CN104350091B - Aqueous polyanion polyethylenimine solution has the purposes of the polymeric film of oxygen barrier property for preparation - Google Patents
Aqueous polyanion polyethylenimine solution has the purposes of the polymeric film of oxygen barrier property for preparation Download PDFInfo
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- CN104350091B CN104350091B CN201380030186.9A CN201380030186A CN104350091B CN 104350091 B CN104350091 B CN 104350091B CN 201380030186 A CN201380030186 A CN 201380030186A CN 104350091 B CN104350091 B CN 104350091B
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- acid
- polymeric film
- polyanion
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- polymer
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000001301 oxygen Substances 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 45
- 229920000447 polyanionic polymer Polymers 0.000 title claims abstract description 31
- 230000004888 barrier function Effects 0.000 title claims abstract description 26
- 229920002873 Polyethylenimine Polymers 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title description 3
- 239000002253 acid Substances 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 12
- 150000007530 organic bases Chemical class 0.000 claims abstract description 7
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 6
- -1 polyethylene Polymers 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- 239000005026 oriented polypropylene Substances 0.000 claims description 11
- 230000035699 permeability Effects 0.000 claims description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
- 239000011976 maleic acid Substances 0.000 claims description 10
- 239000004952 Polyamide Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229920001634 Copolyester Polymers 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 238000004806 packaging method and process Methods 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
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000134 Metallised film Polymers 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005025 cast polypropylene Substances 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
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000000123 paper Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims 1
- JSLMNNPQKHONFW-UHFFFAOYSA-N benzene naphthalene-1-carboxylic acid Chemical compound C1(=CC=CC2=CC=CC=C12)C(=O)O.C1=CC=CC=C1 JSLMNNPQKHONFW-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000002585 base Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- 229920006318 anionic polymer Polymers 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 125000000129 anionic group Chemical group 0.000 description 11
- 239000003431 cross linking reagent Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 229920000867 polyelectrolyte Polymers 0.000 description 5
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- TYMYJUHDFROXOO-UHFFFAOYSA-N 1,3-bis(prop-2-enoxy)-2,2-bis(prop-2-enoxymethyl)propane Chemical compound C=CCOCC(COCC=C)(COCC=C)COCC=C TYMYJUHDFROXOO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000037452 priming Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 101100016388 Arabidopsis thaliana PAS2 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000555268 Dendroides Species 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
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- 101100297150 Komagataella pastoris PEX3 gene Proteins 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 229940045713 antineoplastic alkylating drug ethylene imines Drugs 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical group COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- DWAYUNSAAKQFJZ-UHFFFAOYSA-G magnesium;dipotassium;trisodium;dihydrogen phosphate;hydrogen phosphate;dichloride;sulfate Chemical compound [Na+].[Na+].[Na+].[Mg+2].[Cl-].[Cl-].[K+].[K+].OP(O)([O-])=O.OP([O-])([O-])=O.[O-]S([O-])(=O)=O DWAYUNSAAKQFJZ-UHFFFAOYSA-G 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 101150014555 pas-1 gene Proteins 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229950003937 tolonium Drugs 0.000 description 1
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
The present invention describes the purposes of a kind of aqueous solution comprising at least one polyanion and at least one high molecular weight polyethyleneimine, and it is for providing oxygen barrier property for polymeric film.Described polyanion is the polymer of the acid groups of a kind of alkali neutralization comprising and being selected from inorganic base and monovalence organic base, and described polyanion has the weight average molecular weight of at least 10000g/mol.
Description
The present invention relates to a kind of aqueous solution for for polymeric film provide oxygen barrier property purposes, described aqueous is molten
Liquid includes the polymine of at least one polymer poly anion and at least one high molecular.
When the product of packaging is oxidizable or during to oxygen sensitive, and it is ten that the packaging material of use have oxygen barrier property
Divide important, i.e. packaging material have oxygen permeability or the oxygen permeability of minimum of minimum.Use as packaging material and by example
The polymeric film prepared such as polyolefin (such as polyethylene) or oriented polypropylene (OPP) or polyester (such as polyethylene terephthalate), when
When it uses with the form not being applied, it is generally of of a relatively high oxygen permeability.Therefore, people have pointed out various measure
Improve the oxygen barrier property of these packaging material.
WO 07/002322 describes the coated polymer film with oxygen barrier property.This application composition is along fourth
Enedioic acid/acrylic copolymer and the solution of vinyl alcohol/vinylamine copolymer.After coating procedure, two in application composition
Plant copolymer to cross-link on polymeric film.
WO 98/31719 describes the application composition as barrier coat.This compositions includes that ethylenic is unsaturated
Acid monomers and polyamide, including the cross-linking agent mixed.After coating procedure, caused by the polyreaction of free yl induction and send out
Raw crosslinking.
WO 2011/023587 describes provides the special poly-of oxygen obstruction for the packaging material for being prepared by polymer
The purposes of pentalyte.Polymeric film can coat a kind of aqueous liquid dispersion, and described aqueous liquid dispersion includes passing through in advance water
Dispersion compound polyelectrolyte prepared by bag aqueous emulsion polymerization, or polymeric film coating one include compound polyelectrolyte
Compositions, described polyelectrolyte prepared by anionic polymer and cationic surfactant, or polymeric film be coated with to
Few three layers alternately, the most respectively, a layer in two adjacent layers comprises a kind of anionic polyelectrolyte composition, two phases
Another layer in adjacent bed comprises a kind of cationic polyelectrolyte composition, compound polyelectrolyte be formed at alternating layer relative,
Adjacent interfaces.The hitherto known packaging film with oxygen barrier property is still unsatisfactory, especially when making in high humidity environment
Used time.The barrier coat being such as recorded in WO 2011/023587 needs extra moisture protection system, for protecting insulating layer
Avoid the impact of humidity.
It is an object of the present invention to provide other compositions and method, it makes the oxygen that the polymeric film of preparation has had
Vapour lock separating performance, still has good oxygen barrier property particularly without extra protective coating in high humidity environment.
The invention provides aqueous solution for providing the purposes of oxygen barrier property, described aqueous solution for polymeric film
Comprising at least one polyanion and at least one polymine, wherein polyanion is that one comprises and is selected from by least one
The polymer of the acid groups that the alkali of inorganic base and monovalence organic base neutralizes, described in comprise acid groups polymer have before neutralization
The weight average molecular weight of at least 10000g/mol；And wherein said polymine has the Weight-average molecular of at least 25000g/mol
Amount.
The present invention also provides for a kind of coated polymer film comprising oxygen obstruction coating, and described coated polymer film can pass through
The purposes of the present invention described herein obtains, and wherein at least one side of polymeric film is coated by a kind of aqueous solution, described
Aqueous solution includes at least one polyanion and at least one polymine, and wherein said polyanion is to comprise by least
The polymer of acid groups that a kind of monoacidic base neutralizes, described in comprise acid groups polymer there is before neutralization at least 10000g/
The weight average molecular weight of mol；And wherein said polymine has the weight average molecular weight of at least 25000g/mol.Molecular weight can
With gel permeation chromatography or determination of light scattering.
Coating prepared by polymer aqueous solutions used according to the invention has oxygen barrier property.This barrier property can
Measure with the testing permeability described in embodiment.Term " oxygen barrier property " meaning is to compare uncoated base material, oxygen
Transmitance (OTR) reduces.Test under 23 DEG C and 0% relative humidity, according to the oxygen permeability of the polymeric film of present invention coating
It is preferably smaller than the 20%, especially less than 10% of uncoated polymeric film value, or less than 5%, such as 1 to 3%；At 23 DEG C and 85%
Test under relative humidity, be being preferably smaller than 30% or being less than 20% or less than 10% of its value.
Polymer aqueous solutions preferably comprises 10 to 90 weight %, the polyanion of more preferably 20 to 80 weight %, base
In solid content meter.
Polymer aqueous solutions preferably comprises 10 to 90 weight %, the polymine of more preferably 20 to 80 weight %,
Based on solid content meter.
Polyanion (in terms of without neutralization reagent) and the preferred 10:1 to 10:9 of weight ratio, more preferably 10:2 of polymine
To 10:5 or 10:3 to 10:4.
Polyanion and the total concentration of polymine in aqueous solution, preferably at least 1 weight %, especially at least 5 weights
Amount %, up to 50 weight % or up to 60 weight %, such as 1 to 50 weight % or 5 to 40 weight %.
It is preferably selected such that for every mole of polymine for preparing the amount of the polymine of aqueous solution
Amino, the amount of the anionic group of at least one anionic polymer is such as to be up to 400mol%, or up to
250mol%, preferably 150 to 380mol%, or 180 to 250mol%.
Polyanion is the polymer of the acid groups including neutralization, also referred to as anionic polymer.Anionic polymer is
There is the polymer of anion or acidic-group, especially there is carboxylic acid, phosphoric acid or sulfonic group or the organic polymer of respective acids group
Thing.Term " anionic polymer " also includes the polymer accordingly with acid groups, as long as when they are for the aqueous of the present invention
At least partly neutralized by monoacidic base time in solution.
The example of suitable anion polymer is by can the ethylenic unsaturation anionic monomer of radical polymerization
Raolical polymerizable and formed those.Term " anionic monomer " includes having at least one anion or acidic-group
Monomer, wherein acidic-group can be neutralized by alkali.Anionic polymer group also include by least one anionic monomer with a kind of or
Copolymer prepared by multiple different nonionic, nonacid copolymerisable monomer.Polyanion also can by one or more non-from
Sub-monomer is polymerized, then obtains anionic polymer by hydrolysis and synthesize, non-ionic monomer such as acid derivative such as ethylenic
Unsaturated acid ester.But suitably non-ionic monomer alkyl acrylate, alkyl methacrylate (as tert-butyl acrylate,
Ethyl acrylate etc.) or ethylenic unsaturated acid anhydride such as maleic anhydride.
The example of the ethylenic unsaturation anionic monomer that can be used is Mono-olefinic unsaturation C3To C10Or C3To C5Carboxylic
Acid, such as acrylic acid, methacrylic acid, ethylacrylic acid, butenoic acid, maleic acid, fumaric acid, vinyl sulfonic acid,
Styrene sulfonic acid, acrylamide group methyl propane sulfonic acid, vinyl phosphonate, itaconic acid, and the salt of these acid, such as the alkali gold of these acid
Belong to salt, alkali salt or ammonium salt.In anionic monomer, acrylic acid, methacrylic acid, maleic acid and 2-are preferably used
Acrylamido-2 methyl propane sulfonic acid.Particularly preferably aqueous solution based on acrylic acid polymer.Anionic monomer both can be single
Solely polymerization obtains the homopolymer polymerization that also can be mixed with each other and obtains copolymer.The example of described polymer be acrylic acid homopolymer,
The copolymer of the copolymer of the homopolymer of methacrylic acid, acrylic acid and maleic acid, acrylic acid and methacrylic acid, methyl
Acrylic acid and the copolymer of maleic acid.Preferably, polyanion is selected from can be by the polymer prepared selected from following monomer:
Mono-olefinic unsaturation C3To C10Carboxylic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide group methyl propane sulfonic acid, vinyl phosphonic
Acid and the salt of these acid, preferably acrylic acid, methacrylic acid, maleic acid, itaconic acid.Most preferably polyanion is poly-third
Olefin(e) acid or acrylic acid and the copolymer of maleic acid.
But, anionic polymer also can be polymerized in the presence of at least one other ethylenically unsaturated monomers.Described
But monomer nonionic or can be with cationic charge.The example of non-ionic co-monomers is acrylamide, methacryl
Amine, N-C1To C3-alkyl-acrylamide, N-vinyl formamide, have the acrylate of the monohydric alcohol of 1 to 20 carbon atom,
As being especially acrylic acid methyl ester., ethyl acrylate, Isobutyl 2-propenoate and n-butyl acrylate, there is 1 to 20 carbon atom
The methacrylate of monohydric alcohol, such as methyl methacrylate and ethyl methacrylate and vinyl acetate and vinyl propionate
Ester.
Can be propenoic acid dialkyl amino-ethyl ester, methacrylic acid with the suitable cation monomer of anionic monomer copolymerization
Di-alkyaminoethyl group ester, propenoic acid dialkyl aminopropyl ester, methacrylic acid dialkylamino propyl ester, dialkyl amido
Ethyl acrylamide, di-alkyaminoethyl group Methacrylamide, dialkylamino propyl acrylamide, dialkylamino propyl
Methacrylamide, diallyldimethylammonium chloride, vinyl imidazole and neutralized by acid and/or each quaternized alkali
Property monomer.The single instance of cationic monomer be acrylate, dimethylaminoethyl methacrylate, third
Olefin(e) acid diethylamino ethyl ester, diethyl aminoethyl methacrylate, acrylate propyl ester, methacrylic acid two
Methylamino propyl ester, acrylic acid diethylamino propyl ester and methacrylic acid diethylamino propyl ester, dimethyl aminoethyl third
Acrylamide, dimethyl aminoethyl Methacrylamide, dimethylaminopropylacryl amide, dimethylaminopropyl methyl-prop
Acrylamide, diethylaminoethyl and diethyl amino propyl acrylamide.
Alkaline monomer can be neutralized or quaternized the most to a certain extent, the most in each case, is neutralized
Or quaternized degree is 1 to 99%.The quaternizing agent being preferred for alkaline monomer is dimethyl sulfate.But, monomer is also
Can be quaternized by dithyl sulfate or halogenated hydrocarbons, halogenated hydrocarbons such as chloromethane, chloric ethane or benzyl chloride.Cationic monomer
The net charge that consumption up to makes the polymer obtained be carried is anion at a temperature of pH < 6.0 and 20 DEG C.In gained both sexes
Excessive anionic charge in polymer is for example, at least 5mol%, preferably at least 10mol%.
In preparing anionic polymer, the amount of non-anion nonacidic comonomer used is for making when pH is more than 7 and temperature
Degree is 20 DEG C, and when the polymer with water of formation dilutes, it is water-soluble, and has anionic, net electric charge.The nonacid copolymerization of non-anion
The example of the amount of monomer is, total amount meters based on the whole monomers used in the polymerization, 0 to 99 weight %, preferably 1 to 75
Weight %, usually 1 to 25 weight %.
The example of preferred copolymer is prepared by the acrylamide of the acrylic acid by 25 to 90 weight % and 75 to 10 weight %
Copolymer.Under there are not other Mono-olefinic unsaturated monomers, preferably it is polymerized at least one ethylenic unsaturation C3To C5Carboxylic
Acid.The acrylate homopolymer particularly preferably obtained by acrylic acid radical polymerization under there are not other monomers；Or preferably
Acrylic acid and the copolymer of maleic acid.
In one embodiment, anionic copolymer includes 2-acrylamide-2-methylpro panesulfonic acid (AMPS).Preferably
Acrylic acid and AMPS copolymerization.The amount of AMPS can be such as 0.1 to 15mol% or 0.5 to 10mol% herein, based on the most single
The gauge of body.
Can also carry out in the presence of at least one cross-linking agent for preparing the polyreaction of anionic polymer.In
Be, with there is no cross-linking agent in the presence of polymeric anion monomer compare, this makes copolymer have higher molal weight.Crosslinking used
Agent can include any compound in the molecule with at least two ethylenic unsaturated double-bond.The example of cross-linking agent is three allyls
Base amine, pentaerythritol triallyl ether, pentae-rythritol tetraallyl ether, methylene-bisacrylamide, N, N '-divinyl Asia second
Base urea, including the allyl ether of at least two pi-allyl or have the vinyl ethers of at least two vinyl, wherein said ether spreads out
It is conigenous polyhydric alcohol, such as sorbitol, 1，2-ethandiol, BDO, trimethylolpropane, glycerol, diethylene glycol, and derived from
Sugar, such as sucrose, glucose, mannose；Other examples are to have 2 to 4 carbon atoms and by acrylic or methacrylic acid
The dihydroxylic alcohols being esterified completely, such as Ethylene glycol dimethacrylate, ethylene glycol diacrylate, dimethacrylate butanediol
Ester, butanediol diacrylate, the diacrylate with the Polyethylene Glycol of molecular weight 300 to 600 or dimethylacrylate,
The trimethylene propane triacrylate of ethoxylation or the trimethylene propane trimethyl acrylic ester of ethoxylation, 2,2-are double
(methylol) butanol trimethyl acrylic ester, pentaerythritol triacrylate, tetramethylol methane tetraacrylate and triallyl first
Ammonium chloride.If the present invention solution prepare in use cross-linking agent, the example of each plant demand of cross-linking agent be 0.0005 to
5.0 weight %, preferably 0.001 to 1.0 weight %, based at the whole monomer meters used by polyreaction, premise is at pH > 7 times
Resulting polymers remains water-soluble.The cross-linking agent being preferably used is pentaerythritol triallyl ether, pentae-rythritol tetraallyl
Ether, N, N '-divinyl ethylidene-urea, the allyl ether of sugar (such as sucrose, glucose, mannose), wherein these ethers include
At least two pi-allyl, and triallylamine, and the mixture of these compounds.
If being polymerized at least one anionic monomer in the presence of at least one cross-linking agent, preferably in the presence of following material
The cross-linked copolymer of acrylic acid and/or methacrylic acid is prepared: tetramethylolmethane three by polymeric acrylic acid and/or methacrylic acid
Allyl ether, pentae-rythritol tetraallyl ether, N, N '-divinyl ethylidene-urea, sugar (such as sucrose, glucose, mannose)
Allyl ether, wherein these ethers include at least two pi-allyl, and triallylamine, and the mixture of these compounds.
The amount of cross-linking agent the most used is preferably limited to make the anionic polymer of formation at pH > 7 time in aqueous solution
Solvable degree.
The polymer comprising acid groups weight average molecular weight before neutralizing is at least 10000g/mol, more preferably at least
30000g/mol, such as 10000 to 200000g/mol or 30000 to 150000g/mol.
The acid moiety of polyanion or all neutralized selected from the alkali of inorganic base and monovalence organic base by least one.One
Valency organic base is the organic compound with single basic group, such as single amino group.Alkali is such as NaOH, KOH, Ca
(OH)2、Ba(OH)2, sodium carbonate, potassium carbonate, tertiary sodium phosphate, ammonia and primary organic amine, secondary organic amine or tertiary organic amine.Preferably alkali
For ammonia, sodium hydroxide and triethanolamine.The most volatile alkali, such as ammonia.
The degree of neutralization of polyanion is preferably 30 to 100%, and more preferably 50 to 100%, acid based on anionic polymer
The integral molar quantity meter of group.
Aqueous solution includes at least one polymine.Polymine is to include the polymer of ethylene imine units.
It is preferably branched.Polymine used can be the form of the salt neutralized with appropriate acid, but the most unneutralized form.
In one embodiment of the invention, polymine is selected from highly branched or dendritic polymine.
Highly branched polymine has the feature of highly-branched degree (DB).DB can pass through13C-NMR spectrum measures, preferably at D2O
Middle mensuration, is defined as follows:
DB=D+T/ (D+T+L)
Wherein D (dendroid) is relevant to the quantity of tertiary amine group, and L (wire) is relevant with the quantity of secondary amine group, T (end)
Relevant to the quantity of primary amine.The DB having according to the polymine that the present invention is highly branched is preferably 0.1 to 0.95, or 0.25
To 0.9, more preferably 0.30 to 0.80, particularly preferably at least 0.5.Dendroid polymine has in structure and homogeneous on molecule
Composition (DB=1).
The weight average molecular weight of polymine at least 25000g/mol, more preferably at least 10000g/mol, such as 25000 to
3000000 g/mol or 100000 to 2 million g/mol.The charge density of polymine preferably 1 to 35meq/g, more preferably 5 to
25meq/g.Charge density can be given instruction agent with toluidine blue, drip with potassium polyvinyl sulfate (KPVS) by when pH is 4.5
Determine the determination of aqueous solution of polymine.
Suitably cationic polymer is following epomine, and described epomine is in a small amount of acid or shape
Become in the presence of the compound of acid, prepared by polymerising ethylene imines in an aqueous medium, the described compound forming acid
Example is halogenated hydrocarbons, and such as chloroform, carbon tetrachloride, sym-tetrachloroethane or ethyl chloride, or cationic polymer is chloropropylene oxide and comprises ammonia
The condensation substance of the compound of base, comprises compound e.g. monoamine or the polyamines of amino, as dimethylamine, diethylamine, ethylenediamine, two
Ethylenetriamine and trien or ammonia.Such as, the molecular weight M of described cationic polymerwIt is 25000 to 3 million,
Preferably 100000 to 2 million g/mol.
This kind of cationic polymer also includes that aziridine grafting on the compound with primary amino radical or secondary amino group gathers
Compound, example is the Polyamide amine prepared by dicarboxylic acids and polyamines.If appropriate, the Polyamide amine of aziridine grafting is also
Can react with bifunctional cross-linker, such as with chloropropylene oxide or double chloroethene alcohol ether reactions of poly alkylene glycol.
In one embodiment, polymine is crosslinking.Having at least two can be with the amido of polymine
Any cross-linking agent of the functional group forming covalent bond can be used to crosslinking.Suitably cross-linking agent is for the most preferably having 3 to 20
The alkyl dialdehyde of individual carbon atom, such as glutaraldehyde (1,5-glutaraldehyde).
Aqueous solution can include the water as exclusive solvents or its may also comprise the mixing of water and miscible organic solvents
Thing, described organic solvent is such as methanol, ethanol, acetone or oxolane.Preferably water is exclusive solvents.PH is preferably 6 to 12,
More preferably 7 to 10.
One embodiment of the invention is to comprise the polymeric film of following oxygen obstruction coating, and described oxygen barrier coating passes through
Use above-mentioned aqueous polymer solution to obtain, at least a part of which the one side of polymeric film be coated with include at least one poly-cloudy from
Son and the aqueous solution of at least one polymine, wherein polyanion is to comprise the acidic group neutralized by least one monoacidic base
The polymer of group, and described in comprise acid groups polymer there is before neutralization the weight average molecular weight of at least 10000g/mol；And
And wherein said polymine has the weight average molecular weight of at least 25000g/mol.
Aqueous polymer solution for coating procedure can include other additives or auxiliary agent, as regulated the thickening of rheology
Agent, wetting aid or binding agent.Preferred polymers film base material applies to the polymeric film of packaging.
Preferably polymeric film is prepared by oriented polypropylene (OPP) or polyethylene, and wherein polyethylene can use ethylene by high pressure polymerisation
Method or the method for low-pressure polymerization prepare.The example of other suitable polymer films is prepared by polyester, such as poly terephthalic acid
Glycol ester, and the film prepared by polyamide, polystyrene, polrvinyl chloride.In one embodiment, polymeric film is biological
Degradable, as prepared by biodegradable aliphatic-aromatic copolyesters and/or polylactic acid, example isFilm orFilm.Suitably the example of copolyesters be by such as alkane glycol (especially C2 to C8 alkane glycol, such as BDO) and
Aliphatic dicarboxylic acid (especially C2 to C8 dicarboxylic acids, such as adipic acid) and aromatic dicarboxilic acid (such as p-phthalic acid) are formed.
Preferably polymeric film material is selected from polyethylene terephthalate, oriented polypropylene (OPP), cast polypropylene (casted
Polypropylene), polyethylene, biodegradable aliphatic-aromatic copolyesters, metallized polyethylene terephthalate
Ester, metallized oriented polypropylene (OPP) and polyamide.
The thickness range of polymeric film can be 5 to 200 μm, is 5 to 50 μm in the case of film prepared by polyamide, poly-
It is 10 to 100 μm in the case of film prepared by ethylene glycol terephthalate, is 10 to 100 μ in the case of oriented polypropylene (OPP)
M, is about 100 μm in the case of polychloroethylene film, is about 30-75 μm in the case of film prepared by polystyrene.
Preferably, the oxygen obstruction coating on polymeric film is atresia, its can pass through atomic force microscope (AFM) or
Scanning electron microscope (SEM) is analyzed.
One embodiment of the invention is to form the method with the polymeric film improving oxygen barrier property, its bag
Include:
-use aqueous solution at least one side of polymeric film,
-described aqueous solution includes at least one polyanion and at least one polymine, wherein said poly-the moon from
Son is the polymer comprising the acid groups neutralized by least one monoacidic base, described in comprise the Weight-average molecular of polymer of acid groups
Amount is at least 10000g/mol before neutralization；And the weight average molecular weight of wherein said polymine is at least 25000g/
mol；
Aqueous coating composition can be applied on the backing film that plastics are made with Conventional coaters.If material therefor is net
Shape form, aqueous polymer solution generally can be used by being used by applicator roll in groove and be allowed to smooth by air-brush.Other
The suitable feasible method using coating uses method or the method for spraying of reverse concave surface coating, or uses the coating machine system of roller
System, or other painting methods well known by persons skilled in the art.
Water paint also can be used by the method repeatedly coated, and wherein the first coating is followed by second or is more coated with
Layer.
Other suitable painting methods are known intaglio printing and raised relief printing method.Make with in printing-ink unit
Different with different ink institutes, context of methods such as uses printing process to be used for using aqueous polymer solution.The print that can be mentioned
Brush method is flexographic printing process, and it is known in those skilled in the art as letterpress, as a reality of intaglio printing
The photogravure of example, as the offset printing of an example of offset printing.Be used as modern digital printing, ink jet type is beaten
Print, electrophotography and direct imaging.
In order to realize the further improvement adhered on polymeric film, backing film can use sided corona treatment in advance.It is applied to sheet
The example of the amount on shape material is preferably 0.2 to 50g (polymer, solid)/m2, preferably 0.5 to 20g/m2Or 1 to 15g/m2。
In order to realize the further improvement adhered on polymeric film, can be poly-before base material coats oxygen barrier layer
Precoated shet or priming paint is used on compound film.Described priming paint can be based on polyurethane dispersing liquid class, polyurethane solutions class, solvent-free or molten
Agent base reactive polyurethane class, polyethyleneimine amine, polyacrylate or other priming paint well known by persons skilled in the art.
Once aqueous coating composition has been applied to flat substrates, is evaporated by solvent.To this end, such as, in continuous operation
In the case of material can be made to pass through dry channel, this passage can have infrared radiation device.The material that will have been coated with and be dried subsequently
Material by chill roll and finally batches.It is dried thickness preferably 0.2 to 50 μm of coating, particularly preferred 0.5 to 20 μm, optimum
Select 1-15 μm.
The base material coated by aqueous coating composition shows excellent oxygen obstruction effect, especially at the ring of high humility
In border.The base material being applied can be used for such as packing, and is preferred for food Package.Coating has extraordinary mechanical performance also
Demonstrate the best adhesion (blocking) performance, and substantially free from slight crack.
Oxygen obstruction coating may also used as intercepting the barrier coat of other materials.Described material can be carbon dioxide, nitrogen
Gas, bisphenol-A (BPA), mineral oil, fat, aldehyde, grease, plasticiser, photoinitiator or fragrance matter.
In order to obtain other specific surface propertys or specific paintability, the best printing of coated polymer film
Performance, or the sealing property improved further and non-blocking can or good resistance to water, use and provide these required additionally
It is favourable that the top coat layer of performance carries out overcoating to coating base material.Base material with the aqueous coating composition precoating of the present invention is easy
In by overcoating.For overcoating method, the one in repeatable said method, or any interruption winding and uncoiling can not be carried out
Operate and carry out repetitive coatings with continuous process.Therefore, the position of oxygen barrier layer can in the inside of system, and surface property by
Top coat layer determines.Top coat layer has good adhesiveness to oxygen barrier layer.Due to good moisture-resisting degree, even if relatively high
Under humidity level, the most also need not use extra moisture barrier coatings to guarantee the effectiveness of oxygen barrier layer.
In one embodiment, the polymeric film of the present invention also include except oxygen barrier layer at least one other by
The layer prepared selected from following material: polyacrylate, polyvinylidene chloride (PVDC), wax, epoxy resin, the curable propylene of UV
Acid esters and polyurethane.
In one embodiment of the invention, the polymeric film of the present invention as above and at least one other material
Lamination, the other material of wherein said at least one is selected from polyethylene terephthalate, oriented polypropylene (OPP), polyethylene, casting
Mould polypropylene, biodegradable aliphatic-aromatic copolymer, metallized polyethylene terephthalate, metallized fixed
To polypropylene, polyamide, paper and plate.
Another embodiment of the invention is the packaging of the polymeric film including the invention described above.
Embodiment
The test of oxygen obstruction effect:
Relative humidity (RH) grade is 85% time, the oxygen permeability of the coating on test polymer film.Test is 23 DEG C of temperature
Degree, is carried out under conditions of 100% oxygen.The polymeric film of support materials: boPP (bidirectional oriented polypropylene), thickness 40 μm.?
The oxygen permeability being not coated with overlay film at 85%RH/23 DEG C is: about 975cm3/(m2*d).Method of testing, based on ASTM D3985, uses
Electrical quantity sensor.Each sample is all tested twice and calculates average result.
The transmitance of multilayer system calculates according to following equation:
Wherein, TRAlwaysIt is the oxygen permeability of multilayer film, TRAAnd TRBIt is layer A and the oxygen permeability of layer B respectively.
Polymer samples:
PEI1 polymine aqueous solution, Mw=750000g/mol；
Charge density 17meq/g, pH=11
PEI2 polymine aqueous solution Mw=1300g/mol；
Charge density 16meq/g, pH=11
PVA polyvinylamine aqueous solution, Mw=340000g/mol；
Charge density 13meq/g, pH=7-9
The copolymer (75:25) of PAS1 polyacrylic acid and maleic acid,
Mw=80000g/mol
PAS2 polyacrylic acid, Mw=3000g/mol
Sample P AS1 and PAS2 use ammonia preneutralization with polymine and polyvinylamine before being combined.
Polymer solution coating single in boPP-film table 1 is used for preparing simple layer (embodiment 2-6) or molten with 4 kinds
Liquid coating is used for preparing 4-tunic (embodiment 1).Composition and result are summarized in table 1.
Table 1: the test result of oxygen permeability；Amount in parts by weight
Data show that embodiments of the invention 2 have best oxygen barrier property at high humidity.
Claims (19)
1. aqueous solution for providing a purposes for oxygen barrier property for polymeric film, and described aqueous solution includes at least one
Planting polyanion and at least one polymine, wherein said polyanion is that one comprises by least one selected from inorganic base
With the polymer of the acid groups that the alkali of monovalence organic base neutralizes, and described in comprise acid groups polymer have before neutralization to
The weight average molecular weight of few 10000g/mol；And wherein said polymine has the Weight-average molecular of at least 25000g/mol
Amount.
2., according to the purposes of aforementioned claim, wherein said aqueous solution contains:
(a) polyanion based on solid content meter 10 to 90 weight %；And
(b) polymine based on solid content meter 10 to 90 weight %.
3., according to the purposes any one of aforementioned claim, wherein said polyanion, in terms of without nertralizer, with polyethyleneimine
The weight ratio of amine is 10:2 to 10:5.
4., according to the purposes of claim 1 or 2, wherein said polyanion is selected from can be by the polymerization prepared selected from following monomer
Thing: Mono-olefinic unsaturation C3To C10Carboxylic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamide group methyl propane sulfonic acid, vinyl
Phosphonic acids and the salt of described acid.
5., according to the purposes of claim 1 or 2, wherein said polyanion is selected from can be by the polymerization prepared selected from following monomer
Thing: acrylic acid, methacrylic acid, maleic acid, itaconic acid.
6., according to the purposes of claim 1 or 2, wherein said polyanion is polyacrylic acid or acrylic acid and maleic acid
Copolymer.
7. according to the purposes of claim 1 or 2, the weight average molecular weight of the wherein said polymer comprising acid groups be 10000 to
200000g/mol。
8., according to the purposes of claim 1 or 2, wherein said polymine is branched, the weight average of described polymine
Molecular weight be the charge density of 25000 to 3 million g/mol and described polymine be 1 to 35meq/g.
9., according to the purposes of claim 1 or 2, wherein the degree of neutralization of polyanion is 30 to 100%, wherein the pH of aqueous solution
Be 6 to 12.
10., according to the purposes of claim 1 or 2, wherein alkali is selected from ammonia, sodium hydroxide and triethanolamine.
11. 1 kinds of polymeric films containing oxygen obstruction coating, it obtains according to purposes any one of claim 1 to 10, its
Described at least one side of polymeric film have been coated with a kind of at least one polyanion and at least one polymine of including
Aqueous solution, wherein said polyanion is to be neutralized selected from the alkali of inorganic base and monovalence organic base by least one a kind of comprising
The polymer of acid groups, and described in comprise acid groups polymer there is before neutralization the Weight-average molecular of at least 10000g/mol
Amount；And wherein said polymine has the weight average molecular weight of at least 25000g/mol.
12. polymeric films according to claim 11, wherein test, the oxygen of described coat film under 23 DEG C and 85% relative humidity
Transmitance is less than the 30% of the oxygen permeability being not coated with overlay film.
13. according to the polymeric film according to any one of claim 11 to 12, and wherein the material of polymeric film is selected from gathering benzene
Naphthalate, oriented polypropylene (OPP), polyethylene, cast polypropylene, biodegradable aliphatic-aromatic copolyesters, metal
Polyethylene terephthalate, metallized oriented polypropylene (OPP) and the polyamide changed.
14. according to the polymeric film according to any one of claim 11 to 12, its floating coat thickness after the drying be 0.2 to
50μm。
15. include at least one according to the polymeric film according to any one of claim 11 to 12, wherein said polymeric film
Additionally by the layer prepared selected from following material: the curable propylene of polyacrylate, polyvinylidene chloride, wax, epoxy resin, UV
Acid esters and polyurethane.
16. according to the polymeric film according to any one of claim 11 to 12, wherein oxygen obstruction coating atresia.
17. according to the polymeric film according to any one of claim 11 to 12, and it is laminated with at least one other material, wherein
The other material of described at least one selected from polyethylene terephthalate, oriented polypropylene (OPP), polyethylene, cast polypropylene,
Biodegradable aliphatic-aromatic copolymer, metallized polyethylene terephthalate, metallized oriented polypropylene (OPP),
Polyamide, paper and plate.
18. 1 kinds of packagings, it includes according to the polymeric film according to any one of claim 11 to 17.
The method that 19. 1 kinds of formation has the polymeric film improving oxygen-barrier property, including: at least one side at polymeric film is executed
With aqueous solution, described aqueous solution includes at least one polyanion and at least one polymine, wherein said poly-the moon
Ion is the polymer of a kind of acid groups comprising and being neutralized selected from the alkali of inorganic base and monovalence organic base by least one, and described
The polymer comprising acid groups has the weight average molecular weight of at least 10000g/mol before neutralization；And wherein said polyethyleneimine
Amine has the weight average molecular weight of at least 25000g/mol.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261656035P | 2012-06-06 | 2012-06-06 | |
| US61/656,035 | 2012-06-06 | ||
| EP12171025 | 2012-06-06 | ||
| EP12171025.5 | 2012-06-06 | ||
| PCT/EP2013/060843 WO2013182444A1 (en) | 2012-06-06 | 2013-05-27 | Use of aqueous polyanion-polyethyleneimine solutions for producing polymer films with oxygen-barrier properties |
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| Publication Number | Publication Date |
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| CN104350091A CN104350091A (en) | 2015-02-11 |
| CN104350091B true CN104350091B (en) | 2016-11-30 |
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| CN1590480A (en) * | 2003-08-30 | 2005-03-09 | 刘建林 | Modified polyvingl alcohol coating liquid and its manufucturing technology |
| WO2008042748A2 (en) * | 2006-09-29 | 2008-04-10 | Surmodics, Inc. | Polyelectrolyte media for bioactive agent delivery |
| WO2011023587A2 (en) * | 2009-08-24 | 2011-03-03 | Basf Se | Use of polyelectrolyte complexes for producing polymer films having oxygen barrier properties |
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