CN112608502A - High-toughness biaxially-oriented polylactic acid film, preparation method and application - Google Patents
High-toughness biaxially-oriented polylactic acid film, preparation method and application Download PDFInfo
- Publication number
- CN112608502A CN112608502A CN202011479268.XA CN202011479268A CN112608502A CN 112608502 A CN112608502 A CN 112608502A CN 202011479268 A CN202011479268 A CN 202011479268A CN 112608502 A CN112608502 A CN 112608502A
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- Prior art keywords
- polylactic acid
- film
- copolymer
- layer
- surface layer
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- 229920006381 polylactic acid film Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 76
- 239000004626 polylactic acid Substances 0.000 claims abstract description 76
- 230000004888 barrier function Effects 0.000 claims abstract description 53
- 239000002344 surface layer Substances 0.000 claims abstract description 49
- 239000012792 core layer Substances 0.000 claims abstract description 23
- 239000003607 modifier Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002981 blocking agent Substances 0.000 claims abstract description 6
- 229920005604 random copolymer Polymers 0.000 claims abstract description 5
- 229920005610 lignin Polymers 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- -1 polybutylene adipate Polymers 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 15
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229920000577 Nylon 6/66 Polymers 0.000 claims description 7
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 claims description 7
- 235000012343 cottonseed oil Nutrition 0.000 claims description 7
- 239000002385 cottonseed oil Substances 0.000 claims description 7
- 239000011253 protective coating Substances 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000003851 corona treatment Methods 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 5
- 229920000554 ionomer Polymers 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000009998 heat setting Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- 229920000393 Nylon 6/6T Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 abstract description 2
- 229920005586 poly(adipic acid) Polymers 0.000 abstract description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 4
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a high-toughness biaxially-oriented polylactic acid film, a preparation method and application thereof. The high-toughness biaxially oriented polylactic acid film is prepared by coextrusion and biaxial orientation, wherein the upper surface layer consists of 5-30% of a high-molecular modifier, 68-94.8% of polylactic acid resin, 0.1-1% of a slipping agent and 0.1-1% of an anti-blocking agent; the core layer is composed of at least one of racemic polylactic acid, acrylic acid grafted polylactic acid, lignin grafted polylactic acid, carboxylated nano cellulose grafted polylactic acid, a dextrorotatory polylactic acid-caprolactone random copolymer, a polylactic acid-polyethylene glycol copolymer, a polylactic acid copolymer and a polylactic acid/(poly adipic acid/butylene terephthalate) blend; the lower surface layer consists of 5-30% of a high molecular modifier, 68-94.8% of polylactic resin, 0.1-1% of a slipping agent and 0.1-1% of an anti-blocking agent. The high-toughness biaxially oriented polylactic acid film is used as a base film for preparing a barrier polylactic acid laminated film with the advantages of good transparency, excellent oxygen barrier property and the like.
Description
Technical Field
The invention belongs to the technical field of packaging materials, and particularly relates to a high-toughness biaxially-oriented polylactic acid film, a preparation method and application thereof.
Background
The polylactic acid is a biodegradable polymer formed by ring-opening polymerization of lactic acid or lactide, has rich and renewable raw material sources, can be biodegraded into carbon dioxide and water in nature, and is environment-friendly. Therefore, the film is widely applied to the fields of packaging materials, agricultural films, biomedical materials and the like. However, polylactic acid also has problems such as high brittleness, which limits its application.
In the prior art, the toughness of polylactic acid is generally improved by a method of copolymerizing, blending and compounding the polylactic acid and other tough polymer materials or a method of treating the polylactic acid by using a plasticizer, but the polylactic acid has poor compatibility with most polymer materials, the toughness is improved in a limited manner only by using a physical blending method, when the content of the plasticizer is high, the plasticizer is easy to migrate from the polylactic acid to the surface, and the polylactic acid is easy to be separated from PLA to cause the toughness of the material to be reduced.
On the other hand, when polylactic acid is formed into a film, the oxygen barrier property is still insufficient, and oxygen easily enters the packaging bag through the polylactic acid film, thereby causing problems such as putrefaction and deterioration of the contents of the package. Therefore, the development of polylactic acid films with both barrier property and toughness is still a demand in the industry.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a high-toughness biaxially-oriented polylactic acid film, a preparation method and application thereof, and solves the problems in the background technology.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the high-toughness biaxially-stretched polylactic acid film comprises an upper surface layer, a core layer and a lower surface layer in sequence;
the upper surface layer consists of 5-30% of a high molecular modifier, 68-94.8% of polylactic resin, 0.1-1% of a slipping agent and 0.1-1% of an anti-blocking agent;
the core layer is composed of at least one of racemic polylactic acid, acrylic acid grafted polylactic acid, lignin grafted polylactic acid, carboxylated nano cellulose grafted polylactic acid, a dextrorotatory polylactic acid-caprolactone random copolymer, a polylactic acid-polyethylene glycol copolymer, a polylactic acid copolymer and a polylactic acid/(polybutylene adipate/terephthalate) blend;
the lower surface layer consists of 5-30% of a high molecular modifier, 68-94.8% of polylactic resin, 0.1-1% of a slipping agent and 0.1-1% of an anti-blocking agent.
In a preferred embodiment of the present invention, the polymeric modifier comprises, by mass, 0.5 to 3% of cottonseed oil, 30 to 60% of nano-functional masterbatch, 34 to 68.5% of polylactic acid copolymer, and 1 to 3% of a compatibilizer.
In a preferred embodiment of the present invention, the nano-functional master batch comprises, by mass, 47 to 83.5% of a resin carrier, 15 to 40% of a nano material, 1 to 10% of a rare earth oxide, and 0.5 to 3% of a lubricant.
In a preferred embodiment of the present invention, the resin carrier is racemic polylactic acid, lignin grafted polylactic acid, carboxylated nanocellulose grafted polylactic acid, acrylic acid grafted polylactic acid, polybutylene adipate/terephthalate, polyethylene glycol diacrylate, nylon 612/6 copolymer, nylon 6/66 copolymer, nylon 6/66/11 copolymer, at least one of a nylon 6/66/610 copolymer, polyisobutylene, maleic anhydride grafted linear low density polyethylene, glycidyl methacrylate grafted ethylene-octene block copolymer, ethylene-methacrylate copolymer, ethylene-vinyl acetate copolymer, thermoplastic polyether ester elastomer, core-shell polymer with silicon dioxide as a core and methyl methacrylate as a shell, and polysiloxane/methyl methacrylate core-shell polymer;
the nano material is at least one of aluminum oxide, magnesium oxide, barium sulfate, silicon dioxide, calcium carbonate, zinc oxide, aluminum nitride, nano cellulose, organic silicon nano microspheres, silicon nitride, layered double hydroxide, multi-walled carbon nano tubes and nano graphene/carbon nano tube composites;
the rare earth element in the rare earth oxide is at least one of yttrium, lanthanum, cerium, neodymium, europium or dysprosium;
the lubricant is at least one of polyethylene wax, rare earth aluminate coupling agent, zinc stearate, titanate coupling agent, pentaerythritol stearate and polyethylene glycol.
In a preferred embodiment of the present invention, the compatibilizer is at least one of ethylene/butyl methacrylate/glycidyl methacrylate copolymer, styrene-acrylonitrile grafted glycidyl methacrylate, maleic anhydride grafted polylactic acid, itaconic acid grafted polylactic acid, polyethylene maleic anhydride copolymer, ethylene-zinc methacrylate ionomer, and rare earth ionomer.
In a preferred embodiment of the present invention, the total thickness of the film is 15 to 100 μm, wherein the thickness of the upper surface layer accounts for 8 to 30% of the total thickness, the thickness of the lower surface layer accounts for 8 to 30% of the total thickness, and the thickness of the core layer accounts for 40 to 84% of the total thickness.
The invention also provides a preparation method of the high-toughness biaxially oriented polylactic acid film, which comprises the following steps:
(1) mixing the components in the upper surface layer, the core layer and the lower surface layer according to a formula ratio, and uniformly dispersing the components by a high-speed mixer;
(2) melting and co-extruding the raw materials of the upper surface layer, the core layer and the lower surface layer in three extruders according to a formula ratio, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 15-40 ℃ through a T-shaped die;
(3) synchronously stretching the cast sheet without stretching in the transverse and longitudinal directions, wherein the stretching temperature is 40-125 ℃, and the stretching ratio is 2.0 x 2.0-4.0 x 4.0;
(4) and (4) carrying out heat setting treatment on the film obtained in the step (3) at 50-155 ℃, carrying out corona treatment on at least one surface layer of the film, then rolling and slitting to obtain the high-toughness biaxially-stretched polylactic acid film with the thickness of 15-100 mu m.
The second technical scheme adopted by the invention for solving the technical problems is as follows: provides an application of a high-toughness biaxially oriented polylactic acid film, namely a barrier polylactic acid laminated film, which is sequentially provided with a protective coating, a barrier evaporation layer, a bottom coating and a base film; the base film adopts the high-toughness biaxially oriented polylactic acid film.
In a preferred embodiment of the present invention, the protective coating is self-adhesive modified polyvinyl alcohol with a thickness of 0.5 to 4 μm, and the self-adhesive modified polyvinyl alcohol contains 0.5 wt% of silicon dioxide; the barrier evaporation layer is a silicon oxide layer or an aluminum oxide layer, and the thickness of the barrier evaporation layer is 10-500 nm; the primer layer is formed by coating a coating liquid containing at least one of polyurethane resin, acrylic resin, polyester resin or isocyanate curing agent, and the thickness of the primer layer is 0.5-3 μm.
The invention also provides a preparation method of the barrier polylactic acid laminated film, which comprises the following steps:
unreeling a base film according to specifications, coating a base coat on a corona treatment surface, then putting the base film into a drying oven, drying at the temperature of 60-130 ℃, rolling, and then placing the base film in a curing chamber at the temperature of 40-60 ℃ for curing to obtain a polylactic acid film coated with the base coat;
secondly, a barrier layer is vapor-plated on the bottom coating, then a protective coating is uniformly coated on the surface of the coating of the polylactic acid film with the vapor-plated barrier layer, the coating is dried at constant temperature, and finally the coated film is dried and wound to obtain the barrier polylactic acid laminated film.
Compared with the background technology, the technical scheme has the following advantages:
1. the high-toughness biaxially oriented polylactic acid film has excellent toughness and puncture resistance while maintaining good mechanical properties, and has good adhesion resistance and degradability; the high-toughness biaxially-stretched polylactic acid film prepared by the synchronous biaxially-stretched preparation method has more balanced properties.
2. The barrier polylactic acid laminated film reasonably utilizes the high-toughness biaxially stretched polylactic acid film, retains the advantages of the high-toughness biaxially stretched polylactic acid film, has the advantages of good transparency, excellent oxygen barrier property and the like, can be used for transparent packaging products, and is convenient for consumers to observe the state of contents.
Detailed Description
The terms "upper" and "lower" are used merely to facilitate describing the invention and to simplify the description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
Example 1
The high-toughness biaxially oriented polylactic acid film of the embodiment comprises an upper surface layer, a core layer and a lower surface layer; the upper surface layer comprises 5% of high molecular modifier, 94.6% of polylactic resin, 0.1% of oleamide and 0.3% of calcium carbonate in percentage by mass; the core layer consists of racemic polylactic acid; the lower surface layer consists of 10 percent of high molecular modifier, 89.7 percent of polylactic resin, 0.1 percent of oleamide and 0.2 percent of silicon dioxide;
the macromolecular modifier comprises 0.5% of cottonseed oil, 30% of nano-functional master batch, 68.5% of polylactic acid copolymer and 1% of ethylene/butyl methacrylate/glycidyl methacrylate copolymer;
the nanometer functional master batch consists of 83 percent of racemic polylactic acid, 15 percent of alumina, 1 percent of rare earth yttrium oxide and 1 percent of rare earth aluminate coupling agent;
the preparation method of the embodiment comprises the following steps:
(1) mixing the components in the upper surface layer, the core layer and the lower surface layer according to a formula ratio, and uniformly dispersing the components in a high-speed mixer;
(2) melting and co-extruding the raw materials of the upper surface layer, the core layer and the lower surface layer in three extruders according to a formula ratio, and casting the melt to a chilled roll quenching casting sheet with the surface temperature of 15-40 ℃ through a T-shaped die;
(3) synchronously stretching the cast sheet without stretching in the transverse and longitudinal directions, wherein the stretching temperature is 40-125 ℃, and the stretching ratio is 2.0 x 2.0-4.0 x 4.0;
(4) and (4) carrying out heat setting treatment on the film obtained in the step (3) at 50-155 ℃, carrying out corona treatment on at least one surface layer of the film, then rolling and slitting to obtain the high-toughness biaxially-oriented polylactic acid film with the thickness of 40 micrometers.
Example 2
Example 2 differs from example 1 in that: a high-toughness biaxially oriented polylactic acid film comprises an upper surface layer, a core layer and a lower surface layer; the upper surface layer comprises 15% of high molecular modifier, 84% of polylactic resin, 0.5% of ethylene bis stearamide and 0.5% of calcium carbonate in percentage by mass; the core layer is composed of acrylic acid grafted polylactic acid; the lower surface layer consists of 15 percent of high molecular modifier, 84 percent of polylactic resin, 0.5 percent of ethylene bisstearoyl and 0.5 percent of silicon dioxide;
the macromolecular modifier comprises 1% of cottonseed oil, 40% of nano functional master batch, 57.5% of polylactic acid copolymer and 1.5% of maleic anhydride grafted polylactic acid;
the nanometer functional master batch comprises 40% of poly (butylene adipate)/terephthalate, 30.5% of nylon 6/66 copolymer, 25% of magnesium oxide, 3% of rare earth lanthanum oxide and 1.5% of zinc stearate;
samples were prepared according to the preparation method of example 1, and the total thickness of the obtained high-toughness biaxially-oriented polylactic acid film was 40 μm.
Example 3
Example 3 differs from example 1 in that: a high-toughness biaxially oriented polylactic acid film comprises an upper surface layer, a core layer and a lower surface layer; the upper surface layer is composed of 20% of high molecular modifier, 79% of polylactic resin, 0.4% of silicone powder and 0.6% of talcum powder in percentage by mass; the core layer consists of 95 percent of polylactic acid/(poly adipic acid/butylene terephthalate) blend and 5 percent of acrylic acid grafted polylactic acid; the lower surface layer consists of 18 percent of high molecular modifier, 81 percent of polylactic resin, 0.4 percent of ethylene bisstearoyl and 0.6 percent of silicon dioxide;
the macromolecular modifier comprises 1.5% of cottonseed oil, 50% of nano-functional master batch, 46.5% of polylactic acid copolymer and 2% of polyethylene maleic anhydride copolymer;
the nanometer functional master batch comprises 20% of ethylene-methacrylate copolymer, 43.5% of polyethylene glycol diacrylate, 10% of nanocellulose, 20% of zinc oxide, 5% of rare earth cerium oxide and 1.5% of titanate coupling agent;
samples were prepared according to the preparation method of example 1, and the total thickness of the obtained high-toughness biaxially-oriented polylactic acid film was 40 μm.
Example 4
Example 4 differs from example 1 in that: a high-toughness biaxially oriented polylactic acid film comprises an upper surface layer, a core layer and a lower surface layer; the upper surface layer comprises, by mass, 25% of a high molecular modifier, 73.5% of polylactic resin, 0.8% of erucamide and 0.7% of diatomite; the core layer consists of a dextrorotatory polylactic acid-caprolactone random copolymer; the lower surface layer consists of 20 percent of high molecular modifier, 78.5 percent of polylactic resin, 0.8 percent of erucamide and 0.7 percent of calcium phosphate;
the macromolecular modifier comprises 2% of cottonseed oil, 60% of nano functional master batch, 36% of polylactic acid copolymer and 2% of ethylene-zinc methacrylate ionomer;
the nanometer functional master batch comprises 20.5 percent of polysiloxane/methyl methacrylate core-shell polymer, 35 percent of glycidyl methacrylate grafted ethylene-octene block copolymer, 15 percent of layered double hydroxide, 20 percent of organosilicon nanometer microsphere, 6 percent of rare earth lanthanum oxide, 2 percent of rare earth cerium oxide and 1.5 percent of pentaerythritol stearate;
samples were prepared according to the preparation method of example 1, and the total thickness of the obtained high-toughness biaxially-oriented polylactic acid film was 40 μm.
Example 5
Example 5 differs from example 1 in that: a high-toughness biaxially oriented polylactic acid film comprises an upper surface layer, a core layer and a lower surface layer; the upper surface layer comprises, by mass, 30% of a high molecular modifier, 68.5% of polylactic resin, 1% of erucamide and 0.5% of alumina; the core layer consists of 60 percent of dextrorotatory polylactic acid-caprolactone random copolymer and 40 percent of polylactic acid-polyethylene glycol copolymer; the lower surface layer consists of 10 percent of high molecular modifier, 88.5 percent of polylactic resin, 0.5 percent of erucamide and 1 percent of barium sulfate;
the macromolecular modifier comprises 3% of cottonseed oil, 50% of nano functional master batch, 45% of polylactic acid copolymer and 2% of itaconic acid grafted polylactic acid;
the nanometer functional master batch comprises 40% of racemic polylactic acid, 23.5% of thermoplastic polyether ester elastomer, 15% of calcium carbonate, 15% of aluminum nitride, 5% of rare earth neodymium oxide and 1.5% of polyethylene glycol;
samples were prepared according to the preparation method of example 1, and the total thickness of the obtained high-toughness biaxially-oriented polylactic acid film was 40 μm.
Example 6
A barrier polylactic acid laminated film, which comprises the high-toughness biaxially-oriented polylactic acid film prepared in example 1 and a barrier evaporated silicon oxide layer, wherein a polyurethane resin primer layer is arranged between the high-toughness biaxially-oriented polylactic acid film and the barrier evaporated silicon oxide layer, and a self-adhesive modified polyvinyl alcohol protective layer is arranged on the surface of the barrier evaporated silicon oxide layer;
the thickness of the surface protection coating is 0.5-4 mu m, the thickness of the evaporation barrier layer is 10-500 nm, and the thickness of the bottom coating is 0.5-3 mu m;
the preparation method of the embodiment comprises the following steps:
preparing a high-toughness biaxially-oriented polylactic acid film by the methods (1) to (4) in example 1;
(5) unreeling the high-toughness biaxially-oriented polylactic acid film according to the specification, coating a base coat on the corona treatment surface, then putting the film into a drying oven, drying at the temperature of 60-130 ℃, rolling, and then placing the film in a curing chamber at the temperature of 40-60 ℃ for curing to obtain the polylactic acid film coated with the base coat;
(6) and (3) evaporating and plating a barrier layer on the bottom coating of the polylactic acid film prepared in the step (5), then uniformly coating a protective coating on the surface of the coating of the polylactic acid film with the evaporated barrier layer, drying at constant temperature, and finally drying and rolling the coated film to obtain the barrier polylactic acid laminated film.
Example 7
Example 7 differs from example 6 in that: a barrier polylactic acid laminated film, which comprises the high-toughness biaxially-oriented polylactic acid film prepared in example 2 and a barrier evaporation aluminum oxide layer, wherein an acrylic resin primer layer is arranged between the high-toughness biaxially-oriented polylactic acid film and the barrier evaporation silicon oxide layer, and a self-adhesive modified polyvinyl alcohol protective layer is arranged on the surface of the barrier evaporation silicon oxide layer;
a sample was prepared according to the preparation method of example 6, and the obtained barrier polylactic acid laminated film was obtained.
Example 8
Example 8 differs from example 6 in that: a barrier polylactic acid laminated film, which comprises the high-toughness biaxially-oriented polylactic acid film prepared in example 3 and a barrier evaporated aluminum oxide layer, wherein a polyester resin primer layer is arranged between the high-toughness biaxially-oriented polylactic acid film and the barrier evaporated silicon oxide layer, and a self-adhesive modified polyvinyl alcohol protective layer is arranged on the surface of the barrier evaporated silicon oxide layer;
a sample was prepared according to the preparation method of example 6, and the obtained barrier polylactic acid laminated film was obtained.
Example 9
Example 9 differs from example 6 in that: a barrier polylactic acid laminated film, which comprises the high-toughness biaxially-oriented polylactic acid film prepared in example 4 and a barrier evaporated silicon oxide layer, wherein a polyester resin primer layer is arranged between the high-toughness biaxially-oriented polylactic acid film and the barrier evaporated silicon oxide layer, and a self-adhesive modified polyvinyl alcohol protective layer is arranged on the surface of the barrier evaporated silicon oxide layer;
a sample was prepared according to the preparation method of example 6, and the obtained barrier polylactic acid laminated film was obtained.
Example 10
Example 10 differs from example 6 in that: a barrier polylactic acid laminated film, which comprises the high-toughness biaxially-oriented polylactic acid film prepared in example 5 and a barrier evaporated silicon oxide layer, wherein an acrylic resin primer layer is arranged between the high-toughness biaxially-oriented polylactic acid film and the barrier evaporated silicon oxide layer, and a self-adhesive modified polyvinyl alcohol protective layer is arranged on the surface of the barrier evaporated silicon oxide layer;
a sample was prepared according to the preparation method of example 6, and the obtained barrier polylactic acid laminated film was obtained.
Comparative example 1
A common commercially available 40 μm biaxially oriented polylactic acid film.
First, the relevant performances of the above examples 1 to 5 and comparative example 1 were tested, and the test result data are shown in table 1.
TABLE 1
As can be seen from Table 1, compared with the comparative examples, the high-toughness biaxially-oriented polylactic acid films of examples 1 to 5 have more excellent comprehensive properties, and the mechanical strength and puncture resistance are improved to a certain extent while the toughness is improved.
Secondly, relevant performances of the examples 6-10 and the comparative example 1 are tested, and test result data are shown in a table 2.
TABLE 2
As can be seen from Table 2, the barrier polylactic acid laminated films of examples 6 to 10 have excellent oxygen barrier properties compared to the comparative examples.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A high-toughness biaxially oriented polylactic acid film is characterized in that: sequentially comprises an upper surface layer, a core layer and a lower surface layer;
the upper surface layer consists of 5-30% of a high molecular modifier, 68-94.8% of polylactic resin, 0.1-1% of a slipping agent and 0.1-1% of an anti-blocking agent;
the core layer is composed of at least one of racemic polylactic acid, acrylic acid grafted polylactic acid, lignin grafted polylactic acid, carboxylated nano cellulose grafted polylactic acid, a dextrorotatory polylactic acid-caprolactone random copolymer, a polylactic acid-polyethylene glycol copolymer, a polylactic acid copolymer and a polylactic acid/(polybutylene adipate/terephthalate) blend;
the lower surface layer consists of 5-30% of a high molecular modifier, 68-94.8% of polylactic resin, 0.1-1% of a slipping agent and 0.1-1% of an anti-blocking agent.
2. The high tenacity biaxially stretched polylactic acid film according to claim 1, wherein: the high molecular modifier comprises, by mass, 0.5-3% of cottonseed oil, 30-60% of nano-functional master batch, 34-68.5% of polylactic acid copolymer and 1-3% of compatilizer.
3. A high tenacity biaxially stretched polylactic acid film according to claim 2, wherein: the nanometer functional master batch is composed of 47-83.5% of resin carrier, 15-40% of nanometer material, 1-10% of rare earth oxide and 0.5-3% of lubricant by mass percentage.
4. A high tenacity biaxially stretched polylactic acid film according to claim 3, wherein:
the resin carrier is at least one of racemic polylactic acid, lignin-grafted polylactic acid, carboxylated nanocellulose-grafted polylactic acid, acrylic acid-grafted polylactic acid, polybutylene adipate/terephthalate, polyethylene glycol diacrylate, nylon 612/6 copolymer, nylon 6/66 copolymer, nylon 6/66/11 copolymer, nylon 6/66/610 copolymer, polyisobutylene, maleic anhydride-grafted linear low-density polyethylene, glycidyl methacrylate-grafted ethylene-octene block copolymer, ethylene-methacrylate copolymer, ethylene-vinyl acetate copolymer, thermoplastic polyether ester elastomer, core-shell polymer taking silicon dioxide as core and methyl methacrylate as shell, and polysiloxane/methyl methacrylate core-shell polymer;
the nano material is at least one of aluminum oxide, magnesium oxide, barium sulfate, silicon dioxide, calcium carbonate, zinc oxide, aluminum nitride, nano cellulose, organic silicon nano microspheres, silicon nitride, layered double hydroxide, multi-walled carbon nano tubes and nano graphene/carbon nano tube composites;
the rare earth element in the rare earth oxide is at least one of yttrium, lanthanum, cerium, neodymium, europium or dysprosium;
the lubricant is at least one of polyethylene wax, rare earth aluminate coupling agent, zinc stearate, titanate coupling agent, pentaerythritol stearate and polyethylene glycol.
5. A high tenacity biaxially stretched polylactic acid film according to claim 2, wherein: the compatilizer is at least one of ethylene/butyl methacrylate/glycidyl methacrylate copolymer, styrene-acrylonitrile grafted glycidyl methacrylate, maleic anhydride grafted polylactic acid, itaconic acid grafted polylactic acid, polyethylene maleic anhydride copolymer, ethylene-zinc methacrylate ionomer and rare earth ionomer.
6. The high tenacity biaxially stretched polylactic acid film according to claim 1, wherein: the total thickness of the film is 15-100 mu m, wherein the thickness of the upper surface layer accounts for 8-30% of the total thickness, the thickness of the lower surface layer accounts for 8-30% of the total thickness, and the thickness of the core layer accounts for 40-84% of the total thickness.
7. The method for preparing a high-toughness biaxially stretched polylactic acid film according to any one of claims 1 to 6, wherein: the method comprises the following steps:
(1) mixing the components in the upper surface layer, the core layer and the lower surface layer according to a formula ratio, and uniformly dispersing the components by a high-speed mixer;
(2) melting and co-extruding the raw materials of the upper surface layer, the core layer and the lower surface layer in three extruders according to a formula ratio, and casting the melt to a chilled roll quenching cast sheet with the surface temperature of 15-40 ℃ through a T-shaped die;
(3) synchronously stretching the cast sheet without stretching in the transverse and longitudinal directions, wherein the stretching temperature is 40-125 ℃, and the stretching ratio is 2.0 x 2.0-4.0 x 4.0;
(4) and (4) carrying out heat setting treatment on the film obtained in the step (3) at 50-155 ℃, carrying out corona treatment on at least one surface layer of the film, then rolling and slitting to obtain the high-toughness biaxially-stretched polylactic acid film with the thickness of 15-100 mu m.
8. A barrier polylactic acid laminated film characterized by: a protective coating, a barrier evaporation layer, a bottom coating and a base film are sequentially arranged; the base film is the high-toughness biaxially stretched polylactic acid film as claimed in any one of claims 1 to 7.
9. The barrier polylactic acid laminated film according to claim 8, wherein:
the protective coating is self-adhesive modified polyvinyl alcohol with the thickness of 0.5-4 mu m, and the self-adhesive modified polyvinyl alcohol contains 0.5 wt% of silicon dioxide;
the barrier evaporation layer is a silicon oxide layer or an aluminum oxide layer, and the thickness of the barrier evaporation layer is 10-500 nm;
the primer layer is formed by coating a coating liquid containing at least one of polyurethane resin, acrylic resin, polyester resin or isocyanate curing agent, and the thickness of the primer layer is 0.5-3 μm.
10. The method for producing a barrier polylactic acid laminated film according to any one of claims 8 to 9, wherein:
unreeling a base film according to specifications, coating a base coat on a corona treatment surface, then putting the base film into a drying oven, drying at the temperature of 60-130 ℃, rolling, and then placing the base film in a curing chamber at the temperature of 40-60 ℃ for curing to obtain a polylactic acid film coated with the base coat;
secondly, a barrier layer is vapor-plated on the bottom coating, then a protective coating is uniformly coated on the surface of the coating of the polylactic acid film with the vapor-plated barrier layer, the coating is dried at constant temperature, and finally the coated film is dried and wound to obtain the barrier polylactic acid laminated film.
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