CN110272551A - A kind of polylactic acid film and preparation method thereof - Google Patents
A kind of polylactic acid film and preparation method thereof Download PDFInfo
- Publication number
- CN110272551A CN110272551A CN201910385732.XA CN201910385732A CN110272551A CN 110272551 A CN110272551 A CN 110272551A CN 201910385732 A CN201910385732 A CN 201910385732A CN 110272551 A CN110272551 A CN 110272551A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- cellulose
- film
- layer
- surface layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 229920006381 polylactic acid film Polymers 0.000 title claims abstract description 41
- 239000010410 layer Substances 0.000 claims abstract description 126
- 229920002678 cellulose Polymers 0.000 claims abstract description 72
- 239000001913 cellulose Substances 0.000 claims abstract description 72
- 239000002344 surface layer Substances 0.000 claims abstract description 60
- 229920002101 Chitin Polymers 0.000 claims abstract description 37
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 36
- 239000004626 polylactic acid Substances 0.000 claims abstract description 26
- 239000008187 granular material Substances 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 230000036961 partial effect Effects 0.000 claims abstract description 5
- 238000007766 curtain coating Methods 0.000 claims abstract description 4
- 235000010980 cellulose Nutrition 0.000 claims description 61
- 239000007788 liquid Substances 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 238000007872 degassing Methods 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 7
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 6
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- 238000004132 cross linking Methods 0.000 claims description 5
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- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 4
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 4
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- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 4
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011425 bamboo Substances 0.000 claims description 4
- 210000002421 cell wall Anatomy 0.000 claims description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 4
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- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 4
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 4
- 229960002675 xylitol Drugs 0.000 claims description 4
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 3
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 3
- PFZPMLROUDTELO-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;acetate Chemical compound CC(O)=O.CN1C=CN=C1 PFZPMLROUDTELO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
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- 230000008021 deposition Effects 0.000 claims description 3
- 239000010954 inorganic particle Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- WWFKDEYBOOGHKL-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound Br.CCN1CN(C)C=C1 WWFKDEYBOOGHKL-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical compound Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 241000238557 Decapoda Species 0.000 claims description 2
- SJRXVLUZMMDCNG-UHFFFAOYSA-N Gossypin Natural products OC1C(O)C(O)C(CO)OC1OC1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=C(O)C2=O SJRXVLUZMMDCNG-UHFFFAOYSA-N 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 claims description 2
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- SJRXVLUZMMDCNG-KKPQBLLMSA-N gossypin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=C(O)C2=O SJRXVLUZMMDCNG-KKPQBLLMSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
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- 235000010358 acesulfame potassium Nutrition 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 12
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000010409 thin film Substances 0.000 description 8
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
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- 238000000227 grinding Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
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- 241001330002 Bambuseae Species 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 230000006872 improvement Effects 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
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- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—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
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
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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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance 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
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
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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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/02—Synthetic macromolecular particles
- B32B2264/0214—Particles made of materials belonging to B32B27/00
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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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/02—Synthetic macromolecular particles
- B32B2264/0214—Particles made of materials belonging to B32B27/00
- B32B2264/025—Acrylic resin particles, e.g. polymethyl methacrylate or ethylene-acrylate copolymers
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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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/12—Mixture of at least two particles made of different materials
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/716—Degradable
- B32B2307/7163—Biodegradable
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2317/00—Animal or vegetable based
- B32B2317/18—Cellulose, modified cellulose or cellulose derivatives, e.g. viscose
-
- 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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
-
- 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
- C08J2397/00—Characterised by the use of lignin-containing materials
- C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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Abstract
The present invention relates to a kind of polylactic acid films comprising: the internal layer prepared by copolymer of poly lactic acid；At least one middle layer mainly prepared by cellulose and chitin；At least one surface layer prepared by copolymer of poly lactic acid, is based on surface layer weight, and the cross-linked polymer spheric granules that 0.05wt%-0.6wt% partial size is 2-6 μm is contained on surface layer；Middle layer is between internal layer and surface layer.The invention further relates to a kind of preparation method of polylactic acid film, internal layer, middle layer and surface layer coextrusion curtain coating are compound, and carry out biaxial stretch-formed, and above-mentioned polylactic acid film is made.Containing polylactic acid polymer and the multi-layer co-extruded film of cellulose-chitin prepared by the present invention, reduce coefficient of friction, reduce adhesion, increase heat sealability, reduce and be electrostatically-formed and film dust suction, and its biodegradable is strong, cellulose-periostracum have gas be difficult to by crystal structure, the invasion of oxygen can be effectively kept out, the film of preparation is more suitable as the packing film of fresh food.
Description
Technical field
The invention belongs to technical field of film preparation more particularly to a kind of polylactic acid film and preparation method thereof.
Background technique
Polylactic acid is biodegradable or compost the polymer generated by lactic acid polycondensation.For producing the list of polylactic acid
There are two types of optically active isomers, i.e. D-ALPHA-Hydroxypropionic acid and Pfansteihl for body tool.When two kinds of isomers are combined together and polymerize, they
Relative quantity generate have different crystallinity (amorphous state to semi-crystalline state), crystallization behavior and fusing point various polymer.This type
The polymer of type can be obtained from Cargill-Dow, and its represent type commercial polymer grade as PLA4042.TM. and
PLA4060.TM..Two kinds of optical isomers of the lactic acid of two kinds of resins in varing proportions, Pfansteihl and D-ALPHA-Hydroxypropionic acid are combined
Preparation.The final crystallinity and crystallization behavior of the relative scale control polymer of two kinds of isomers and different physically and thermally
Property.
When commercially available polylactic acid polymer (PLA) coextrusion and it is biaxial stretch-formed when, prepared film has excellent saturating
Lightness and gloss, but show goodish as coefficient of friction (the surface slipperiness energy as defined by COF) and undesirable
Film curls into, therefore is in processing or by being easy to be scraped off when fixed equipment component on packing machine.Furthermore, it is necessary to mistake
Film product is pulled through packing machine by big power, is led to breakage of thin film applied and is generated fold and folding line.The film prepared by unmodified PLA
Also it easily shows adhesion roll-good form, especially when by surface treatment, such as passes through corona common in thin film industry, fire
Flame or method of plasma processing.Other than above-mentioned adhesion, formed in winding on finder and in recoil and incision
Whole roller is also extremely difficult.This undesirable roller is formed and the trend of adhesion causes excessive film to lose the manufacture efficiency with difference.Cause
This, it is necessary to the PLA film prepared by commercial resins is modified.
United States Patent (USP) US6713174, which is disclosed, is made single layer biaxially oriented film for polylactic acid polymer, can for producing
Hot sticky single thin film.Although embodiment shows the silica of 2.5 μm of the addition into polymer, there is no remember for its full text
It carries and silica performance improvement obtained and its economic influence to Biaxially oriented film produced is added, also do not refer to
Improve correlated performance using multilayer film.
In addition, improved using anti-block particulates film performance be also it is well known that but in the case where single thin film,
The incorporation of additive must pass through the whole thickness of polymer.Because it is two adjacent thin that anti-block particulates are designed to control
The surface reagent of contact area between film layer or film surface and adjacent surface, such as metal on process equipment or rubber cover
The roller of lid.Therefore, had several drawbacks in that using tool: benefit possessed by most of particle can be incorporated in far from surface due to them
Film inside and lose；A greater amount of anti-block particulates needed for must using than improving surface property, this leads to resist blocking and that
The increased costs of grain, and expensive but efficient additive, such as spherical cross-linked silicone will be used by limitation, such as
Tospearl.TM. or the acrylic acid sphere of crosslinking, such as Epostar.TM.；Additional non-functional is used in the core
Particle will increase amount of light scatter by film haze measurement, and reduce the value and aesthstic attractive force of film, and influence display packing production
The ability of product.
The biaxial orientation polylactic acid that United States Patent (USP) US6649732B2 discloses a kind of transparent high-barrier ceramic coated is thin
Film is prepared by 100% Poly-L-lactide that Pfansteihl polymerization generates.Film can contain anti-block particulates, and limitation is ceramic painting
The surface covered must have reduced particulate load and at least be not above 1.89 μm of protrusion across the deposition surface.The film
It also needs to add antisatic additive, such as anion and cationic surfactant and nonionic surfactant, to reduce
Electrostatic in film.But the patent does not mention anti-block particulates and generates the influence of performance to film electrostatic, and focuses on
Improve transparent obstructive performance when coated ceramic barrier layer.Resist blocking and that is also added into coextruded layer without discussing for the patent
Grain, and suggest being added anti-block particulates into lactic acid monomer before the polymerization to ensure good dispersion.The patent also describes
Polylactic acid film can be coextruded with the second resin, but it does not refer to the property of second of resin, it is not indicated that change
Improvement of the process performance of kind film to made by it.
The heat sealability of the plural layers of United States Patent (USP) US6649732 passes through addition polyolefin layer such as polypropylene or polyethylene
It controls, this may also need to add before add hot sealing layer adhesion-promoting layer to be added to film surface.Adhesion-promoting layer is
It is added to the layer of film surface by coating method, and can be polyester, acrylic resin, polyurethane or two or more materials
The copolymer of material.Alternatively, suitable adhesive phase can be used by dry method or squeeze out laminating method for the heat sealing layer of polyolefin
It is added in film.
United States Patent (USP) US6703115 discloses a kind of plural layers, with 70 to 100% polylactic acid sandwich layer and 0 to
30% filler and a second layer, the second layer include 20 to 80% one or more thermoplastic polymers and 80 to
20% inorganic filler, the WVTR of inorganic filler when stretching are greater than the WVTR of the thermoplastic material of the second layer.Of the invention is thin
Film is not filled by filler in sandwich layer and surface layer.
The film of above-mentioned prior art preparation sometimes can also be using polyethylene, polyvinyl chloride, polyvinylidene chloride etc.
The polymer plastic bed of material, this kind of material itself are difficult to degrade, and generate serious " white pollution " to environment.In addition, freezing or adding
In hot situation, plastics have chemical change, in harmful substance permeated into food, enter human body with food, to endanger
Human health.In addition, the gas barrier property of the film produced in the prior art is poor, adhesion inhibiting properties are poor, and easily electrostatic produces
It is raw.Therefore, carrying out the preparation of packing film using biodegradable and reproducible material is extremely to pay close attention at present.
Cellulose and chitin are most common two kinds of organic macromolecules on the earth, are generally deposited in the life entity of nature
?.Cellulose is the skeleton structure in plant cell wall, and from a wealth of sources and rich reserves are linear macromolecule polysaccharide, have
The characteristics such as degradable, pollution-free and good mechanical performance.Chitin mostlys come from insect or shellfish, in nature
Reserves be only second to cellulose, compatibility is good, and derivative species are more.
Although having realized the preparation of cellulose membrane at present, its film prepared there are tensile properties poor, cracky, waste product
The disadvantages of rate is high, and have no that cellulose and chitin can prepare the report of film jointly.
Summary of the invention
In order to overcome the defects of the prior art, the present invention relates to a kind of polylactic acid film and preparation method thereof, the films
For the oriented multilayer film of coextrusion, comprising biodegradable polylactic acid and cellulose and chitin, the oriented multi-layer is poly-
Lactic acid film is used as one of food and industrial packaging application without support or laminate packaging film.Polylactic acid of the present invention
There is film the adhesion of improved coefficient of friction and reduction and electrostatic to generate, and show the winding significantly improved, cutting, vacuum
Metallization and packing machine operation, and there is excellent gas barrier property, biodegradability and the feature of environmental protection.
To realize purpose above, the present invention adopted the following technical scheme that:
The first purpose of the invention is to provide a kind of polylactic acid films comprising:
One internal layer, is prepared by copolymer of poly lactic acid；
At least one middle layer, preparation component includes: cellulose and chitin；
At least one surface layer, is prepared by copolymer of poly lactic acid, wherein is based on surface layer weight, the surface layer is contained
The cross-linked polymer spheric granules that the partial size of 0.05wt%-0.6wt% is 2-6 μm；
Wherein, the middle layer is between the internal layer and surface layer.
In order to advanced optimize above-mentioned polylactic acid film, the technical measures that the present invention takes further include:
Further, the mass ratio of the cellulose and chitin is 1~5:1.More preferably 2~3:1, more preferably
2.5:1.
Further, the cellulose is selected from wood-cellulose, grass fiber element, bamboo fiber element, gossypin, crudefiber crop
At least one of cellulose or microcrystalline cellulose.
Further, the chitin is from the ectoskeleton of crab or shrimp, squid parietal bone, the cuticula of insect and fungi
At least one of cell wall.
Further, the prepared composition of the middle layer further includes polylactic acid polymer, with cellulose and chitin
Total mass ratio is 2~4:1.
Further, the surface layer and internal layer have identical or different polymer.
Further, the surface layer polymer is the poly (lactic acid) composition that fusing point is lower than the internal layer polymer.
Further, the crystallinity of the surface layer polymer is lower than the crystallinity of the internal layer polymer.
Further, the surface layer is attached at least one surface of the middle layer, and only one surface layer includes institute
State cross-linked polymer spheric granules.
Further, the metal vacuum of the film surface opposite with the surface layer containing cross-linked polymer spheric granules deposition
Metallization.
Further, vacuum-deposited metal is aluminium.
Further, the cross-linked polymer spheric granules is the polymethylsilsesquioxane of crosslinking or the acrylic acid of crosslinking
Resin.
Further, the content of the cross-linked polymer spheric granules be surface layer polymer weight 0.01wt% extremely
0.5wt%.
Further, one or two surface of the polylactic acid film is subjected to corona, flame or corona treatment.
Further, the internal layer is blended with the cavitation agent selected from incompatible polymer or inorganic particle, the inorganic particulate
Grain forms a series of microvoids when stretching in the range of 0.1-4.0 microns, and each microvoid includes that at least one gap is drawn
Send out particle.
Further, the middle layer is coloring.
Further, the coloring pigment of the middle layer is TiO2。
A second object of the present invention is to provide a kind of preparation methods of polylactic acid film comprising following steps: passing through
Independent extrusion prepares internal layer, middle layer and surface layer；Internal layer, middle layer and surface layer will be prepared and carry out coextrusion curtain coating in a predetermined order
It is compound, and carry out biaxial stretch-formed, any above-mentioned polylactic acid film is made；
Wherein, the preparation step of the middle layer includes:
Chitin is added in ionic liquid according to the concentration of 0.5~2.5wt%, stirring and dissolving 3 at 70~100 DEG C~
Cellulose dispersion liquid is added in 6h, and 1~2h is stirred at 90~120 DEG C, obtains chitin-cellulose mixed liquor, adjusts PH to close to 7,
The cellulose nano-fibrous mixing film liquid of chitin-is made in ground 30~60min；Suitable plasticising is added in mixing film liquid
Agent is heated to 30~50 DEG C and is uniformly mixed, 10~30min of evacuation and centrifugal degassing at 2500~4500r/min, using extrusion work
The middle layer is made in skill.
In order to advanced optimize above-mentioned preparation method, the technical measures that the present invention takes include:
Further, the ionic liquid includes 1- ethyl-3-methylimidazole acetate, 1- methylimidazole acetate, 1,
3- methylimidazole acetate, 1- butyl -3- methylimidazole acetate, glycine hydrochloride, 1- butyl -3- methylimidazole villaumite
Or 1- ethyl-3-methylimidazole bromide.
Further, the plasticizer is selected from one or more of glycerol, polyethylene glycol, sorbierite, xylitol.
Further, the preparation step of the cellulose dispersion liquid includes: that cellulose and polyalcohol is taken to carry out heating swollen
Processing is added acid and is stirred mixing and the further processing of heating swollen, cellulose dispersion liquid is made.
Further, the specific preparation step of the cellulose dispersion liquid includes: to take bone dry fiber plain, is ground into particle
Shape crosses 20~50 meshes；Cellulose is uniformly mixed with polyalcohol with solid-to-liquid ratio 1:5~10, in 100~120 DEG C of heating swollens 1
~3h；It is added acid relative to system gross mass 0.2~0.45% in cellulose after swollen, mechanical stirring and 80~
Cellulose dispersion liquid is made in 100 DEG C of 1~4h of oil bath heating swollen and mechanical stirring.
Further, the polyalcohol is propylene glycol, glycerine or butantriol；The acid is sulfuric acid, hydrochloric acid or phosphoric acid.
Further, mechanical lapping equipment is colloid mill or ultramicro grinding instrument, milling time 10-40min.
Further, the chitin is ground into graininess before ionic liquid is added, and crosses 20~50 meshes.
Further, the middle layer further includes following steps: by chitin-cellulose middle layer by plasticising processing
It is pre-mixed in premixing machine with polylactic acid polymer, after being sufficiently mixed uniformly, by mixed material blending extrusion, to obtain
Polylactic acid-cellulose-chitin middle layer is made；Wherein, the initial temperature of premixing is 55~65 DEG C, and the revolving speed of premixing machine is
800~1000 turns/min, premixing is 30~45min；The condition of blending extrusion are as follows: melting extrusion temperature is 180~200
℃。
In particular it relates to a kind of biodegradable film of coextrusion, it includes in copolymer of poly lactic acid
Layer (sandwich layer) and at least one middle layer and at least one surface layer, more specifically up to four copolymer of poly lactic acid surface layers,
Its fusing point is identical or lower as sandwich layer, and preferably three layers and two layers of middle layer, the chitin and fibre of two layers of middle layer
The proportion of dimension element may be the same or different.For at least one outermost surface layer, the spheric granules prepared by cross-linked polymer,
It is preferably selected from poly methyl silsesquioxane and acrylic resin, the poly methyl silsesquioxane that most preferred diameters are 2-6 μm, with table
The amount of the 0.0-0.6wt% of layer weight is added, and preferably 2.0-4.5 μm of granularity is added with the amount of the 0.1-0.3wt% of surface layer weight
Enter.The relative thickness for selecting sandwich layer, middle layer and surface layer allows the final surface skin depth after stretching at 0.5 to 3 μm
Between change, preferably 0.8 to 1.8 μm, and unrelated with final film thickness.
Plural layers can be orientated in certain sequence or simultaneously, use industry common or stenter well known in the art
Technique production.Under the specific condition of sequence orientation, step is described as follows:
By the way that polymer is melted separately in individual extruder, add the particles in the polymer feed of extruder,
And it mixes and disperses to prepare each layer of film in the polymer during polymer melting.Each layer is filtered to ensure
Melt cleaning, without removing the particle of addition and combining each layer in multi-cavity die head.Those skilled in the art should understand that
, the combination of multilayer melt can also be carried out with coextrusion supply head, or be made in coextrusion supply head and multi-cavity die-head combination
With.When multilayer melt is squeezed out from die head, using pinning mechanism well known in the art, such as electrostatic pinning, air knife, vacuum tank,
The combination (such as air knife and electrostatic edge pinning) of additional pressure area chill roll or each method, is suppressed to cooling chromium plating
On casting roller.By the cooling cast film of casting roller to set surface layer, middle layer and the molecular structure of sandwich layer, taken for subsequent
To.When removing from casting section, cast-sheet is transported to the finder of machine direction with uniform speed, at such speeds,
Cast-sheet contacts with a series of roller of heating and is heated to draft temperature.Lead to the sheet material of heating between two rolls
It crosses, second roller is driven with the speed for being higher than first roller, along axial direction or machine direction (MD) oriented film.The machine direction
Tensile speed ratio (MDX) can be 2 to 6 times, preferably 2.5 to 4 times.Then cooling MD is drawn after stretching in other heat transfer roll
The film stretched, and be transferred in stenter and carry out laterally (TD) orientation.The TD is orientated by by preheating, stretching and annealing portion
Stretching in the heating furnace of composition is completed.It is stretching between two continuous tracks and carries out, wherein continuous chain has folder
Son, edge of the clip designed for clamping MD stretched sheet.In regenerator section, track is substantially parallel and its width is approximate
In the width of MD stretched sheet.Then track dissipates, and forces chain to separate and stretches the film being clipped in clip.TD stretching can
To be 2 times to 6 times, preferably 2.5 to 4 times of original width of chain separation.Then make track in the end of stretched portion with most
Whole width parallel, and by film heating to the temperature for being suitable for that film is made to crystallize and anneal, while the film is limited in clip.
This crystallization and annealing select the contraction of film when reducing reheating to obtain required film in subsequent conversion operation
The condition of contraction.If desired, chain separation can slightly be reduced to improve the dimensional stability of film, this is known in the art
's.Then track exits baking oven, and film quenches in air, then releases from clip.After release, by the film of stretching
The thickness uniformity of film is measured by thickness scanning movement.The adjustment of the manually or automatically die head of mode can be carried out, with basis
It needs or it is expected to improve the uniformity of thickness.Then the edge of the film stretched is cut off its to remove that it is fixed by clip
Remaining thickness area, then by removal partial mill to reuse.If desired, the trimming part of grinding can directly be added
It returns in film manufacturing processes, or is granulated in a separate operation and is added back in film manufacturing processes or resells for other mesh
's.Then by film by web process system, and surface treatment step is carried out in one or both sides, then by it wound on mother
In version or roll, for subsequent cutting and conversion process.
Film produced shows excellent mist degree and gloss value, and it is online under show low and uniform COF,
And additional time or temperature are not needed to reduce COF.In addition, compound is handled to by it in operating winding and subsequent
He prevent adhesion particle manufacture film in, electrostatic generates significant reduction, and when rubbing on design on fabric surface and be maintained at light
Show that reduced electrostatic generates and dust absorption when on the container of the particles such as matter cigarette ash, while which raises the barriers to water oxygen
Property, and biodegradable, it is abundant and very environmentally friendly to prepare raw material sources.
It is readily apparent that the film for the middle layer (transparent or coloring) being applied between sandwich layer and surface layer can increase film
Sliding capability.Optionally, sandwich layer can be mixed with incompatible material, such as calcium carbonate or the incompatible polymerization of other PLA
Object, they, which are dispersed in PLA and generate gap, causes particle, and the sandwich layer of cavitation is generated when stretching, obtains opaque film.
The present invention by adopting the above technical scheme, compared with prior art, has the following technical effect that
The present invention relates to the production of the multi-layer co-extruded film comprising biodegradable copolymer of poly lactic acid, the copolymers
It is processed with improved process performance and web, while having the advantage that reduction COF (coefficient of friction), reduce adhesion, increased
Add heat sealability, improve printing, improve the adhesiveness of metalization layer, and it is surprising reduce be electrostatically-formed and reduce film suction
Dirt.When compared with unmodified membrane, a small amount of spherical cross-linked polymer base particle is added in the thin surface layer of coextrusion PLA film
Show unexpected film performance, and with the film (as known to the skilled person two modified with anti-block particulates
Silica) compared to when, performance is also unexpected.
The present invention overcomes the defect of the prior art by producing plural layers, and wherein surface-active anti-block particulates can be with
It is added for placing the most useful superficial layer of particle, while substantially reducing the amount of required additive, reduce the cost of film.This
Outside, lower light scattering, the total mist degree of film due to caused by the scattering particles not from sandwich layer significant can reduce.Particle adds
Adding the adhesion for leading to film to be inclined to significantly reduces, and improves the manufacturability of product by reducing the waste material in manufacture.
Spheric granules is added in surface layer to generate localized variation in the surface roughness of film, when film and such as roller
Surface contact or during fabrication wound upon themselves when, the film tend to capture specific thicknesses air layer.This controlled sky
Gas-bearing formation seems to make film surface far from the surface being in contact with it, and which improve the formation of the winding of film and cutting volume, and help
(this leads to film blocking) is bonded in reducing contact of the film with film.When on the membrane surface use low melting point PLA resin with
When increasing improved printing performance and when these film surface layers are handled in subsequent conversion process with improve wetability and
When adhesiveness, this is obvious.Only addition particle is enough to assign beneficial effect on a surface, while allowing using nothing
Particle surface improves the metallization pattern of film.In the present invention, it has been found that it is such as poly- to add spherical cross-linked polymer base particle
Methyl silsesquioxane base particle (Tospearl.TM.) significantly improves the process performance of film and significantly reduces film
Antistatic property, thus compared with the film containing silica or other particles that prevent adhesion, with lower dust absorption.
In the present invention, particle is added in molten polymer is by being directly added into extruder, and then the routine of PLA is squeezed
It melts out, and particle is directly mixed and be dispersed in and is completed in high viscosity melting PLAX.By particle and solid polymer pellets
Mix together with a small amount of compatible oil, and with polymeric aggregate physical blending, the polymeric aggregate, which is used as, to be mixed or optional
, make its transfer and with other mixed with polymers.It has been found that this mixing and dispersion level are enough discrete particles, this and beauty
The introduction of state patent No.6,649,732 is opposite.In the present invention, it will be sealed by the coextrusion of heat-sealable polylactic acid layers
Property be added in film, and sealant adhesiveness it is excellent and do not need addition adhesion-promoting layer.
In addition, the present invention is also provided in the film containing cellulose-chitin middle layer, raw material sources are wide
General, cellulose and chitin are most common two kinds of organic macromolecules on the earth, generally existing in the life entity of nature,
More easily biological-degradable；Film containing above-mentioned cellulose-periostracum can more keep out the invasion of oxygen than conventional preservative film, because
Its with gas be difficult to by crystal structure, can allow food materials continue it is fresh-keeping more long.
Polylactic acid polymer of the present invention is combined with each other prepared film performance with cellulose-chitin biological raw material and is better than
Polylactic acid film and cellulose-chitin film that each raw material is prepared separately, and its tensile property is excellent, in preparation process and makes
It is relatively low with breakage rate in the process, it is with a wide range of applications.
Specific embodiment
The present invention relates to a kind of polylactic acid films comprising: an internal layer is prepared by copolymer of poly lactic acid；At least one
Middle layer, prepared composition include: cellulose and chitin；At least one surface layer, is prepared by copolymer of poly lactic acid,
In, it is based on surface layer weight, cross-linked polymer spherical that the partial size of 0.05wt%-0.6wt% is 2-6 μm is contained on the surface layer
Grain；Wherein, the middle layer is between the internal layer and surface layer.The invention further relates to a kind of preparation sides of polylactic acid film
Method comprising following steps: internal layer, middle layer and surface layer are prepared by individually extrusion；To prepare internal layer, middle layer and surface layer by
It is compound that predetermined order carries out coextrusion curtain coating, and carries out biaxial stretch-formed, and above-mentioned polylactic acid film is made；Wherein, the middle layer
Preparation step include: by chitin according to 0.5~2.5wt% concentration be added ionic liquid in, stirred at 70~100 DEG C molten
3~6h is solved, cellulose dispersion liquid is added, stirs 1~2h at 90~120 DEG C, obtains chitin-cellulose mixed liquor, adjust PH extremely
Close to 7, ground 30~60min, the cellulose nano-fibrous mixing film liquid of chitin-is made；It is added in mixing film liquid appropriate
Plasticizer be heated to 30~50 DEG C and be uniformly mixed, 10~30min of evacuation and centrifugal degassing at 2500~4500r/min is used
The middle layer is made in extrusion process.
With reference to embodiment, the specific embodiment of the present invention is further described.Following embodiment is only used for more
Add and clearly demonstrate technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
Five layer laminated films are prepared by the main layer or internal layer (sandwich layer) that individually squeeze out PLA4042.TM..It is squeezed out on the sandwich layer
The superficial layer of other two PLA4042.TM., every layer of ball by the poly methyl silsesquioxane preparation being crosslinked containing 0.2wt%
Shape particle surface layer, average grain diameter are 2.0 μm (Tospearl.TM.120A), and the final skin depth after stretching is 0.8-1.4 μm,
It is spare after above-mentioned internal layer and surface layer preparation.
Wherein middle layer the preparation method is as follows:
Ovendriedwood cellulose is taken, graininess is ground into, crosses 30 meshes；By cellulose and glycerine with solid-to-liquid ratio (g/mL)
It is uniformly mixed for 1:5, in 110 DEG C of oil bath heating swollen 2h；It is added in cellulose after swollen relative to system gross mass
0.25% sulfuric acid；By mixture in 90 DEG C of oil bath heating swollen 2h and mechanical stirring, churned mechanically revolving speed is 80r/min,
Cellulose dispersion liquid is obtained, it is spare；
It takes over dry squid parietal bone chitin 3 times of squid parietal bone chitin (weight of ovendriedwood cellulose be), grinding
At graininess, 30 meshes are crossed, is added in 1- ethyl-3-methylimidazole Acetate Solution according to the concentration of 2.0wt%, is stirred at 85 DEG C
Mix dissolution 3h；The cellulose dispersion liquid of above-mentioned preparation is added, stirs 1h at 100 DEG C, obtains chitin-cellulose mixed liquor, adopts
With sodium hydroxide tune PH to close to 7, through colloidal grinding 40min, the cellulose nano-fibrous mixing film liquid of chitin-is made；Mixed
Closing and mass concentration is added in film liquid is that 0.28% glycerol is heated to 40 DEG C and is uniformly mixed, the evacuation and centrifugal degassing at 3000r/min
Other two middle layer is made using extrusion process in 15min.
By the layer of above-mentioned preparation with surface layer-middle layer-internal layer-middle layer-surface layer sequence merge in a mold with 150~
It 200 DEG C and is cast on cooling chill roll.The sheet material so produced is transferred on machine-direction oriented machine (MDO), and is being set
To be reheated on 55-70 DEG C of hot-rolling, ideally at 60-62 DEG C.Then sheet material is driven at two with friction speed
It is stretched between roller, about 3 times of the speed increase between the first and second rollers.Then the sheet material of stretching is passed through into a series of chill rolls
And be transferred in stenter and carry out cross directional stretch, sheet material is introduced into one group of clip being located on parallel chain in stenter,
The parallel chain is advanced at uniform intervals with uniform speed and is preheated in forced ventilation baking oven with 50-65 DEG C.
Next, 65-75 DEG C at a temperature of by the diverging of baking oven chain, film is stretched 3 times on the direction transverse direction (TD).Then
At about 135-145 DEG C, preferably 141 DEG C are annealed and are crystallized in the chain separation part assembled in parallel or slightly, and heat-shaping is thin
Film simultaneously increases its crystallinity and reduces its tendency shunk when reheating.Next, discharging and turning film from clip
Film measuring system is moved on to determine its thickness uniformity, then cuts and removes the remaining margo for clip.Then
By film by surface treatment station and handle to it is required level to improve processing film and conversion, and be wound into home roll with for
Cutting operation afterwards.Prepared film shows excellent process performance and winding performance, while keeping excellent optical lens
Lightness and unexpected low electrostatic generate and dust suction tendency.The film also has good hot slip and impressionability, gas
Barrier property.
Embodiment 2
Film is prepared by embodiment 1, the difference is that the average grain diameter that anti-block particulates contain 0.05-2.5wt% is
4-5 μm of silica dioxide granule surface layer.The film so produced shows improved process performance and resistance to blocking, but due to
Unpleasant haze is horizontal and shows the clarity gone on business.Its reduce electrostatic generate and reduce dirt absorption in terms of not
There is improvement, but its gas barrier property is more excellent.
Embodiment 3
Film is prepared by embodiment 1, two of them surface layer is made of heat sealable 4060 copolymer of PLA, and is contained
The surface layer of the spheric granules by the poly methyl silsesquioxane preparation being crosslinked of 0.2wt%.The film so produced shows to change
Into heat sealability and show excellent process performance and winding performance, while keeping excellent optical clarity and unexpected
Low electrostatic generate and dust suction tendency and gas barrier property.
Embodiment 4
Metallized substrate is prepared by embodiment 1, two of them surface layer is made of heat sealable 4060 copolymer of PLA, and
And spherical by the poly methyl silsesquioxane preparation being crosslinked with the 0.2wt% of surface layer poidometer is contained on an only surface
Grain.Another surface layer is made of pure PLA4060.TM. (being free of spheric granules), and passes through sided corona treatment.What is so produced is thin
Film shows improved heat sealability and shows excellent process performance and winding performance, while keeping excellent optical clarity
With unexpected low electrostatic generation and dust suction tendency and gas barrier property.
Embodiment 5
The film of embodiment 3 extrusion is laminated to the second outside printed polymeric online, the second outside printed polymeric
Net can be used for filling in vertical forming and produce polybag on sealing machine.Laminated product shows improved property on packing machine
Can, compared with the film layer of unmodified surface layer film and embodiment 2 suppresses standby film, which has good
Bag forming property simultaneously shows low transmission power, and its anti-steam ability is preferable, is more suitable for food fresh keeping.
Embodiment 6
Prepare film by embodiment 1, the difference is that middle layer the preparation method is as follows:
It takes over dry bamboo fiber plain, is ground into graininess, cross 50 meshes；By cellulose and glycerine with solid-to-liquid ratio (g/mL)
It is uniformly mixed for 1:8, in 120 DEG C of oil bath heating swollen 3h；It is added in cellulose after swollen relative to system gross mass
0.45% hydrochloric acid；By mixture in 100 DEG C of oil bath heating swollen 3h and mechanical stirring, churned mechanically revolving speed is 100r/
Min obtains cellulose dispersion liquid, spare；
The cuticula chitin 5 times of chitin (weight of over dry bamboo fiber element be) for taking exhausted insect, is ground into particle
Shape crosses 50 meshes, is added in 1,3- methylimidazole Acetate Solution according to the concentration of 1.0wt%, stirring and dissolving 5h at 90 DEG C；
The cellulose dispersion liquid of above-mentioned preparation is added, stirs 1.5h at 110 DEG C, chitin-cellulose mixed liquor is obtained, using hydroxide
Potassium tune PH is pulverized instrument and grinds 30min, the cellulose nano-fibrous mixing film liquid of chitin-is made to close to 7；It is mixing
It is that 0.42% xylitol is heated to 50 DEG C and is uniformly mixed that mass concentration is added in film liquid, the evacuation and centrifugal degassing at 4000r/min
Individual two middle layers are made using extrusion process in 25min.
Embodiment 7
Prepare film by embodiment 1, the difference is that middle layer the preparation method is as follows:
Over dry microcrystalline cellulose is taken, graininess is ground into, crosses 40 meshes；By cellulose and glycerine with solid-to-liquid ratio (g/mL)
It is uniformly mixed for 1:10, in 100 DEG C of oil bath heating swollen 1h；It is added in cellulose after swollen relative to system gross mass
0.2% hydrochloric acid；By mixture in 80 DEG C of oil bath heating swollen 4h and mechanical stirring, churned mechanically revolving speed is 90r/min, is obtained
Cellulose dispersion liquid is obtained, it is spare；
The ectoskeleton chitin 2 times of chitin (weight of over dry microcrystalline cellulose be) for taking exhausted crab, is ground into graininess,
40 meshes are crossed, are added in 1- butyl -3- methylimidazole Acetate Solution according to the concentration of 2.5wt%, stirring and dissolving 6h at 70 DEG C；
The cellulose dispersion liquid of above-mentioned preparation is added, stirs 1h at 120 DEG C, chitin-cellulose mixed liquor is obtained, using potassium hydroxide
It adjusts PH to close to 7, is pulverized instrument and grind 60min, the cellulose nano-fibrous mixing film liquid of chitin-is made；In hybrid films
It is that 0.34% xylitol is heated to 30 DEG C and is uniformly mixed that mass concentration is added in liquid, the evacuation and centrifugal degassing at 2500r/min
Individual two middle layers are made using extrusion process in 30min.
Embodiment 8
Prepare film by embodiment 1, the difference is that, wherein 1 middle layer the preparation method is as follows:
It takes over dry bast-fibre plain, is ground into graininess, cross 50 meshes；By cellulose and butantriol with solid-to-liquid ratio (g/mL)
It is uniformly mixed for 1:6, in 105 DEG C of oil bath heating swollen 2.5h；It is added in cellulose after swollen relative to system gross mass
0.35% phosphoric acid；By mixture in 100 DEG C of oil bath heating swollen 1h and mechanical stirring, churned mechanically revolving speed is 100r/
Min obtains cellulose dispersion liquid, spare；
The cell wall chitin 1.5 times of chitin (weight of over dry bast-fibre element be) for taking fungi, is ground into particle
Shape crosses 50 meshes, is added in 1- butyl -3- methylimidazole villaumite solution according to the concentration of 1.7wt%, stirring and dissolving at 100 DEG C
3.5h；The cellulose dispersion liquid of above-mentioned preparation is added, stirs 1.5h at 100 DEG C, obtains chitin-cellulose mixed liquor, uses
To close to 7, through colloidal grinding 60min, the cellulose nano-fibrous mixing film liquid of chitin-is made in sodium hydroxide tune PH；It is mixing
It is that 0.25% polyethylene glycol is heated to 45 DEG C and is uniformly mixed that mass concentration is added in film liquid, is centrifuged at 4500r/min de-
10min is steeped, wherein 1 middle layer is made using extrusion process.
Wherein another 1 middle layer the preparation method is as follows:
Its preparation step is identical as the wherein preparation step of 1 middle layer, at 4500r/min after evacuation and centrifugal degassing 10min,
By film liquid and polylactic acid polymer PLA4042.TM. (its weight be the gross mass of cellulose and chitin 3 times) in premixing machine
In be pre-mixed, initial temperature is 60 DEG C, and the revolving speed of premixing machine is 1000 turns/min, after being sufficiently mixed uniformly, by mixture
Expect that blending extrusion, extrusion temperature are 190 DEG C, other 1 polylactic acid-cellulose-chitin middle layer is made to obtain.
Comparative example 1
Film is prepared by embodiment 1, the difference is that, internal layer and surface layer are only set, middle layer, structure are not provided with
Form is surface layer-internal layer-surface layer.
To the biological degradability and gas permeability progress performance verification of film prepared by embodiment 1,6,7,8 and comparative example 1.
Its result is as follows:
| Membrane sample | Biological degradability | Oxygen permeability (cc/m2/ day atm) |
| Embodiment 1 | 81 | 100 |
| Embodiment 6 | 79 | 92 |
| Embodiment 7 | 80 | 96 |
| Embodiment 8 | 82 | 120 |
| Comparative example 1 | 85 | 200 |
As can be seen from the above embodiments, the twin shaft prepared by the present invention containing polylactic acid polymer, cellulose and chitin
Oriented film, safety and sanitation, biological degradability is good, has preferable mechanical property, inoxidizability, barrier properties for gases, and its
Adhesion and electrostatic with improved coefficient of friction and reduction generate, and show significantly improved winding, cutting, vacuum metal
Change and packing machine operates and substantially reduce electrostatic generation, while there is improved hot slip.
In the present invention, it is additionally arranged middle layer, chitin and the compound preparation nanometer middle layer of cellulose are used, by day
What right organic macromolecule material was constituted, there is excellent biodegradability, while its expansion that can effectively obstruct gas molecule
It dissipates, the film especially prepared is more suitable as the packing film of fresh food, by the method for starvation, in favor of extending
The fresh keeping time of food materials.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (20)
1. a kind of polylactic acid film characterized by comprising
One internal layer, is prepared by copolymer of poly lactic acid；
At least one middle layer, prepared composition include: cellulose and chitin；
At least one surface layer, is prepared by copolymer of poly lactic acid, wherein is based on surface layer weight, the surface layer is contained
The cross-linked polymer spheric granules that the partial size of 0.05wt%-0.6wt% is 2-6 μm；
Wherein, the middle layer is between the internal layer and surface layer.
2. a kind of polylactic acid film according to claim 1, which is characterized in that the mass ratio of the cellulose and chitin
For 1~5:1.
3. a kind of polylactic acid film according to claim 1, which is characterized in that the cellulose be selected from wood-cellulose,
At least one of grass fiber element, bamboo fiber element, gossypin, bast-fibre element or microcrystalline cellulose.
4. obtaining a kind of polylactic acid film according to claim 1, which is characterized in that the chitin is from crab or shrimp
At least one of ectoskeleton, squid parietal bone, the cuticula of insect and cell wall of fungi.
5. a kind of polylactic acid film according to claim 1, which is characterized in that the prepared composition of the middle layer further includes
Polylactic acid polymer is 2~4:1 with the total mass ratio of cellulose and chitin.
6. a kind of polylactic acid film according to claim 1, which is characterized in that the surface layer and internal layer have identical or not
Same polymer.
7. a kind of polylactic acid film according to claim 1, which is characterized in that the surface layer polymer is lower than institute for fusing point
State the poly (lactic acid) composition of internal layer polymer.
8. polylactic acid film according to claim 1, which is characterized in that the crystallinity of the surface layer polymer is lower than described
The crystallinity of internal layer polymer.
9. a kind of polylactic acid film according to claim 1, which is characterized in that the surface layer is attached to the middle layer
At least one surface, and only one surface layer includes the cross-linked polymer spheric granules.
10. a kind of polylactic acid film according to claim 9, which is characterized in that with contain cross-linked polymer spheric granules
Surface layer it is opposite film surface deposition metal vacuum metallization.
11. a kind of polylactic acid film according to claim 1, which is characterized in that the cross-linked polymer spheric granules is
The polymethylsilsesquioxane of crosslinking or the acrylic resin of crosslinking.
12. a kind of polylactic acid film according to claim 1, which is characterized in that the cross-linked polymer spheric granules
Content is the 0.01wt% to 0.5wt% of surface layer polymer weight.
13. a kind of polylactic acid film according to claim 1, which is characterized in that one of the polylactic acid film or two
A surface is subjected to corona, flame or corona treatment.
14. a kind of polylactic acid film according to claim 1, which is characterized in that the internal layer polymerize with selected from incompatible
The cavitation agent of object or inorganic particle is blended, and the inorganic particle is formed a series of in the range of 0.1-4.0 microns when stretching
Microvoid, each microvoid include that particle is caused at least one gap.
15. a kind of preparation method of polylactic acid film, which comprises the steps of: by individually extrusion prepare internal layer,
Middle layer and surface layer；Internal layer, middle layer and surface layer will be prepared, and to carry out coextrusion curtain coating in a predetermined order compound, and carries out twin shaft drawing
It stretches, the polylactic acid film as described in any one of claim 1~14 is made；
Wherein, the preparation step of the middle layer includes:
Chitin is added in ionic liquid according to the concentration of 0.5~2.5wt%, 3~6h of stirring and dissolving, adds at 70~100 DEG C
Enter cellulose dispersion liquid, stir 1~2h at 90~120 DEG C, obtain chitin-cellulose mixed liquor, adjusts PH to close to 7, grind
The cellulose nano-fibrous mixing film liquid of chitin-is made in 30~60min；Suitable plasticizer heating is added in mixing film liquid
It is uniformly mixed to 30~50 DEG C, 10~30min of evacuation and centrifugal degassing at 2500~4500r/min, is made using extrusion process
The middle layer.
16. the preparation method of polylactic acid film according to claim 15, which is characterized in that the ionic liquid includes 1-
Ethyl-3-methylimidazole acetate, 1- methylimidazole acetate, 1,3- methylimidazole acetate, 1- butyl -3- methylimidazole
Acetate, glycine hydrochloride, 1- butyl -3- methylimidazole villaumite or 1- ethyl-3-methylimidazole bromide.
17. the preparation method of polylactic acid film according to claim 15, which is characterized in that the plasticizer is selected from sweet
One or more of oil, polyethylene glycol, sorbierite, xylitol.
18. the preparation method of polylactic acid film according to claim 15, which is characterized in that the cellulose dispersion liquid
Preparation step includes: that cellulose and polyalcohol is taken to carry out heating swollen processing, and acid is added and is stirred mixing and further heating
Swollen processing, is made cellulose dispersion liquid.
19. the preparation method of polylactic acid film according to claim 18, which is characterized in that the cellulose dispersion liquid
Preparation step includes: to take bone dry fiber plain, is ground into graininess, crosses 20~50 meshes；By cellulose and polyalcohol with solid-to-liquid ratio
1:5~10 are uniformly mixed, in 100~120 DEG C of 1~3h of heating swollen；It is added in cellulose after swollen total relative to system
Fiber is made in the acid of quality 0.2~0.45%, mechanical stirring and in 80~100 DEG C of 1~4h of oil bath heating swollen and mechanical stirring
Plain dispersion liquid.
20. the preparation method of polylactic acid film according to claim 18, which is characterized in that the polyalcohol is the third two
Alcohol, glycerine or butantriol；The acid is sulfuric acid, hydrochloric acid or phosphoric acid.
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Application publication date: 20190924 |