CN114643768A - Food-grade air-resistance light-transmitting multilayer film - Google Patents
Food-grade air-resistance light-transmitting multilayer film Download PDFInfo
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- CN114643768A CN114643768A CN202210424769.0A CN202210424769A CN114643768A CN 114643768 A CN114643768 A CN 114643768A CN 202210424769 A CN202210424769 A CN 202210424769A CN 114643768 A CN114643768 A CN 114643768A
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- Prior art keywords
- pet
- multilayer film
- food
- raw materials
- mxd6
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- 239000010410 layer Substances 0.000 claims abstract description 69
- 229920001634 Copolyester Polymers 0.000 claims abstract description 52
- 239000003365 glass fiber Substances 0.000 claims abstract description 50
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims abstract description 48
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 229940123973 Oxygen scavenger Drugs 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000012792 core layer Substances 0.000 claims abstract description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000013305 food Nutrition 0.000 claims abstract description 15
- 230000003287 optical effect Effects 0.000 claims abstract description 15
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000002667 nucleating agent Substances 0.000 claims abstract description 12
- 238000004806 packaging method and process Methods 0.000 claims abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 239000012745 toughening agent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 65
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 42
- 229920001400 block copolymer Polymers 0.000 claims description 35
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 24
- 230000004888 barrier function Effects 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical group [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- -1 polytetramethylene Polymers 0.000 claims description 13
- 239000005995 Aluminium silicate Substances 0.000 claims description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 4
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 3
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 claims description 3
- 229960002479 isosorbide Drugs 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 8
- 239000003814 drug Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 74
- 239000005020 polyethylene terephthalate Substances 0.000 description 74
- 239000000463 material Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 25
- 238000001125 extrusion Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000002457 bidirectional effect Effects 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
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- 230000005540 biological transmission Effects 0.000 description 6
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- 230000003179 granulation Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- LCHWKMAWSZDQRD-UHFFFAOYSA-N silylformonitrile Chemical compound [SiH3]C#N LCHWKMAWSZDQRD-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
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- 238000004381 surface treatment Methods 0.000 description 4
- 239000003484 crystal nucleating agent Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000007 Nylon MXD6 Polymers 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920006039 crystalline polyamide Polymers 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- 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
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/12—Polyester-amides
-
- 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
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a food-grade air-resistance light-transmitting multilayer film and a manufacturing method thereof. The copolyester inner layer comprises the following raw materials: modified copolyester chips obtained by copolymerizing terephthalic acid, ethylene glycol and a third monomer, a deoxidant, an optical open master batch and a crystallization nucleating agent are adopted; the PET/MXD6 blended core layer comprises the following raw materials: PET, MXD6, an oxygen scavenger and a compatilizer; the glass fiber reinforced outer layer comprises the following raw materials: PET, MXD6, superfine glass fiber and a toughening agent; the oxygen scavenger is a composition of an oxidizable polyether matrix and a cobalt salt catalyst. On the basis of selecting polymer materials such as PET, MXD6 and the like with good air resistance, the invention further uses the high-efficiency deoxidant, so that the product has good light transmittance, heat resistance and mechanical property, has ultrahigh air resistance, and can be applied to packaging in the fields of foods, medicines, medical instruments and the like.
Description
Technical Field
The invention belongs to the field of high-air-resistance films for blocking water vapor, oxygen and the like, and particularly relates to a food-grade air-resistance light-transmitting multilayer film.
Background
Packages for personal care, medical, pharmaceutical, household, industrial, food and beverage products require high barrier properties to gases such as water vapor, oxygen and carbon dioxide to preserve the freshness of the package contents. Packaging containers made of glass or metal provide an excellent barrier to the egress of substances from the container and to the ingress of substances from the environment. Containers made in whole or in part from polymers typically do not have the shelf life or barrier properties of glass or metal containers.
The high-barrier PET film has good long-term heat resistance and mechanical property, low cost and high cost performance, is widely applied to the fields of food packaging, medicine storage and the like, effectively prolongs the quality guarantee period and improves the economic benefit. Poly (m-xylylene adipamide) (MXD6) is a crystalline polyamide resin, is polymerized by m-xylylenediamine and adipic acid, has the characteristics of high heat distortion temperature, excellent barrier property and the like, and is expected to improve the barrier property of the material while keeping the heat resistance of the material by blending PET and MXD6 into a high-molecular composite barrier material. And a good index of refraction match between PET and MXD6 gives a blend that is nearly as transparent as PET. The composite material is a multi-phase solid material formed by combining two or more substances with different physical and chemical properties; because of 'making good for the weakness' and 'synergistic effect' among all the components, the defect of a single material is overcome. The barrier polymer material is a material having a certain shielding ability against small molecular substances such as gas and liquid. However, the existing barrier films in the market have the problems that the barrier performance is not excellent enough, the comprehensive performances such as the mechanical property of the modified film are obviously reduced, the manufacturing process is complicated, the practicability is difficult, and whitening turbidity is generated during heating sterilization to lose the light transmittance.
Patent CN107513257A discloses a barrier polymer composite material, which comprises PET and MXD6, and the material comprises the following components by weight: 50-90% of PET, 10-50% of MXD6 and 100% of the total weight of PET and MXD 6. The barrier property of the barrier polymer composite material is higher than that of a single-component polymer barrier material; the process is simple and the production period is short; the processing process is clean and pollution-free; the characteristics of different materials can be exerted, so that the composite material can have the characteristics of multiple materials at the same time; different materials can be compounded together without or with little adhesive, so the efficiency is high and the cost is low; even if the two polymers used have a large difference in melt viscosity, coextrusion compounding is still possible. However, the material has limited gas resistance, poor heat resistance and light transmittance, and is easy to generate whitening turbidity when heated at high temperature, so that the application requirement of the gas resistance material in the field of food cannot be met.
Meanwhile, the oxygen scavenger is added into the raw materials, so that the air resistance of the material can be further improved. Patent CN1430645A discloses an oxygen barrier composition comprising an oxygen barrier polymer, an oxygen scavenging polymer and an oxidation catalyst. The composition may be in the form of a physical blend or a cross-linked blend, the oxygen barrier polymer is polyethylene terephthalate (PET) or a polyamide other than MXD6, the oxygen scavenging polymer is a polyamide derived at least in part from a xylylenediamine type monomer, and the oxidation catalyst is a transition metal salt of a transition metal selected from the group consisting of cobalt, copper, nickel, iron, manganese, and the like. The invention is used for food packaging and uses an oxygen scavenger, but the whole air resistance and light transmittance are poor, and the preparation cost is high, so that the invention is not suitable for large-scale application in the food field.
Therefore, how to effectively improve the air resistance of the material while ensuring the light transmission, heat resistance and mechanical properties of the material so as to meet the packaging requirements of products such as personal care, medical treatment, medicines, foods, beverages and the like becomes a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the food-grade gas resistance light-transmitting multilayer film which has the advantages of improved gas resistance performance, simple process and easy operation on the basis of not influencing other performances such as light-transmitting performance, heat resistance, mechanical property and the like of the film.
Specifically, the invention provides a food-grade air-resistance light-transmitting multilayer film, which comprises the following layers:
inner copolyester layer: the raw materials comprise the following components in percentage by weight: 91-95% of modified copolyester chips obtained by copolymerization of terephthalic acid, ethylene glycol and a third monomer, 1-2% of deoxidant, 1-5% of optical open master batch and 1-2% of crystallization nucleating agent.
PET/MXD6 blended core layer: the raw materials comprise the following components in percentage by weight: 70-85% of PET, 610-20% of MXD, 1-3% of oxygen scavenger and 4-9% of compatilizer; MXD6(meta-xylylene adipamide) is poly (m-xylylene adipamide), commonly known as nylon MXD6, is a crystalline semi-aromatic polyamide obtained by condensation polymerization of adipic acid and m-xylylene diamine, is mainly used for high-permeability-resistant films and high-strength air-barrier structural materials, and has the greatest characteristic that the air resistance is not reduced along with the increase of humidity.
Glass fiber reinforced outer layer: the raw materials comprise the following components in percentage by weight: 70-85% of PET, 78-15% of MXD65, 5-15% of superfine glass fiber and 3-5% of toughening agent;
wherein the oxygen scavenger is a composition of an oxidizable polyether matrix and a cobalt salt catalyst; preferably, a combination of an oxidizable polyether matrix and cobalt stearate is used; more preferably, the composition of the polytetramethylene ether glycol-b-PET block copolymer and cobalt stearate is used as an oxygen scavenger, no induction period is needed before the oxygen scavenging activity is obtained, the service life of the material can be effectively prolonged, meanwhile, the national regulation is required to be met for food and medicine contact materials, or basically no oxygen scavenger is migrated from a mixture containing the oxygen scavenger to the content of a package for a part of packages, and the composition using the oxygen scavenger is safe and nontoxic, and can meet the requirement of the food, the medicine and the like on the safety of the package materials.
The raw materials of each layer are co-extruded to form a film, and the film is biaxially stretched to obtain the food-grade air-resistance light-transmitting multilayer film with the thickness of 75-200 mu m. For each layer thickness, the copolyester inner layer was obtained experimentally: PET/MXD6 blended core layer: the thickness ratio of the glass fiber reinforced outer layer is (2-3): (2-3): (4-6), the film product having the above thickness is selected so as to sufficiently satisfy the requirements of gas barrier properties, heat resistance, light transmittance and mechanical properties.
Further, the cobalt salt catalyst is cobalt stearate, and the content of the cobalt salt catalyst accounts for 1-10% of the total weight of the oxygen scavenger.
Further, the oxidizable polyether matrix is a polytetramethylene ether glycol-b-PET block copolymer, wherein the content of polytetramethylene ether glycol (PTMEG) accounts for more than 50 percent of the total weight of the block copolymer, and preferably more than 55 percent.
Further, the preparation method of the oxygen scavenger comprises the following steps: preparing a block copolymer by mixing polytetramethylene ether glycol (PTMEG) and PET at the temperature of 220-250 ℃;
adding cobalt salt catalyst into the block copolymer, mixing, extruding and pelletizing.
Further, the temperature of the above-mentioned mixing reaction was gradually raised from 220 ℃ to 250 ℃ at a rate of 10 ℃/1 hour to 15 ℃/1 hour.
Further, the above mixing reaction is carried out in the presence of a catalyst, wherein the catalyst comprises a titanium-based catalyst in an amount of 0.1 to 0.5% relative to the total weight of polytetramethylene ether glycol (PTMEG) and PET. By the preparation method of gradually increasing the temperature, the chain segments of the raw materials are fully activated, the polymerization effect is good, and the content of polytetramethylene ether glycol (PTMEG) is high, so that the yield of the deoxidant is effectively improved.
Further, the third monomer is at least one of 1, 4-cyclohexanediol, 1, 3-cyclopentanediol and isosorbide, and the molar ratio of the third monomer to the ethylene glycol is 0.1:10-0.8: 10.
Further, the optical open master batch is a mixed product of barium sulfate and the modified copolyester, the mass fraction of the barium sulfate is 2-5%, and the particle size is 1.2-1.6 mu m; the crystallization nucleating agent is a mixed product of nano kaolin and modified copolyester, the mass fraction of the nano kaolin is 1-3%, and the particle size is 30-80 nm.
The regularity of PET molecular chains is damaged by introducing a third monomer, the molecular chains are prevented from being piled up to form a large crystal region, the scattering of visible light caused by the large-size crystal region when the visible light passes through the film is reduced, and meanwhile, barium sulfate with the refractive index close to that of PET is selected as an opening agent, so that the influence of the film opening agent on light transmittance is greatly reduced.
Furthermore, the superfine glass fiber is modified by a silane coupling agent, the diameter is less than 5 μm, and the length-diameter ratio is 3: 1 to 5: 1. the silane coupling agent can be at least one of vinyl silane coupling agent, amino silane coupling agent, epoxy silane coupling agent and cyano silane coupling agent.
The compatilizer used in the invention is preferably semi-aromatic polyester amide, and the toughening agent is preferably at least one of AX8900 and EMA.
In a second aspect, a package is made using a food-grade, gas-resistant, light-transmitting multilayer film.
The invention has the advantages that:
1) compared with the prior art, the food-grade gas-resistance light-transmitting multilayer film and the packaging bag and other products made of the multilayer film have better gas resistance performance of water vapor, oxygen, carbon dioxide and other gases; the composition of the polytetramethylene ether glycol (PTMEG) -b-PET block copolymer and the cobalt salt catalyst is used as the deoxidant, no induction period exists before the deoxidant activity is obtained, the service life of the material can be effectively prolonged, and meanwhile, the deoxidant composition is safe and non-toxic and can meet the requirement of food and medicine on the safety of a packaging material;
2) the products provided by the invention all have excellent heat resistance and good light transmission, and the phenomenon of whitening and turbidity cannot be generated after heating, so that the light transmission of the film is not influenced;
3) the selection and arrangement sequence of the layers from inside to outside are favorable for the overall multi-layer film to show high air resistance, heat resistance, light transmission and good mechanical property. Firstly, utilizing a copolyester inner layer with better gas resistance and a PET/MXD6 blend to be matched with a safe deoxidant to obtain the copolyester inner layer with over-high gas resistance and the PET/MXD6 blend core layer; secondly, the overall mechanical property of the product is improved by using the modified superfine glass fiber, and the reinforced outer layer is not in direct contact with the content, so that the packaging safety is ensured; in addition, the PET/MXD6 blending core layer uses the high-efficiency compatilizer semi-aromatic polyesteramide, so that the blending core layer presents a submicron-grade compatibility level, the bonding performance and the mechanical performance in the blending core layer and between the blending core layer and the copolyester inner layer as well as between the blending core layer and the glass fiber reinforced outer layer can be improved, and a stable multilayer film product can be obtained.
4) The invention adopts the coextrusion process to manufacture the multilayer film, does not need to use additional adhesive/layer, does not need other special processes to obtain a satisfactory product, has simple and convenient operation and has considerable practical value.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples.
A food-grade air-resistance light-transmitting multilayer film comprises a copolyester inner layer, a PET/MXD6 blending core layer and a glass fiber reinforced outer layer. The copolyester inner layer comprises the following raw materials: the modified copolyester chip is obtained by copolymerizing terephthalic acid, ethylene glycol and a third monomer, wherein the third monomer is at least one of 1, 4-cyclohexanediol, 1, 3-cyclopentanediol and isosorbide; the oxygen scavenger is a composition of an oxidizable polyether matrix and a cobalt salt catalyst; the optical open master batch is a mixed product of barium sulfate and the modified copolyester; the crystallization nucleating agent is a mixed product of nano kaolin and the modified copolyester.
The PET/MXD6 blending core layer comprises the following raw materials: PET, MXD6, an oxygen scavenger and a compatilizer, wherein the compatilizer is semi-aromatic polyester amide.
The glass fiber reinforced outer layer comprises the following raw materials: PET, MXD6, superfine glass fiber and a toughening agent; modifying the superfine glass fiber by adopting a silane coupling agent; the toughening agent is at least one of AX8900 and EMA.
The oxidizable polyether matrix is a polytetramethylene ether glycol-b-PET block copolymer, wherein the content of polytetramethylene ether glycol (PTMEG) accounts for more than 50 percent of the total weight of the block copolymer. The cobalt salt catalyst is cobalt stearate, and the content of the cobalt salt catalyst accounts for 1-10% of the total weight of the oxygen scavenger.
The preparation method of the oxygen scavenger comprises the following steps:
preparing a block copolymer by mixing polytetramethylene ether glycol (PTMEG) and PET at the temperature of 220-250 ℃; adding cobalt salt catalyst into the block copolymer, mixing, extruding and pelletizing.
The preparation method of the food-grade air-resistance light-transmitting multilayer film comprises the following steps:
the preparation and the sufficient mixing of the raw materials of each layer comprise the following steps:
inner copolyester layer:
firstly, respectively preparing modified copolyester slices, optical open-ended master batches and a crystallization nucleating agent, and concretely, the method comprises the following steps:
preparation of modified copolyester chips: mixing a third monomer and ethylene glycol with a catalyst according to a molar ratio of 0.1:10-0.8:10, mixing with terephthalic acid, heating, vacuumizing for reaction, reducing pressure after the reaction is finished, discharging, cooling, and pelletizing to prepare modified copolyester chips;
preparing the optical open master batch: grinding part of the modified copolyester chips into powder, mixing with barium sulfate with the mass fraction of 2% -5% and the particle size of 1.2-1.6 mu m and a dispersing agent, and extruding and granulating by a double screw;
preparation of a crystallization nucleating agent: grinding part of the modified copolyester into powder, mixing with 1-3 mass percent of nano kaolin with the particle size of 30-80nm and a dispersing agent, and extruding and granulating by a double screw;
after the preparation, feeding 91-95% of modified copolyester chips, 1-2% of deoxidant, 1-5% of optical open master batch and 1-2% of crystallization nucleating agent into a mixer for fully mixing according to weight percentage.
PET/MXD6 blended core layer:
mixing 70-85% of PET, 610-20% of MXD and 4-9% of semi-aromatic polyester amide compatilizer according to weight percentage; then adding 1-3% of deoxidant and fully mixing;
glass fiber reinforced outer layer:
step one, preparing superfine glass fiber:
drying the chopped glass fiber with the diameter of less than 5 mu m at the temperature of 400-500 ℃ to remove surface moisture; milling for a certain time by a planetary ball mill, and sieving to obtain a length-diameter ratio of 3: 1 to 5: 1 of an ultrafine glass fiber; placing the superfine glass fiber in a solution of 3-8 wt% of silane coupling agent, carrying out surface treatment for 2-4h at 50-80 ℃, cooling and filtering to obtain modified superfine glass fiber;
secondly, adding 70-85 wt% of PET, 5-15 wt% of MXD65-15 wt% of the superfine glass fiber and 3-5 wt% of the toughening agent into a mixer for fully mixing;
and finally, feeding the fully mixed raw materials of each layer into three extruders for melting, extruding the melted raw materials through a co-extrusion die head to form a film, and performing bidirectional stretching, wherein the bidirectional stretching mode comprises synchronous stretching or asynchronous stretching, the stretching ratio is 3.3-3.6 times, and the stretching ratio in the MD direction is consistent with that in the TD direction. Wherein the longitudinal stretching is divided into a preheating section, a stretching section and a cooling shaping section, the temperature of the preheating section is 65-85 ℃, the temperature of the stretching section is 100-120 ℃, and the temperature of the cooling shaping section is 20-45 ℃; the transverse stretching is divided into a preheating section, a stretching section, a shaping section and a cooling section, wherein the temperature of the preheating section is 80-95 ℃, the temperature of the stretching section is 110-.
Example 1
The preparation method of the oxygen scavenger comprises the following steps:
putting polytetramethylene ether glycol (PTMEG), PET and a catalyst into a reaction mixing device, heating from 220 ℃ to 250 ℃ at a heating rate of 15 ℃/h, and carrying out mixing reaction to prepare a block copolymer, wherein the content of the polytetramethylene ether glycol (PTMEG) accounts for 55% of the total weight of the block copolymer; according to the mass percentage, 5 percent of cobalt stearate is added into 95 percent of the block copolymer to be fully mixed, and then the mixture is extruded and granulated to obtain the composition of the polytetramethylene ether glycol-b-PET block copolymer and the cobalt stearate.
The preparation method of the food-grade air-resistance light-transmitting multilayer film comprises the following steps:
extruding the three-layer raw materials of the copolyester inner layer, the PET/MXD6 blending core layer and the glass fiber reinforced outer layer by a three-layer extruder, and performing biaxial tension to obtain the food-grade air-resistance light-transmitting multilayer film. The method specifically comprises the following steps:
preparation and mixing of raw materials:
inner copolyester layer: in the embodiment, 1,4 cyclohexanediol with a molar ratio of 0.2:10, ethylene glycol and a catalyst are mixed, then mixed with terephthalic acid, heated and vacuumized to react, after the reaction is finished, the pressure is reduced, the material is discharged, cooled and cut into particles to prepare copolyester chips; grinding part of the modified copolyester chips into powder, mixing the powder with barium sulfate with the particle size of 1.4 mu m and a dispersing agent, and performing twin-screw extrusion granulation to prepare an optical open master batch, wherein the mass fraction of the barium sulfate is 3%; and grinding part of the modified copolyester into powder, mixing the powder with 40nm nano kaolin and a dispersing agent, and performing twin-screw extrusion granulation to prepare the crystal nucleating agent, wherein the mass fraction of the nano kaolin is 2%. 95% of the modified copolyester chips, 1.5% of the oxygen scavenger, 1.5% of the optical open-ended master batch and 2% of the crystallization nucleating agent are fed into a mixer to be fully mixed according to weight percentage.
In this embodiment, the weight percentages of the raw materials in the PET/MXD6 blended core layer are: 83% of PET, 610% of MXD, 2% of the deoxidant and 5% of semi-aromatic polyesteramide. The PET, MXD6 and the semi-aromatic polyester amide were mixed, and then the oxygen scavenger was added.
Glass fiber reinforced outer layer: in this example, chopped glass fibers having a diameter of 5 μm were dried at 400-500 ℃ for 2h to remove surface moisture; milling for a certain time by a planetary ball mill, and sieving to obtain a product with a length-diameter ratio of 3: 1 to 5: 1 of an ultrafine glass fiber; placing the superfine glass fiber in a solution of a cyano silane coupling agent with the weight percentage of 5%, carrying out surface treatment for 3h at 70 ℃, cooling and filtering to obtain the modified superfine glass fiber; adding 72 percent of PET, 615 percent of MXD, 9 percent of the superfine glass fiber and 89004 percent of AX into a mixer by weight percent, and fully mixing.
Co-extrusion and stretching:
and (3) respectively feeding the fully mixed raw materials into three extruders for melting, extruding the melted raw materials into a film through a co-extrusion die head, performing bidirectional stretching at a multiplying power of 3.4 multiplied by 3.4, shaping, and then feeding the film into a traction rolling system to obtain the food-grade gas-resistance light-transmitting multilayer film with the thickness of 75 microns.
Example 2
The preparation method of the oxygen scavenger comprises the following steps:
putting polytetramethylene ether glycol (PTMEG), PET and a catalyst into a reaction mixing device, heating from 220 ℃ to 250 ℃ at a heating rate of 10 ℃/h, and carrying out mixing reaction to prepare a block copolymer, wherein the content of the polytetramethylene ether glycol (PTMEG) accounts for 60% of the total weight of the block copolymer; according to the mass percentage, 10 percent of cobalt stearate is added into 90 percent of the block copolymer to be fully mixed, and then the mixture is extruded and granulated to obtain the composition of the polytetramethylene ether glycol-b-PET block copolymer and the cobalt stearate.
The preparation method of the food-grade air-resistance light-transmitting multilayer film comprises the following steps:
extruding the three-layer raw materials of the copolyester inner layer, the PET/MXD6 blending core layer and the glass fiber reinforced outer layer by a three-layer extruder, and performing biaxial tension to obtain the food-grade air-resistance light-transmitting multilayer film. The method specifically comprises the following steps:
preparation and mixing of raw materials:
inner copolyester layer: in the embodiment, 1,4 cyclohexanediol with a molar ratio of 0.2:10, ethylene glycol and a catalyst are mixed, then mixed with terephthalic acid, heated and vacuumized to react, after the reaction is finished, the pressure is reduced, the material is discharged, cooled and cut into particles to prepare copolyester chips; grinding part of the modified copolyester chips into powder, mixing the powder with barium sulfate with the particle size of 1.4 mu m and a dispersing agent, and performing twin-screw extrusion granulation to prepare an optical open master batch, wherein the mass fraction of the barium sulfate is 3%; and grinding part of the modified copolyester into powder, mixing the powder with 40nm nano kaolin and a dispersing agent, and performing twin-screw extrusion granulation to prepare the crystal nucleating agent, wherein the mass fraction of the nano kaolin is 2%. According to weight percentage, 95 percent of the modified copolyester chips, 2 percent of the deoxidant, 1.5 percent of the optical open-ended master batch and 1.5 percent of the crystallization nucleating agent are fed into a mixer for fully mixing.
In this embodiment, the weight percentages of the raw materials in the PET/MXD6 blended core layer are: 77% of PET, 615% of MXD, 3% of deoxidant and 5% of semi-aromatic polyester amide. The PET, MXD6 and the semi-aromatic polyester amide were mixed, and then the oxygen scavenger was added.
Glass fiber reinforced outer layer: in this example, chopped glass fibers having a diameter of 5 μm were dried at 400-500 ℃ for 2h to remove surface moisture; milling for a certain time by a planetary ball mill, and sieving to obtain a length-diameter ratio of 3: 1 to 5: 1 of ultra-fine glass fibers; placing the superfine glass fiber in a solution of a cyano silane coupling agent with the weight percentage of 5%, carrying out surface treatment for 3h at 70 ℃, cooling and filtering to obtain the modified superfine glass fiber; adding 72 percent of PET, 615 percent of MXD, 9 percent of superfine glass fiber and 89004 percent of AX into a mixer by weight percent, and fully mixing.
Co-extrusion and stretching:
and (3) respectively feeding the fully mixed raw materials into three extruders for melting, extruding the melted raw materials into a film through a co-extrusion die head, performing bidirectional stretching at a multiplying power of 3.4 multiplied by 3.4, shaping, and then feeding the film into a traction rolling system to obtain the food-grade gas-resistance light-transmitting multilayer film with the thickness of 75 microns.
Comparative example 1
The preparation method of the oxygen scavenger comprises the following steps:
putting polytetramethylene ether glycol (PTMEG), PET and a catalyst into a reaction mixing device, heating from 220 ℃ to 250 ℃ at a heating rate of 15 ℃/h, and carrying out mixing reaction to prepare a block copolymer, wherein the content of the polytetramethylene ether glycol (PTMEG) accounts for 55% of the total weight of the block copolymer; according to the mass percentage, 5 percent of cobalt stearate is added into 95 percent of the block copolymer to be fully mixed, and then the mixture is extruded and granulated to obtain the composition of the polytetramethylene ether glycol-b-PET block copolymer and the cobalt stearate.
The preparation method of the food-grade air-resistance light-transmitting multilayer film comprises the following steps:
extruding the two layers of raw materials of the copolyester inner layer and the PET/MXD6 blending core layer by an extruder to obtain the film without the glass fiber reinforced outer layer. The method specifically comprises the following steps:
preparation and mixing of raw materials:
inner copolyester layer: in the comparative example, 1,4 cyclohexanediol with a molar ratio of 0.2:10, ethylene glycol and a catalyst are mixed, then mixed with terephthalic acid, heated and vacuumized to react, and after the reaction is finished, the pressure is reduced, the material is discharged, cooled and cut into grains to prepare copolyester chips; grinding part of the modified copolyester chips into powder, mixing the powder with barium sulfate with the particle size of 1.4 mu m and a dispersing agent, and performing twin-screw extrusion granulation to prepare an optical open master batch, wherein the mass fraction of the barium sulfate is 3%; and grinding part of the modified copolyester into powder, mixing the powder with 40nm nano kaolin and a dispersing agent, and performing twin-screw extrusion granulation to prepare the crystal nucleating agent, wherein the mass fraction of the nano kaolin is 2%. 95% of the modified copolyester chips, 1.5% of the oxygen scavenger, 1.5% of the optical open-ended master batch and 2% of the crystallization nucleating agent are fed into a mixer to be fully mixed according to weight percentage.
In the comparative example, the weight percentages of the raw materials in the PET/MXD6 blending core layer are as follows: 83% of PET, 610% of MXD, 2% of deoxidant and 5% of semi-aromatic polyester amide. Mixing the PET, the MXD6 and the semi-aromatic polyester amide, and adding the oxygen scavenger.
Glass fiber reinforced outer layer: in this comparative example, there is no outer fiberglass reinforcing layer.
Co-extrusion and stretching:
and respectively feeding the fully mixed raw materials of each layer into two extruders for melting, extruding the materials through a co-extrusion die head to form a film, performing bidirectional stretching at a multiplying power of 3.4 multiplied by 3.4, shaping, and then feeding the film into a traction rolling system to obtain a film with the thickness of 75 microns.
Comparative example 2
The preparation method of the oxygen scavenger comprises the following steps:
putting polytetramethylene ether glycol (PTMEG), PET and a catalyst into a reaction mixing device, heating from 220 ℃ to 250 ℃ at a heating rate of 15 ℃/h, and carrying out mixing reaction to prepare a block copolymer, wherein the content of the polytetramethylene ether glycol (PTMEG) accounts for 55% of the total weight of the block copolymer; according to the mass percentage, 5 percent of cobalt stearate is added into 95 percent of the block copolymer to be fully mixed, and then the mixture is extruded and granulated to obtain the composition of the polytetramethylene ether glycol-b-PET block copolymer and the cobalt stearate.
The preparation method of the food-grade air-resistance light-transmitting multilayer film comprises the following steps:
extruding two layers of raw materials of the PET/MXD6 blending core layer and the glass fiber reinforced outer layer by an extruder, and performing biaxial tension to obtain the food-grade air-resistance light-transmitting multilayer film. The method specifically comprises the following steps:
preparation and mixing of raw materials:
in the comparative example, the weight percentages of the raw materials in the PET/MXD6 blending core layer are as follows: 83% of PET, 610% of MXD, 2% of deoxidant and 5% of semi-aromatic polyester amide. The PET, MXD6 and the semi-aromatic polyester amide were mixed, and then the oxygen scavenger was added.
Glass fiber reinforced outer layer: in this comparative example, chopped glass fibers having a diameter of 5 μm were dried at 400-500 ℃ for 2 hours to remove surface moisture; milling for a certain time by a planetary ball mill, and sieving to obtain a length-diameter ratio of 3: 1 to 5: 1 of an ultrafine glass fiber; placing the superfine glass fiber in a solution of a cyano silane coupling agent with the weight percentage of 5%, carrying out surface treatment for 3h at 70 ℃, cooling and filtering to obtain the modified superfine glass fiber; according to weight percentage, PET72 percent, MXD 615 percent, the superfine glass fiber 9 percent and AX 89004 percent are added into a mixer to be fully mixed.
Co-extrusion and stretching:
and respectively feeding the fully mixed raw materials of each layer into two extruders for melting, extruding the materials through a co-extrusion die head to form a film, performing bidirectional stretching at a multiplying power of 3.4 multiplied by 3.4, shaping, and then feeding the film into a traction rolling system to obtain a film with the thickness of 75 microns.
Comparative example 3
The preparation method of the oxygen scavenger comprises the following steps:
putting polytetramethylene ether glycol (PTMEG), PET and a catalyst into a reaction mixing device, heating from 220 ℃ to 250 ℃ at a heating rate of 15 ℃/h, and carrying out mixing reaction to prepare a block copolymer, wherein the content of the polytetramethylene ether glycol (PTMEG) accounts for 55% of the total weight of the block copolymer; according to the mass percentage, 5 percent of cobalt stearate is added into 95 percent of the block copolymer to be fully mixed, and then the mixture is extruded and granulated to obtain the composition of the polytetramethylene ether glycol-b-PET block copolymer and the cobalt stearate.
The preparation method of the food-grade air-resistance light-transmitting multilayer film comprises the following steps:
extruding the single-layer PET/MXD6 blended core layer raw material through an extruder, and performing biaxial tension to obtain the food-grade air-resistance light-transmitting multilayer film. The method specifically comprises the following steps:
preparation and mixing of raw materials:
in the comparative example, the weight percentages of the raw materials in the PET/MXD6 blending core layer are as follows: 83% of PET, 610% of MXD, 2% of deoxidant and 5% of semi-aromatic polyester amide. Mixing the PET, the MXD6 and the semi-aromatic polyester amide, and adding the oxygen scavenger.
Co-extrusion and stretching:
the fully mixed raw materials are sent into an extruder to be melted and extruded into a film through a co-extrusion die head, and the film is stretched and shaped in a bidirectional way at a multiplying power of 3.4 multiplied by 3.4 and then enters a traction rolling system to obtain a film with the thickness of 75 mu m.
Comparative example 4
The common PET raw material is extruded by an extruder and is subjected to biaxial tension of 3.4 multiplied by 3.4 to obtain a film with the thickness of 75 μm.
The performance test was performed on the above-mentioned examples 1, 2, 3, and 4, and the test results are shown in tables 1 and 2.
The film performance test method comprises the following steps:
1. light transmittance: according to ISO13468, the test is carried out using BYK HAZE-gard i, Germany.
2. Mechanical properties: tensile strength, elongation at break were measured according to ASTM D882.
3. Heat shrinkage ratio: tested according to ASTM D1204.
4. Moisture permeability test: the test is carried out according to GB 1037 cup method which is a test method for the water vapor permeability of plastic films and sheets, and a W3/031 water vapor permeability tester is used for carrying out a water vapor permeability test for 24 hours.
5. And (3) testing air permeability: the oxygen permeability was measured for 24 hours using a Classic2016 pressure differential pressure gas permeameter, according to GB 1038 "Plastic film and sheet gas permeability test method-pressure differential method".
TABLE 1 test results of light transmittance, mechanical properties and heat resistance of samples
TABLE 2 gas resistance Performance test results of the samples
As can be seen from tables 1 and 2, examples 1 and 2 having three-layer structures of the copolyester inner layer, the PET/MXD6 blend core layer and the glass fiber reinforced outer layer all have better effects in terms of mechanical properties, heat shrinkability and air resistance, and the main reason is that the three-layer film is reasonably arranged and cooperated with each other in structure and composition, on one hand, the copolyester inner layer and the PET/MXD6 blend core layer provide satisfactory air resistance, and the glass fiber reinforced outer layer improves the overall mechanical properties of the multilayer film; on the other hand, the PET, MXD6 and the compatilizer in the PET/MXD6 blending core layer are matched to enable the layer to have a submicron level compatibility level, and the components of the PET/MXD6 blending core layer respectively have similar compositions with the inner layer component and the outer layer component, so that the adhesion of the PET/MXD6 blending core layer respectively with the copolyester inner layer and the glass fiber reinforced outer layer is improved, a multilayer film product with stable interlayer adhesion performance is obtained, and the comprehensive performances of the multilayer film, such as mechanics, heat resistance and the like, are further improved. Although the copolyester is of a multilayer structure, due to the low crystallinity of the copolyester inner layer, the refractive index of the PET and the MXD6 which are well matched, and the control of the dosage and the size of various additives, a multilayer film product with good light transmission performance can be obtained, and the packaging requirements of light transmission and good air resistance performance are met.
Comparing examples 1 and 2, example 2 has longer mixing reaction time in the preparation of the oxygen scavenger, higher content of polytetramethylene ether glycol (PTMEG) in the block copolymer, and higher content of the oxygen scavenger in the copolyester inner layer and the PET/MXD6 blending core layer, thereby showing higher gas resistance.
In comparison, the comparative example 1 has no glass fiber reinforced outer layer, the reduction of the mechanical property is obvious under the condition of the same film thickness, the stress safety and the stability of the product in the transportation and use processes are not ensured, and the superfine glass fiber modified by the cyano silane coupling agent has obvious effect on the improvement of the overall mechanical property of the outer layer and even the multilayer film. Comparative example 2 has no copolyester inner layer, and its mechanical properties are reduced less remarkably, but its heat shrinkage and gas barrier properties are reduced more remarkably, and thus it can be seen that the copolyester inner layer contributes more to the heat resistance and gas barrier properties of the multilayer film. Comparative example 3 has only a single layer of PET/MXD6 blend modified film, equivalent to only the original PET/MXD6 blend core layer, and it can be seen from the data that the combination of properties of the core layer itself at equivalent thickness is clearly inferior to those of examples 1 and 2. Comparative example 4 is a PET film only, and its gas resistance and heat resistance hardly satisfy the packaging requirements of the present invention. In conclusion, the design and matching of the multilayer structure selected by a plurality of experiments in the invention have obvious scientificity and importance.
The foregoing describes preferred embodiments of the present invention, and is intended to provide a clear and concise description of the spirit and scope of the invention, and not to limit the same, but to include all modifications, substitutions, and alterations falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A food-grade gas-barrier light-transmitting multilayer film comprising the following layers:
inner copolyester layer: the raw materials comprise the following components in percentage by weight: 91-95% of modified copolyester chips obtained by copolymerizing terephthalic acid, ethylene glycol and a third monomer, 1-2% of deoxidant, 1-5% of optical open master batch and 1-2% of crystallization nucleating agent;
PET/MXD6 blended core layer: the raw materials comprise the following components in percentage by weight: 70-85% of PET, 610-20% of MXD, 1-3% of oxygen scavenger and 4-9% of compatilizer;
glass fiber reinforced outer layer: the raw materials comprise the following components in percentage by weight: 70-85% of PET, 78-15% of MXD65, 5-15% of superfine glass fiber and 3-5% of toughening agent;
wherein the oxygen scavenger is a composition of an oxidizable polyether matrix and a cobalt salt catalyst;
the raw materials of each layer are co-extruded to form a film, and the film is biaxially stretched to obtain the food-grade air-resistance light-transmitting multilayer film with the thickness of 75-200 mu m.
2. The food grade gas barrier light transmissive multilayer film of claim 1, wherein the cobalt salt catalyst is cobalt stearate in an amount of 1-10% by weight of the oxygen scavenger.
3. The food grade gas barrier light transmitting multilayer film of claim 2, wherein the oxidizable polyether matrix is a polytetramethylene ether glycol-b-PET block copolymer having a polytetramethylene ether glycol (PTMEG) content of greater than 50% by weight of the total weight of the block copolymer.
4. A food grade gas barrier light transmitting multilayer film according to claim 3 wherein said oxygen scavenger is prepared by a method comprising:
preparing a block copolymer by mixing polytetramethylene ether glycol (PTMEG) and PET at the temperature of 220-250 ℃;
adding cobalt salt catalyst into the block copolymer, mixing, extruding and pelletizing.
5. The food-grade gas-barrier light-transmitting multilayer film according to claim 4, wherein the temperature of the mixing reaction is gradually increased from 220 ℃ to 250 ℃ at a rate of 10 ℃/h to 15 ℃/h.
6. The food grade gas barrier light transmitting multilayer film of claim 4, wherein the mixing is performed in the presence of a catalyst, wherein the catalyst comprises a titanium based catalyst in an amount of 0.1 to 0.5% relative to the total weight of polytetramethylene ether glycol (PTMEG) and PET.
7. The food-grade gas-barrier light-transmitting multilayer film according to any one of claims 1 to 6, wherein the third monomer is at least one of 1, 4-cyclohexanediol, 1, 3-cyclopentanediol, and isosorbide, and the molar ratio of the third monomer to ethylene glycol is 0.1:10 to 0.8: 10.
8. The food-grade gas-barrier light-transmitting multilayer film according to claim 7, wherein the optical open-ended master batch is a mixture of barium sulfate and the modified copolyester, the mass fraction of the barium sulfate is 2-5%, and the particle size is 1.2-1.6 μm; the crystallization nucleating agent is a mixed product of nano kaolin and the modified copolyester, the mass fraction of the nano kaolin is 1-3%, and the particle size is 30-80 nm.
9. The food-grade gas-resistive light-transmitting multilayer film according to claim 8, wherein the superfine glass fibers are modified by silane coupling agent, the diameter is less than 5 μm, and the length-diameter ratio is 3: 1 to 5: 1.
10. a packaging bag made of the food grade gas-resistant light-transmitting multilayer film according to any one of claims 1 to 9.
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