need to meet the requirement of full degradation.
Detailed Description
The present invention is further illustrated by the following specific examples.
The main production equipment for manufacturing the multilayer co-extrusion fully-degradable high-barrier packaging film is a five-layer co-extrusion blow molding machine set. Other devices, as not specifically indicated, employ conventional production equipment in the art.
The raw materials used in the examples of the present invention are shown in table 1 below, but not limited thereto:
table 1 main raw material manufacturers of examples of the present invention
| Name of auxiliary agent | Manufacturer(s) | Number plate |
| Carbodiimide hydrolysis resistance agent | Shanghai Lai Security Co Ltd | STABAXOL I |
| Anti-ultraviolet light agent | Chunpu chemical Co., Ltd | UV-531 |
| Multi-reactive functional group compatibilizer | Basf-Fr | ADR-4400 |
The multilayer co-extrusion fully-degradable high-barrier packaging film is structurally five-layer structure comprising A, B, C, D and E. The materials used for each layer were:
the melt index of the blend of PLA, PBAT, hydrolysis resistant agent and UV resistant agent used in A is 1-10 g/min.
The blend of PLA and the multi-functional compatibilizer used in B and D has a melt index of 1 to 10 g/min.
The melt index of PGA used in the above-mentioned C is 1 to 10 g/min.
The melt index of the PLA and PCL blend used in E is 1-10 g/min.
And (3) processing at the temperature of 160-230 ℃ by adopting a multilayer coextrusion blow molding machine, cooling, and then drawing and rolling to obtain the multilayer coextrusion fully-degradable high-barrier packaging film.
Table 2 shows the composition and structure of the products of examples 1-11:
TABLE 2 examples 1-11 compositions and Structure of packaging film products
TABLE 3 detection data of various properties of the multi-layer co-extruded fully-degradable high-barrier packaging film in examples 1 to 11
Therefore, the multilayer co-extrusion fully-degradable high-barrier packaging film provided by the invention is produced by a multilayer co-extrusion method, the PGA material which is very easy to hydrolyze is placed in the middle layer, and the material is isolated from the outside, so that the problem of performance reduction caused by very easy hydrolysis of the material in the early stage is solved; the outer layer is made of PLA and PBAT materials with good weather resistance, the materials have good toughness and hardness, the film has good protection performance, and the durability of the film is further improved by matching with a hydrolysis resistant agent and an anti-ultraviolet light agent; the inner layer adopts PLA and PCL blend, and has good heat sealability. The adhesive resin between the functional layers is PLA and polyfunctional compatibilizer, and the adhesive force between the layers is improved through reactive compatibilization. The packaging film prepared by the method has good barrier property and long shelf life, and the compost is fully degraded, thereby meeting the requirement of environmental protection.
The above-mentioned embodiments are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to make the content of the present invention more fully understood and implemented by those skilled in the art, and should not be used for explaining the limitation of the protection scope of the present patent application. All equivalent changes and modifications made according to the spirit of the present invention should fall within the scope of the present patent application.
Claims (10)
1. A multilayer co-extrusion full-degradation high-barrier packaging film is characterized in that: is composed of 5 layers:
the first layer is an outer protective layer A, and the component of the first layer is a blend of polylactic acid, a copolymer of butanediol adipate and butanediol terephthalate, a hydrolysis resistant agent and an anti-ultraviolet agent;
the second layer is an adhesive layer B, and the component of the adhesive layer B is a blend of polylactic acid and a multi-active functional group compatibilizer;
the third layer is a high barrier layer C, and the component of the high barrier layer C is polyglycolide;
the fourth layer is an adhesive layer D, and the component of the adhesive layer D is a blend of polylactic acid and a multi-active functional group compatibilizer;
the fifth layer is a heat sealing layer E, and the component of the heat sealing layer E is a blend of polylactic acid and polycaprolactone.
2. The multilayer co-extrusion fully-degradable high-barrier packaging film as claimed in claim 1, wherein in the outer protective layer A, the proportion of the copolymer of butylene adipate and butylene terephthalate is 30-40 wt%, the proportion of the hydrolysis-resistant agent is 0.3-0.5 wt%, and the proportion of the ultraviolet-resistant agent is 0.3-0.5 wt%.
3. The multilayer co-extrusion fully-degradable high-barrier packaging film as claimed in claim 1 or 2, wherein the adhesive layers B and D and the multi-active functional group compatibilizer account for 3-4 wt%.
4. The multilayer co-extruded fully degradable high barrier packaging film as claimed in one of claims 1 to 3, wherein the heat sealing layer E, polycaprolactone, is 15wt% -25 wt%.
5. The multilayer co-extruded fully degradable high barrier packaging film according to any one of claims 1 to 4 wherein the blend of polylactic acid, butylene adipate and butylene terephthalate, hydrolysis resistance agent and UV resistance agent in the outer protective layer has a melt index of 1 to 10 g/min.
6. The multilayer co-extruded fully degradable high barrier packaging film according to any one of claims 1 to 5 wherein said UV resistant agent is selected from one of UV-531, UV-329, UV-326 and UV-328.
7. The multilayer co-extruded fully degradable high barrier packaging film according to one of claims 1 to 6, wherein in the adhesive layer B and the adhesive layer D, the melt index of the blend of polylactic acid and the multi-active functional group compatibilizer is 1 to 10 g/min; in the barrier layer C, the melt index of polyglycolide is 1-10 g/min.
8. The multilayer co-extruded fully degradable high barrier packaging film according to any one of claims 1 to 7, wherein the multi-reactive functional group compatibilizer is one selected from diisocyanate, dianhydride, styrene-glycidyl methacrylate copolymer, and styrene-maleic anhydride copolymer.
9. The multilayer co-extruded fully degradable high barrier packaging film according to one of claims 1 to 8, wherein the melt index of the blend of PLA and PCL in the heat seal layer E is 1 to 10 g/min; the film thickness of the multilayer co-extrusion fully-degradable high-barrier packaging film is preferably 20-50 microns, wherein the thickness of the layer A accounts for 15-20% of the total thickness, the thickness of the layer B accounts for 5-10% of the total thickness, the thickness of the layer C accounts for 40-50% of the total thickness, the thickness of the layer D accounts for 5-10% of the total thickness, and the thickness of the layer E accounts for 15-20% of the total thickness.
10. A method for preparing the multilayer co-extrusion fully degradable high-barrier packaging film as claimed in any one of claims 1 to 9, which is characterized in that a multilayer co-extrusion method is adopted, co-extrusion is carried out at the temperature of 160-230 ℃, and traction and rolling are carried out after cooling.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113733678A (en) * | 2021-09-06 | 2021-12-03 | 东莞市博晨塑料科技有限公司 | Fully-degradable high-barrier co-extrusion bag and preparation method thereof |
| CN114434929A (en) * | 2022-01-28 | 2022-05-06 | 上海乐纯生物技术有限公司 | Degradable film of disposable bag for bio-pharmaceuticals and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160058605A1 (en) * | 2013-05-17 | 2016-03-03 | Hollister Incorporated | Biodegradable odor barrier film |
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2021
- 2021-05-27 CN CN202110587994.1A patent/CN113211920A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160058605A1 (en) * | 2013-05-17 | 2016-03-03 | Hollister Incorporated | Biodegradable odor barrier film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113733678A (en) * | 2021-09-06 | 2021-12-03 | 东莞市博晨塑料科技有限公司 | Fully-degradable high-barrier co-extrusion bag and preparation method thereof |
| CN114434929A (en) * | 2022-01-28 | 2022-05-06 | 上海乐纯生物技术有限公司 | Degradable film of disposable bag for bio-pharmaceuticals and application thereof |
| CN114434929B (en) * | 2022-01-28 | 2022-09-16 | 上海乐纯生物技术有限公司 | Degradable film of disposable bag for bio-pharmaceuticals and application thereof |
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