JP4573507B2 - Gas barrier coating agent and gas barrier film using the same - Google Patents
Gas barrier coating agent and gas barrier film using the same Download PDFInfo
- Publication number
- JP4573507B2 JP4573507B2 JP2003295827A JP2003295827A JP4573507B2 JP 4573507 B2 JP4573507 B2 JP 4573507B2 JP 2003295827 A JP2003295827 A JP 2003295827A JP 2003295827 A JP2003295827 A JP 2003295827A JP 4573507 B2 JP4573507 B2 JP 4573507B2
- Authority
- JP
- Japan
- Prior art keywords
- gas barrier
- coating agent
- barrier coating
- film
- agent according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 230000004888 barrier function Effects 0.000 title claims description 89
- 239000011248 coating agent Substances 0.000 title claims description 49
- -1 alkali metal salt Chemical class 0.000 claims description 54
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 150000004703 alkoxides Chemical class 0.000 claims description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims description 20
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 150000003839 salts Chemical group 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002952 polymeric resin Substances 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 description 72
- 235000002639 sodium chloride Nutrition 0.000 description 43
- 229920003169 water-soluble polymer Polymers 0.000 description 20
- 239000002585 base Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910000147 aluminium phosphate Chemical class 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical class [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000005033 polyvinylidene chloride Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical class [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical class [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- IZXRSZNHUSJWIQ-UHFFFAOYSA-N 2-methylpropan-2-ol;titanium Chemical compound [Ti].CC(C)(C)O.CC(C)(C)O.CC(C)(C)O.CC(C)(C)O IZXRSZNHUSJWIQ-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- NDSXSCFKIAPKJG-UHFFFAOYSA-N CC(C)O[Ti] Chemical compound CC(C)O[Ti] NDSXSCFKIAPKJG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002558 Curdlan Polymers 0.000 description 1
- 239000001879 Curdlan Substances 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
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- 229920001218 Pullulan Polymers 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical compound CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Chemical class 0.000 description 1
- 239000001110 calcium chloride Chemical class 0.000 description 1
- 229910001628 calcium chloride Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
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- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 229940078035 curdlan Drugs 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Chemical class 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- JEQPWXGHMRFTRF-UHFFFAOYSA-N n,n'-bis(2-methylpropyl)methanediimine Chemical compound CC(C)CN=C=NCC(C)C JEQPWXGHMRFTRF-UHFFFAOYSA-N 0.000 description 1
- CMESPBFFDMPSIY-UHFFFAOYSA-N n,n'-diphenylmethanediimine Chemical compound C1=CC=CC=C1N=C=NC1=CC=CC=C1 CMESPBFFDMPSIY-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Chemical class 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- WVULZDFWPQCPPJ-UHFFFAOYSA-N potassium;hydrochloride Chemical compound Cl.[K] WVULZDFWPQCPPJ-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Chemical class 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- OQTSOKXAWXRIAC-UHFFFAOYSA-N tetrabutan-2-yl silicate Chemical compound CCC(C)O[Si](OC(C)CC)(OC(C)CC)OC(C)CC OQTSOKXAWXRIAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- BCLLLHFGVQKVKL-UHFFFAOYSA-N tetratert-butyl silicate Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BCLLLHFGVQKVKL-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 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
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Description
この発明は、ガスバリア性塗工剤及びこれを用いたガスバリア性フィルムに関する。 The present invention relates to a gas barrier coating agent and a gas barrier film using the same.
食品や薬品の包装分野において、内容物の品質劣化を防ぐ目的で、酸素ガスバリア性等のガスバリア性に優れている包装材料が使用されている。このようなガスバリア性フィルムとしては、ポリ塩化ビニリデンを積層したフィルム、ポリビニルアルコール系樹脂を用いたフィルム等が知られている。特に、上記ポリ塩化ビニリデンを積層したフィルムは、食品包装用として幅広く使用されている。 In the field of food and medicine packaging, packaging materials having excellent gas barrier properties such as oxygen gas barrier properties are used for the purpose of preventing the quality deterioration of contents. As such a gas barrier film, a film in which polyvinylidene chloride is laminated, a film using a polyvinyl alcohol resin, and the like are known. In particular, a film in which the above-mentioned polyvinylidene chloride is laminated is widely used for food packaging.
しかし、上記ポリ塩化ビニリデンを積層したフィルムは、近年のダイオキシンをはじめとする環境問題から、使用が控えられる傾向にある。また、上記ポリビニルアルコール系樹脂を用いたフィルムは、ポリビニルアルコール系樹脂が水酸基を含有するため、高湿度下でのガスバリア性が低下する問題点を有する。 However, the film in which the polyvinylidene chloride is laminated tends to be refrained from use due to environmental problems such as dioxin in recent years. Moreover, since the film using the said polyvinyl alcohol-type resin contains a hydroxyl group, it has the problem that the gas barrier property under high humidity falls.
これに対し、高湿度下でのガスバリア性を向上させる方法として、ポリビニルアルコール系樹脂あるいはエチレン−ビニルアルコールコポリマーとアルコキシシランを含有する組成物を、ゾル−ゲル法によって重縮合した複合ポリマーをフィルムに塗工した例が特許文献１，２に開示されている。 On the other hand, as a method for improving gas barrier properties under high humidity, a composite polymer obtained by polycondensation of a composition containing a polyvinyl alcohol resin or an ethylene-vinyl alcohol copolymer and an alkoxysilane by a sol-gel method is used as a film. Examples of coating are disclosed in Patent Documents 1 and 2.
しかしながら、上記の各特許文献に記載のガスバリア組成物では、組成物をフィルムに塗工する際、熱処理を行う乾燥時間が短かったり、乾燥温度が低かったりすると、高湿度下におけるガスバリア性が必ずしも十分ではなくなってしまう。このため、実生産において十分なガスバリア性を発現させようとすると、時間がかかりすぎ、生産性が低くなることがあった。 However, in the gas barrier composition described in each of the above patent documents, when the composition is applied to a film, if the drying time for heat treatment is short or the drying temperature is low, the gas barrier property under high humidity is not always sufficient. It will disappear. For this reason, when it was going to express sufficient gas-barrier property in actual production, it took too much time and productivity might become low.
そこでこの発明は、塗工フィルムの実生産において、生産性を高め、ガスバリア性をより向上させたガスバリア性フィルムを作製する塗工剤を提供することを目的とする。 Therefore, an object of the present invention is to provide a coating agent for producing a gas barrier film having improved productivity and improved gas barrier property in actual production of a coated film.
この発明は、水溶性高分子、金属アルコキシドの加水分解物及び／又はその縮合物、並びに、アルカリ金属塩及び／又はアルカリ土類金属塩を含有する、ガスバリア性塗工剤によって、上記の課題を解決したのである。 The present invention solves the above problem by using a gas barrier coating agent containing a water-soluble polymer, a hydrolyzate of metal alkoxide and / or a condensate thereof, and an alkali metal salt and / or an alkaline earth metal salt. It was solved.
この発明にかかるガスバリア性塗工剤を、基材の少なくとも片面に塗工してガスバリア性フィルムを作製すると、ガスバリア性塗工剤に含まれる水溶性高分子と、金属アルコキシドの加水分解物及び／又はその縮合物とが重縮合反応を起こすことにより、有機物と無機物とが複合した緻密な構造体を形成して一定のガスバリア性を発現させる。また、アルカリ金属塩及び又はアルカリ土類金属塩を含有しているために、さらにガスバリア性を向上させる効果もあるので、高湿度条件下でも非常に優れたガスバリア性を発現するガスバリア性フィルムを得ることができる。 When the gas barrier coating agent according to the present invention is applied to at least one surface of the substrate to produce a gas barrier film, the water-soluble polymer contained in the gas barrier coating agent, the hydrolyzate of metal alkoxide, and / or Alternatively, by causing a polycondensation reaction with the condensate, a dense structure in which an organic substance and an inorganic substance are combined is formed, and a certain gas barrier property is exhibited. In addition, since it contains an alkali metal salt and / or alkaline earth metal salt, it also has an effect of improving gas barrier properties, so that a gas barrier film that exhibits excellent gas barrier properties even under high humidity conditions is obtained. be able to.
この発明にかかるガスバリア性塗工剤を塗工することにより、高湿度条件下でも高いガスバリア性を有するフィルムを得ることができる。 By applying the gas barrier coating agent according to the present invention, a film having a high gas barrier property can be obtained even under high humidity conditions.
以下、この発明について詳細に説明する。
この発明にかかるガスバリア性塗工剤は、水溶性高分子、金属アルコキシドの加水分解物及び／又はその縮合物、並びに、アルカリ金属塩及び／又はアルカリ土類金属塩を含有する、ガスバリア性塗工剤である。
The present invention will be described in detail below.
A gas barrier coating agent according to the present invention comprises a water-soluble polymer, a hydrolyzate of metal alkoxide and / or a condensate thereof, and an alkali metal salt and / or an alkaline earth metal salt. It is an agent.
具体的に、上記アルカリ金属塩としては、リチウムやナトリウム、カリウム、ルビジウム、セシウム等を含有した塩が挙げられる。また、上記アルカリ土類金属塩としては、マグネシウムやカルシウム、ストロンチウム、バリウム等を含有した塩が挙げられる。これらは強酸由来の塩でも、弱酸由来の塩でも、どちらであってもよい。すなわち、上記強酸由来の塩としては、例えば、塩酸のアルカリ金属塩である塩化ナトリウムや塩化カリウム、アルカリ土類金属塩である塩化マグネシウムや塩化カルシウム、硫酸のアルカリ金属塩である硫酸ナトリウムや硫酸カリウム、硫酸のアルカリ土類金属塩である硫酸マグネシウムや硫酸カルシウム、硝酸のアルカリ金属塩である硝酸ナトリウムや硝酸カリウム、硝酸のアルカリ土類金属塩である硝酸マグネシウムや硝酸カルシウム等が挙げられる。また、上記弱酸由来の塩としては、例えば、炭酸のアルカリ金属塩である炭酸ナトリウムや炭酸カリウム、炭酸のアルカリ土類金属塩である炭酸マグネシウムや炭酸カルシウム、リン酸のアルカリ金属塩であるリン酸ナトリウムやリン酸カリウム、リン酸のアルカリ土類金属塩であるリン酸マグネシウムやリン酸カルシウム、さらには、酢酸やプロピオン酸、ブタン酸等のカルボン酸のアルカリ金属塩やアルカリ土類金属塩が挙げられる。また、複数のアルカリ金属元素やアルカリ土類金属元素を含有する複合塩であってもよい。さらに、上記アルカリ金属塩や上記アルカリ土類金属塩は、人工又は天然由来のどちらでも構わない。これらの塩の中では、アルカリ金属塩の方が好ましく、ナトリウム塩又はカリウム塩であればより好ましい。最も好ましいのは、ナトリウム又はカリウムの塩酸塩、すなわち、塩化ナトリウム又は塩化カリウムである。 Specifically, examples of the alkali metal salt include salts containing lithium, sodium, potassium, rubidium, cesium and the like. Examples of the alkaline earth metal salt include salts containing magnesium, calcium, strontium, barium and the like. These may be either a salt derived from a strong acid or a salt derived from a weak acid. That is, examples of the salt derived from the strong acid include sodium chloride and potassium chloride, which are alkali metal salts of hydrochloric acid, magnesium chloride and calcium chloride, which are alkaline earth metal salts, and sodium sulfate and potassium sulfate, which are alkali metal salts of sulfuric acid. And magnesium sulfate and calcium sulfate which are alkaline earth metal salts of sulfuric acid, sodium nitrate and potassium nitrate which are alkali metal salts of nitric acid, and magnesium nitrate and calcium nitrate which are alkaline earth metal salts of nitric acid. Examples of the salt derived from the weak acid include sodium carbonate and potassium carbonate which are alkali metal salts of carbonic acid, magnesium carbonate and calcium carbonate which are alkaline earth metal salts of carbonic acid, and phosphoric acid which is an alkali metal salt of phosphoric acid. Sodium, potassium phosphate, magnesium phosphate and calcium phosphate, which are alkaline earth metal salts of phosphoric acid, and alkali metal salts and alkaline earth metal salts of carboxylic acids such as acetic acid, propionic acid, and butanoic acid. Further, it may be a composite salt containing a plurality of alkali metal elements or alkaline earth metal elements. Furthermore, the alkali metal salt and the alkaline earth metal salt may be either artificial or naturally derived. Among these salts, alkali metal salts are preferable, and sodium salts or potassium salts are more preferable. Most preferred is sodium or potassium hydrochloride, i.e. sodium chloride or potassium chloride.
上記アルカリ金属塩及び／又はアルカリ土類金属塩の添加量は、金属アルコキシドの加水分解物及び／又はその縮合物に含まれる金属元素に対して、０．０５〜５ｍｏｌ％であるのがよく、０．１〜４ｍｏｌ％であれば望ましく、０．２〜３ｍｏｌ％であればさらに望ましい。この添加量が０．０５ｍｏｌ％未満であったり、または、５ｍｏｌ％を超えてしまうと、上記ガスバリア性塗工剤を塗工したフィルムの、高湿度下におけるガスバリア性が十分なものではなくなってしまうことがある。 The addition amount of the alkali metal salt and / or alkaline earth metal salt is preferably 0.05 to 5 mol% with respect to the metal element contained in the hydrolyzate of metal alkoxide and / or the condensate thereof, If it is 0.1-4 mol%, it is desirable, and if it is 0.2-3 mol%, it is still more desirable. If this addition amount is less than 0.05 mol% or exceeds 5 mol%, the gas barrier property under high humidity of the film coated with the gas barrier coating agent is not sufficient. Sometimes.
上記ガスバリア性塗工剤中に、架橋剤が添加されていると、塗工した際のガスバリア性が向上するので望ましい。上記架橋剤は、上記ガスバリア性塗工剤中の他の成分と架橋反応し得るものであれば特に制限されるものではない。具体的には、エポキシ基、カルボジイミド基、アルデヒド基のうち、少なくとも一種類の官能基を、分子中に少なくとも一個有する化合物が挙げられる。この中でも、カルボジイミド基を含有する化合物（以下、「特定カルボジイミド化合物」と称する。）が最も好ましい。この例としては、ジシクロヘキシルカルボジイミド、ジイソブチルカルボジイミド、ジイソプロピルカルボジイミド、ジフェニルカルボジイミド等のモノカルボジイミド化合物、ポリウレタンの技術分野において公知のジイソシアネート化合物の脱炭酸反応によって得られるポリカルボジイミド化合物等があげられる。上記のポリウレタンの技術分野において公知のジイソシアネート化合物としては、メチレンジフェニルジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、ナフチレンー１，５−ジイソシアネート、テトラメチルキシリレンジイソシアネート、イソホロンジイソシアネート、水添キシリレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、ヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート、ノルボルネン・ジイソシアネート、トリメチルヘキサメチレンジイソシアネート等があげられる。この中でも、特に親水性のカルボジイミド化合物が好適であり、具体例としては、日清紡（株）製：商品名 カルボジライト等があげられる。 When a crosslinking agent is added to the gas barrier coating agent, it is desirable because the gas barrier property upon coating is improved. The crosslinking agent is not particularly limited as long as it can undergo a crosslinking reaction with other components in the gas barrier coating agent. Specific examples include compounds having at least one functional group in the molecule among an epoxy group, a carbodiimide group, and an aldehyde group. Among these, a compound containing a carbodiimide group (hereinafter referred to as “specific carbodiimide compound”) is most preferable. Examples thereof include monocarbodiimide compounds such as dicyclohexylcarbodiimide, diisobutylcarbodiimide, diisopropylcarbodiimide and diphenylcarbodiimide, and polycarbodiimide compounds obtained by decarboxylation of diisocyanate compounds known in the technical field of polyurethane. Diisocyanate compounds known in the polyurethane technical field include methylene diphenyl diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane. Examples include diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, and trimethylhexamethylene diisocyanate. Among these, hydrophilic carbodiimide compounds are particularly suitable, and specific examples include Nisshinbo Co., Ltd. product name: Carbodilite.
上記の特定のカルボジイミド基を有する化合物の添加量は、特に限定されないが、水溶性高分子内の反応性基１ｍｏｌに対して、１×１０-3〜０．０５ｍｏｌがよく、２×１０-3〜０．０１ｍｏｌが好ましい。１×１０-3ｍｏｌより少ないと、上記ガスバリア性塗工剤を塗工することで形成されるガスバリア性塗工層の緻密さが欠け、十分なガスバリア性が発現しにくくなる傾向がある。一方、０．０５ｍｏｌより多いと、溶液がゲル化したり、得られるガスバリア性フィルムの性能が低下する傾向がある。 The addition amount of the compound having the specific carbodiimide group is not particularly limited, but is preferably 1 × 10 −3 to 0.05 mol with respect to 1 mol of the reactive group in the water-soluble polymer, and 2 × 10 −3. -0.01 mol is preferred. When the amount is less than 1 × 10 −3 mol, the gas barrier coating layer formed by applying the gas barrier coating agent lacks the density, and sufficient gas barrier properties tend to be hardly exhibited. On the other hand, when it exceeds 0.05 mol, the solution tends to gel, or the performance of the obtained gas barrier film tends to deteriorate.
上記水溶性高分子とは、水溶性を有する高分子物質をいい、官能基として、水酸基、アミノ基、酸アミド基、チオール基、カルボキシル基、スルホン酸基、リン酸基等を有するものがあげられる。この水溶性高分子の例としては、ポリビニルアルコール系重合体、エチレン−ビニルアルコール共重合体、カルボキシメチルセルロース、 ヒドロキシエチルセルロース、ヒドロキシメチルセルロース、アミロース、アミロペクチン、 プルラン、 カードラン、ザンタン、キチン、 キトサン、ポリアクリル酸、 ポリアクリル酸ナトリウム、 ポリベンゼンスルホン酸、 ポリベンゼンスルホン酸ナトリウム、ポリエチレンイミン、ポリアリルアミン、ポリアクリルアミド、ゼラチン、ポリビニルピロリドン等や、これらの共重合体、変性体等の誘導体があげられる。これらの中でも、高分子中に窒素含有官能基を２個以上含有する水溶性高分子が好ましく、ポリアクリルアミドが特に好ましい。ポリアクリルアミドを用いることにより、得られるガスバリア性塗工剤を塗工する後述の基材と、この基材に上記ガスバリア性塗工剤を塗工して形成されるガスバリア性塗工層との密着性が向上し、より良好な性能が得られる。これらは、少なくとも１種が使用され、１種のみを使用してもよく、２種以上を混合して使用してもよい。 The water-soluble polymer refers to a water-soluble polymer substance, and those having a functional group having a hydroxyl group, an amino group, an acid amide group, a thiol group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. It is done. Examples of this water-soluble polymer include polyvinyl alcohol polymers, ethylene-vinyl alcohol copolymers, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan, and polyacryl. Derivatives such as acid, sodium polyacrylate, polybenzenesulfonic acid, sodium polybenzenesulfonate, polyethyleneimine, polyallylamine, polyacrylamide, gelatin, polyvinylpyrrolidone, and their copolymers and modified products are exemplified. Among these, a water-soluble polymer having two or more nitrogen-containing functional groups in the polymer is preferable, and polyacrylamide is particularly preferable. By using polyacrylamide, adhesion between a base material described later on which the obtained gas barrier coating agent is applied and a gas barrier coating layer formed by applying the gas barrier coating agent to this base material Improves the performance. At least one of these may be used, and only one may be used, or two or more may be mixed and used.
上記水溶性高分子の重量平均分子量は、特に限定されないが、５００〜２０００万が好ましく、５０００〜１５００万がより好ましい。５００より小さいと、最終的に得られる塗工剤のガスバリア性が悪くなる傾向がある。一方、２０００万より大きいと、水溶液とした場合の粘度が高くなりすぎる傾向がある。 Although the weight average molecular weight of the said water-soluble polymer is not specifically limited, 500-20 million are preferable and 5000-15 million are more preferable. If it is less than 500, the gas barrier property of the finally obtained coating agent tends to be poor. On the other hand, when it is larger than 20 million, the viscosity of the aqueous solution tends to be too high.
上記の金属アルコキシドとは、下記の化学式（Ｉ）であらわされる化合物をいう。
Ｒ1 m Ｍ（ＯＲ2 ）n （Ｉ）
上記式（Ｉ）において、Ｍは金属元素であり、ケイ素、チタン、ジルコニウム、アルミニウム等から選ばれる少なくとも一種の金属元素であると望ましい。Ｒ1 は、水素原子又は炭素数１〜４の低級アルキル基であると望ましく、Ｒ2 は炭素数１〜４のアルキル基であると望ましい。Ｒ1 とＲ2 とは同一であってもよいし、違っていてもよい。また、ｍは０以上、ｎは１以上の整数で、かつ、ｍ＋ｎは金属元素Ｍの原子価と一致するものである。
The above metal alkoxide refers to a compound represented by the following chemical formula (I).
R 1 m M (OR 2 ) n (I)
In the above formula (I), M is a metal element, and is preferably at least one metal element selected from silicon, titanium, zirconium, aluminum and the like. R 1 is preferably a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and R 2 is preferably an alkyl group having 1 to 4 carbon atoms. R 1 and R 2 may be the same or different. M is an integer of 0 or more, n is an integer of 1 or more, and m + n corresponds to the valence of the metal element M.
上記金属アルコキシドは、その加水分解物及び／又はその縮合物を使用するので、触媒の作用で加水分解及び縮合するものであれば特に限定されない。この金属アルコキシドの例としては、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリイソプロポキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリイソプロポキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、トリメチルメトキシシラン、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン、テトラ−ｎ−プロポキシシラン、テトラ−ｎ−ブトキシシラン、テトラ−ｔｅｒｔ−ブトキシシラン、テトラ−ｓｅｃ−ブトキシシラン等のアルコキシシラン化合物、テトラメトキシチタン、テトラエトキシチタン、テトライソプロポキシチタン、テトラ−ｎ−プロポキシチタン、テトラ−ｎ−ブトキシチタン、テトラ−ｔｅｒｔ−ブトキシチタン、テトラ−ｓｅｃ−ブトキシチタン等のチタンアルコキシド化合物、テトラメトキシジルコニウム、テトラエトキシジルコニウム、テトライソプロポキシジルコニウム、テトラ−ｎ−プロポキシジルコニウム、テトラ−ｎ−ブトキシジルコニウム、テトラ−ｔｅｒｔ−ブトキシジルコニウム、テトラ−ｓｅｃ−ブトキシジルコニウム等のジルコニウムアルコキシド化合物、トリメトキシアルミニウム、トリエトキシアルミニウム、トリイソプロポキシアルミニウム、トリ−ｎ−プロポキシアルミニウム、トリ−ｎ−ブトキシアルミニウム、トリ−ｔｅｒｔ−ブトキシアルミニウム、トリ−ｓｅｃ−ブトキシアルミニウム等のアルミニウムアルコキシド化合物等があげられる。これらの中でも、アルコキシシラン化合物が最も好適である。これらは、少なくとも１種が使用され、１種のみを使用してもよく、２種以上を併用してもよい。 Since the said metal alkoxide uses the hydrolyzate and / or its condensate, if it hydrolyzes and condenses by the effect | action of a catalyst, it will not specifically limit. Examples of the metal alkoxide include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, n-propyltrimethoxysilane, and n-propyl. Triethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, trimethylmethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n- Alkoxysilane compounds such as butoxysilane, tetra-tert-butoxysilane, tetra-sec-butoxysilane, tetramethoxy titanium, tetraethoxy titanium, teto Titanium alkoxide compounds such as isopropoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-tert-butoxy titanium, tetra-sec-butoxy titanium, tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, Zirconium alkoxide compounds such as tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, tetra-tert-butoxyzirconium, tetra-sec-butoxyzirconium, trimethoxyaluminum, triethoxyaluminum, triisopropoxyaluminum, tri-n- Propoxyaluminum, tri-n-butoxyaluminum, tri-tert-butoxyaluminum, tri-sec-butoxyaluminum Aluminum alkoxide compounds such as beam and the like. Of these, alkoxysilane compounds are most preferred. At least one of these may be used, and only one may be used, or two or more may be used in combination.
上記金属アルコキシドの添加量は、上記水溶性高分子１００重量部に対して、対応する金属酸化物換算で８０〜１４００重量部がよく、１４０〜１０００重量部が好ましく、１６０〜６００重量部であればより好ましい。８０重量部より少ないと、十分なガスバリア性や耐熱水性が発現しにくくなる傾向にある。また、１４００重量部より多いと、得られるガスバリア性塗工剤からなるガスバリア性塗工層の脆性が増し、性能が悪くなる傾向がある。 The addition amount of the metal alkoxide is preferably 80 to 1400 parts by weight, preferably 140 to 1000 parts by weight, and 160 to 600 parts by weight, in terms of the corresponding metal oxide, with respect to 100 parts by weight of the water-soluble polymer. More preferable. When the amount is less than 80 parts by weight, sufficient gas barrier properties and hot water resistance tend to be hardly exhibited. On the other hand, when the amount is more than 1400 parts by weight, the brittleness of the resulting gas barrier coating layer made of the gas barrier coating agent tends to increase and the performance tends to deteriorate.
上記金属アルコキシドの加水分解反応や縮合反応を行うためには、水、加水分解反応や縮合反応を行う触媒、及び有機溶媒が用いられる。さらに、上記の水溶性高分子と金属アルコキシドの加水分解物及び／又はその縮合物の結合性をより向上するため、下記の一般式（ＩＩ）で示される有機官能基及び加水分解基を有するシラン化合物（以下、「特定シラン化合物」と称する。）を添加してもよい。
Ｒ3 p Ｓｉ（ＯＲ4 ）q （ＩＩ）
上記式（ＩＩ）において、Ｒ3 は上記水溶性高分子と反応し得る有機官能基であるビニル基、メルカプト基、アミノ基、エポキシ基、イソシアネート基のうち少なくとも一種類を、少なくとも一つ含有していることが望ましく、エポキシ基を含有していればより望ましい。また、Ｒ4 は炭素数１〜４のアルキル基であることが望ましい。なお、ｐ及びｑは１以上の整数であり、かつ、ｐ＋ｑ＝４の等式が成り立つ。
In order to perform the hydrolysis reaction or condensation reaction of the metal alkoxide, water, a catalyst for performing the hydrolysis reaction or condensation reaction, and an organic solvent are used. Furthermore, in order to further improve the binding properties of the hydrolyzate and / or condensate of the above water-soluble polymer and metal alkoxide, a silane having an organic functional group and a hydrolyzable group represented by the following general formula (II) A compound (hereinafter referred to as “specific silane compound”) may be added.
R 3 p Si (OR 4 ) q (II)
In the above formula (II), R 3 contains at least one of a vinyl group, a mercapto group, an amino group, an epoxy group, and an isocyanate group, which are organic functional groups capable of reacting with the water-soluble polymer. It is desirable that it contains an epoxy group, and it is more desirable. R 4 is preferably an alkyl group having 1 to 4 carbon atoms. Note that p and q are integers of 1 or more, and the equation p + q = 4 holds.
上記金属アルコキシドの加水分解反応及びその縮合反応、又はそれらの反応生成物と上記水溶性高分子との重縮合反応は、酸性条件、塩基性条件のいずれの条件下においても促進される。なお、上記ガスバリア性塗工剤には、ガスバリア性が劣化しない範囲内で、上記の加水分解反応及び重縮合反応を起こすための、一般に知られている触媒を添加してもよい。 The hydrolysis reaction of the metal alkoxide and the condensation reaction thereof, or the polycondensation reaction between the reaction product and the water-soluble polymer are promoted under both acidic conditions and basic conditions. The gas barrier coating agent may be added with a generally known catalyst for causing the hydrolysis reaction and polycondensation reaction as long as the gas barrier property does not deteriorate.
酸性条件下における上記触媒となる酸触媒としては、例えば、塩酸、硝酸、硫酸等の鉱酸、リン酸、酢酸、クエン酸、シュウ酸、ｐ−トルエンスルホン酸等の有機酸が挙げられる。また、塩基性条件下における上記触媒としては、例えば、水酸化ナトリウム、水酸化カルシウム、水酸化マグネシウム等の無機塩基、アンモニア、ピリジン、トリエチルアミン、Ｎ，Ｎ−ジメチルベンジルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン等の有機塩基が挙げられる。これらの中でも、酸性条件が好ましく、塩酸が特に好ましい。さらに、これらの触媒は、１種のみを使用してもよく、２種以上を併用してもよい。さらにまた、触媒は、加水分解反応を目的とする触媒と、重縮合反応を目的にする触媒とに分けて用いてもよい。 Examples of the acid catalyst that serves as the catalyst under acidic conditions include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as phosphoric acid, acetic acid, citric acid, oxalic acid, and p-toluenesulfonic acid. Examples of the catalyst under basic conditions include inorganic bases such as sodium hydroxide, calcium hydroxide and magnesium hydroxide, ammonia, pyridine, triethylamine, N, N-dimethylbenzylamine, tripropylamine, and tributylamine. And organic bases such as tripentylamine. Among these, acidic conditions are preferable, and hydrochloric acid is particularly preferable. Furthermore, these catalysts may use only 1 type and may use 2 or more types together. Furthermore, the catalyst may be divided into a catalyst for the hydrolysis reaction and a catalyst for the polycondensation reaction.
上記の触媒の添加量は、特に限定されず、溶液がゲル化しない範囲内で、任意の量を添加することができる。 The addition amount of said catalyst is not specifically limited, Arbitrary amounts can be added within the range in which a solution does not gel.
上記有機溶媒は、上記の金属アルコキシドを溶解させ、さらに、上記水溶性高分子の水溶液と相溶するものであれば特に限定はされないが、メタノール、エタノール、プロパノール、ブタノール等の低級アルコールが好ましい。これらは、１種のみを使用してもよく、２種以上を併用してもよい。 The organic solvent is not particularly limited as long as it dissolves the metal alkoxide and is compatible with the aqueous solution of the water-soluble polymer, but is preferably a lower alcohol such as methanol, ethanol, propanol, or butanol. These may use only 1 type and may use 2 or more types together.
上記有機溶媒の添加量は、特に限定されないが、上記の金属アルコキシド１００重量部に対し、２〜５００重量部がよく、１０〜３００重量部が好ましい。２重量部より少ないと、上記の金属アルコキシドが十分に溶解せず、加水分解反応が抑制される。一方、５００重量部より多いと、水溶性高分子の溶解性が低下する傾向がある。 Although the addition amount of the organic solvent is not particularly limited, it is preferably 2 to 500 parts by weight and preferably 10 to 300 parts by weight with respect to 100 parts by weight of the metal alkoxide. When the amount is less than 2 parts by weight, the metal alkoxide is not sufficiently dissolved, and the hydrolysis reaction is suppressed. On the other hand, when the amount is more than 500 parts by weight, the solubility of the water-soluble polymer tends to decrease.
上記ガスバリア性塗工剤のｐＨは、１．０〜５．０であることが望ましく、１．１〜４．５であればより望ましく、１．５〜３．５であれば最も望ましい。もし上記塗工剤のｐＨが５．０より高いと、すぐに溶液がゲル化して塗工不能になっていまう。一方で、ｐＨが１．０より低いと、ガスバリア性が劣化することはないが、酸性が強すぎるために製造が困難となり、望ましくない。このようにｐＨが１．０〜５．０の間から外れてしまった場合は、水酸化ナトリウム等の塩基、塩酸等の酸を添加して、ｐＨを１．０〜５．０の間に調整しなおすことが望ましい。 The pH of the gas barrier coating agent is preferably 1.0 to 5.0, more preferably 1.1 to 4.5, and most preferably 1.5 to 3.5. If the pH of the coating agent is higher than 5.0, the solution immediately gels and cannot be applied. On the other hand, if the pH is lower than 1.0, the gas barrier property is not deteriorated, but the production is difficult because the acidity is too strong, which is not desirable. In this way, when the pH is out of the range of 1.0 to 5.0, a base such as sodium hydroxide or an acid such as hydrochloric acid is added to adjust the pH to between 1.0 and 5.0. It is desirable to readjust.
また、上記低級アルコールは、上記水溶性高分子が析出しない範囲内で添加することが望ましい。 The lower alcohol is preferably added within a range where the water-soluble polymer does not precipitate.
次に、この発明にかかるガスバリア性塗工剤の製造方法について説明する。この発明にかかるガスバリア性塗工剤は、上記の各種原料を混合することにより製造される。このとき、上記の金属アルコキシドは、あらかじめ加水分解したものを用いてもよい。 Next, the manufacturing method of the gas barrier coating agent concerning this invention is demonstrated. The gas barrier coating agent according to the present invention is produced by mixing the various raw materials described above. At this time, the metal alkoxide may be hydrolyzed in advance.
上記ガスバリア性塗工剤の各種原料の混合順序は、特に制限されないが、金属アルコキシドを直接加える場合の一例を以下に示す。まず、上記水溶性高分子の水溶液に上記低級アルコール及び上記酸触媒を添加し、次いで、上記金属アルコキシド及び、必要に応じて上記特定シラン化合物を混合して、溶液を完全に溶解させる。次に必要に応じて、上記特定カルボジイミド化合物を加える。その次に、アルカリ金属塩及び／又はアルカリ土類金属塩を添加し、さらにその他の各種添加剤を必要に応じて加えることができる。 Although the mixing order of the various raw materials of the gas barrier coating agent is not particularly limited, an example in the case of directly adding a metal alkoxide is shown below. First, the lower alcohol and the acid catalyst are added to the aqueous solution of the water-soluble polymer, and then the metal alkoxide and, if necessary, the specific silane compound are mixed to completely dissolve the solution. Next, the said specific carbodiimide compound is added as needed. Next, an alkali metal salt and / or an alkaline earth metal salt can be added, and various other additives can be added as necessary.
この発明にかかるガスバリア性塗工剤を含有する塗工剤を、基材の少なくとも片面に塗工することによって、ガスバリア性フィルムを製造することができる。 A gas barrier film can be produced by applying a coating agent containing the gas barrier coating agent according to the present invention to at least one surface of a substrate.
上記基材としては、ガス透過性の有無に関わらず、基材としての強度を有していればよく、ナイロン６、ナイロン６６、ナイロン４６等のポリアミド樹脂、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等のポリエステル樹脂、ポリプロピレン、ポリエチレン等のポリオレフィン樹脂、及びそれらの混合樹脂から選ばれる少なくとも１種の樹脂からなる高分子樹脂フィルム、又はそれらの高分子樹脂フィルムの積層体があげられる。この高分子樹脂フィルムは、未延伸フィルムであってもよく、また、延伸フィルムであってもよい。 The base material may have any strength as a base material regardless of gas permeability, such as polyamide resin such as nylon 6, nylon 66, nylon 46, polyethylene terephthalate, polyethylene naphthalate, polybutylene. Examples thereof include a polymer resin film composed of at least one resin selected from polyester resins such as naphthalate, polyolefin resins such as polypropylene and polyethylene, and mixed resins thereof, and laminates of these polymer resin films. This polymer resin film may be an unstretched film or a stretched film.
なお、上記基材の表面には、接着性を向上させるため、公知のコロナ放電処理、 火炎処理、 紫外線処理、 アンカーコート剤塗布処理などを行ってもよい。 In addition, in order to improve adhesiveness, you may perform the well-known corona discharge process, a flame process, an ultraviolet-ray process, an anchor coating agent application | coating process, etc. on the surface of the said base material.
上記塗工とは、基材表面に上記ガスバリア性塗工剤を塗工し、上記ガスバリア性塗工層を形成させる方法であれば特に限定されるものではなく、グラビアコーティング、リバースロールコーティング、ワイヤーバーコーティング、ダイコーティング等の通常の塗工方法を採用することができる。なお、上記塗工は、フィルムの延伸前であっても延伸後であってもよい。 The coating is not particularly limited as long as it is a method for coating the base material surface with the gas barrier coating agent and forming the gas barrier coating layer. Gravure coating, reverse roll coating, wire Conventional coating methods such as bar coating and die coating can be employed. The coating may be performed before or after stretching the film.
上記ガスバリア性塗工層の厚みは、乾燥後で厚み０．０５〜３μｍが好ましく、０．１〜２μｍがより好ましい。 The thickness of the gas barrier coating layer is preferably 0.05 to 3 [mu] m, more preferably 0.1 to 2 [mu] m after drying.
上記ガスバリア性塗工剤を上記基材に塗工することによって形成されるガスバリア性塗工層の乾燥は特に限定されないが、基材の融点及び軟化点以下の温度で行うことができ、架橋反応が十分に行われる温度でよい。 The drying of the gas barrier coating layer formed by applying the gas barrier coating agent to the substrate is not particularly limited, but can be performed at a temperature below the melting point and softening point of the substrate, and the crosslinking reaction. The temperature may be sufficient.
さらに、上記ガスバリア性塗工剤を塗工し、乾燥させた基材を、エージングすることによって、形成されたガスバリア性塗工層の架橋密度を増大させ、よりバリア性を向上させることができる。このエージングの温度や時間は、特に限定されないが、２０〜１２０℃で１〜１５０時間が好ましく、３０〜７０℃で６〜１００時間がより好ましい。 Furthermore, by aging the substrate coated with the gas barrier coating agent and dried, the crosslink density of the formed gas barrier coating layer can be increased, and the barrier property can be further improved. Although the temperature and time of this aging are not specifically limited, 1-150 hours are preferable at 20-120 degreeC, and 6-100 hours are more preferable at 30-70 degreeC.
上記温度が２０℃より低いと、エージング時間がかかりすぎる傾向にあり、一方、１２０℃を超えると、基材にダメージを与える場合がある。また、上記時間が、１時間より短いと、十分に架橋密度を増大させることができない場合がある。一方、１５０時間を超えてもよいが、特に性能向上に与える効果はない。 If the temperature is lower than 20 ° C., the aging time tends to be excessive, while if it exceeds 120 ° C., the substrate may be damaged. If the time is shorter than 1 hour, the crosslinking density may not be increased sufficiently. On the other hand, although it may exceed 150 hours, it has no effect on performance improvement.
上記ガスバリア性塗工剤は、例えば、溶液を加熱する等の操作によって、急激に有機物と無機物とを複合化させてしまうと、多孔質な構造となってしまい、十分な性能が得られない場合がある。このため、基材に塗工、乾燥させてから、上記エージング等の操作で徐々に反応させることによって、より緻密な構造を造ることができる。 The gas barrier coating agent has a porous structure when the organic substance and the inorganic substance are rapidly combined by an operation such as heating the solution, for example, and sufficient performance cannot be obtained. There is. For this reason, after making it apply | coat and dry to a base material and making it react gradually by operation, such as said aging, a more precise structure can be made.
上記ガスバリア性フィルムは、非常に緻密な構造を有するガスバリア性塗工層を有するので、高湿度条件下で十分なガスバリア性を発揮し、また、表面の平滑性及び透明性に優れる。このガスバリア性フィルムは、具体的には、２３℃９０％ＲＨの高湿度条件下において、このガスバリア性フィルム１μｍあたりの酸素透過度が、５ｃｃ／ｍ2 ・ｄａｙ・ａｔｍ以下であることが好ましく、２ｃｃ／ｍ2 ・ｄａｙ・ａｔｍ以下であればより好ましく、低いほどより好ましい。もし５ｃｃ／ｍ2 ・ｄａｙ・ａｔｍを超えると、バリア性包装材料として実用性に欠ける。 Since the gas barrier film has a gas barrier coating layer having a very dense structure, it exhibits a sufficient gas barrier property under high humidity conditions, and is excellent in surface smoothness and transparency. Specifically, the gas barrier film preferably has an oxygen permeability of 5 cc / m 2 · day · atm or less per 1 μm of the gas barrier film under a high humidity condition of 23 ° C. and 90% RH. It is more preferable if it is 2 cc / m 2 · day · atm or less, and it is more preferable as it is lower. If it exceeds 5 cc / m 2 · day · atm, it is not practical as a barrier packaging material.
この発明にかかるガスバリア性フィルムは、そのままガスバリア性フィルムとして使用する以外に、このガスバリア性フィルムを他のフィルム又はシートに少なくとも１層積層することにより、積層体を形成させて使用してもよい。この積層体はガスバリア性を有する積層体として使用することができる。 The gas barrier film according to the present invention may be used as a gas barrier film as it is, as well as by forming at least one layer of this gas barrier film on another film or sheet to form a laminate. This laminate can be used as a laminate having gas barrier properties.
以下、実験例と比較例により、この発明をさらに具体的に説明する。まず、使用原料及び評価方法について下記に示す。 Hereinafter, the present invention will be described more specifically with reference to experimental examples and comparative examples. First, the raw materials used and the evaluation method are shown below.
［使用原料］
（水溶性高分子）
・ポリアクリルアミド・・・東京化成工業（株）製：試薬（１０％水溶液 重量平均分子量７０万〜１００万 以下、「ＰＡＭ」と略す。）
・ポリビニルアルコール・・・（株）クラレ製：ＰＶＡ１１７（平均重合度１７００ 以下、「ＰＶＡ」と略す。）
[Raw materials]
(Water-soluble polymer)
Polyacrylamide: manufactured by Tokyo Chemical Industry Co., Ltd .: Reagent (10% aqueous solution, weight average molecular weight 700,000 to 1,000,000 or less, abbreviated as “PAM”)
Polyvinyl alcohol: Kuraray Co., Ltd .: PVA117 (average polymerization degree 1700 or less, abbreviated as “PVA”)
（金属アルコキシド）
・テトラエトキシシラン・・・コルコート（株）製：エチルシリケート（以下、「ＴＥＯＳ」と略す。）
(Metal alkoxide)
Tetraethoxysilane: Colcoat Co., Ltd .: ethyl silicate (hereinafter abbreviated as “TEOS”)
（特定カルボジイミド化合物）
・日清紡（株）製：カルボジライト Ｖ−０２−Ｌ２（有効成分４０重量％ カルボジイミド当量３８５）
(Specific carbodiimide compound)
-Nisshinbo Co., Ltd .: Carbodilite V-02-L2 (active ingredient 40% by weight carbodiimide equivalent 385)
（特定シラン化合物）
・３−グリシドキシプロピルトリメトキシシラン・・・信越シリコーン（株）製：ＫＢＭ−４０３
(Specific silane compounds)
-3-glycidoxypropyltrimethoxysilane ... Shin-Etsu Silicone Co., Ltd. product: KBM-403
［フィルムのガスバリア性の評価方法］
酸素透過度試験機（Ｍｏｄｅｒｎ Ｃｏｎｔｏｒｏｌ社製、ＯＸ−ＴＲＡＮ２／２０）により、２３℃、相対湿度９０％ＲＨ雰囲気下における酸素透過度を測定した。フィルムのガスバリア性は、基材の種類や厚み、及び、積層させるガスバリア性塗工層の厚みにより変化するため、下記の式に従ってコート層１μｍあたりの酸素透過度（Ｐsample）（単位：ｃｃ・１μｍ／ｍ2 ・ｄａｙ・ａｔｍ）を算出した。
[Method for evaluating gas barrier properties of film]
The oxygen permeability under an atmosphere of 23 ° C. and a relative humidity of 90% RH was measured with an oxygen permeability tester (manufactured by Modern Control, OX-TRAN 2/20). Since the gas barrier property of the film changes depending on the type and thickness of the base material and the thickness of the gas barrier coating layer to be laminated, the oxygen permeability per 1 μm of the coating layer (P sample ) (unit: cc · 1 μm / m 2 · day · atm) was calculated.
１／Ｐtotal ＝１／Ｐsample＋１／Ｐbase
Ｐtotal ：測定結果
Ｐsample：コート層の酸素透過度
Ｐbase：コート層を積層する前の基材フィルムの酸素透過度
1 / P total = 1 / P sample + 1 / P base
Ptotal : Measurement result Psample : Oxygen permeability of the coat layer Pbase : Oxygen permeability of the base film before laminating the coat layer
（実験例１〜３，参考例１）
水溶性高分子（ＰＡＭ：実験例１・２・４、ＰＶＡ：実験例３）の２重量％水溶液２５０ｇ（固形分５ｇ）を調製し、次いでこれに、エタノール７５ｇ、２Ｎ塩酸水溶液を１５ｇ、金属アルコキシドとしてＴＥＯＳを７５ｇ、特定シラン化合物としてＫＢＭ−４０３を７．５ｇ、架橋剤としてＶ−０２−Ｌ２を０．５ｇを順次添加し、液が均一になるまで攪拌した。その後、それぞれアルカリ金属塩又はアルカリ土類金属塩として、塩化ナトリウム（実験例１）１ｍｏｌ％、塩化カリウム（実験例２）０．５ｍｏｌ％、硝酸カルシウム（参考例１）２ｍｏｌ％、塩化マグネシウム（実験例３）０．５ｍｏｌ％添加し、攪拌した。なお、添加量の単位は金属アルコキシドであるＴＥＯＳの加水分解物及び／又はその縮合物中に含まれる金属元素に対するｍｏｌ％である。
(Experimental Examples 1-3, Reference Example 1 )
250 g of a 2 wt% aqueous solution (5 g of solid content) of a water-soluble polymer (PAM: Experimental Examples 1 and 2 and PVA: Experimental Example 3) was prepared, and then 75 g of ethanol and 15 g of a 2N aqueous hydrochloric acid solution were added to the metal. 75 g of TEOS as the alkoxide, 7.5 g of KBM-403 as the specific silane compound, and 0.5 g of V-02-L2 as the cross-linking agent were sequentially added and stirred until the liquid became uniform. Thereafter, as an alkali metal salt or alkaline earth metal salt, sodium chloride (Experimental Example 1) 1 mol%, potassium chloride (Experimental Example 2) 0.5 mol%, calcium nitrate ( Reference Example 1 ) 2 mol%, magnesium chloride (experimental) Example 3 ) 0.5 mol% was added and stirred. The unit of the addition amount is mol% with respect to the metal element contained in the hydrolyzate of TEOS which is a metal alkoxide and / or the condensate thereof.
得られたガスバリア性塗工剤を、基材フィルムである延伸ポリエステルフィルム（東洋紡（株）製：Ｅ５１００、厚さ１２μｍ）のコロナ処理面に、乾燥後の厚みが１μｍになるようにメイヤーバーで塗工した。その後、１００℃の条件下、熱風乾燥機中で１分間、乾燥・熱処理を行い、ガスバリア性フィルムとした。得られたガスバリア性フィルムを用いて上記の試験を行った。その結果を表１に示す。 The obtained gas barrier coating agent is applied to a corona-treated surface of a stretched polyester film (Toyobo Co., Ltd .: E5100, thickness 12 μm) as a base film with a Meyer bar so that the thickness after drying becomes 1 μm. Coated. Thereafter, drying and heat treatment were performed for 1 minute in a hot air drier at 100 ° C. to obtain a gas barrier film. Said test was done using the obtained gas-barrier film. The results are shown in Table 1.
（比較例１）
アルカリ金属塩もアルカリ土類金属塩も添加しないこと以外は、実験例１と同様の手順により、ガスバリア性塗工剤を作製し、同様の手順により乾燥・熱処理した。その結果を表１に示す。
(Comparative Example 1)
A gas barrier coating agent was prepared by the same procedure as in Experimental Example 1 except that neither an alkali metal salt nor an alkaline earth metal salt was added, and was dried and heat-treated by the same procedure. The results are shown in Table 1.
（比較例２）
実験例１において、塩化ナトリウムの代わりにジメチルベンジルアミン０．２ｍｏｌ％を用いる以外は、実験例１と同様の手順により、ガスバリア性塗工剤を作製し、同様の手順により乾燥・熱処理した。その結果を表１に示す。
(Comparative Example 2)
In Experimental Example 1, a gas barrier coating agent was prepared by the same procedure as in Experimental Example 1 except that 0.2 mol% of dimethylbenzylamine was used instead of sodium chloride, and dried and heat-treated by the same procedure. The results are shown in Table 1.
（比較例３）
比較例２において、水溶性高分子であるＰＡＭの代わりにＰＶＡを用いる以外は、比較例２と同様の手順により、ガスバリア性塗工剤を作製し、同様の手順により乾燥・熱処理した。その結果を表１に示す。
(Comparative Example 3)
In Comparative Example 2, a gas barrier coating agent was prepared by the same procedure as Comparative Example 2, except that PVA was used instead of PAM, which is a water-soluble polymer, and dried and heat-treated by the same procedure. The results are shown in Table 1.
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| JP4808472B2 (en) * | 2005-11-09 | 2011-11-02 | 三井化学東セロ株式会社 | Gas barrier film, gas barrier laminate and method for producing the same |
| CN116097153A (en) * | 2020-09-14 | 2023-05-09 | 东丽株式会社 | Method for producing coated silicone member |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11256094A (en) * | 1998-03-10 | 1999-09-21 | Nippon Shokubai Co Ltd | Surface-treated resin molded item |
| JP2002138109A (en) * | 2000-07-28 | 2002-05-14 | Kuraray Co Ltd | Method of producing vinylalcoholic polymer composition |
| JP2003205582A (en) * | 2002-01-11 | 2003-07-22 | Rengo Co Ltd | Gas barrier film |
-
2003
- 2003-08-20 JP JP2003295827A patent/JP4573507B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11256094A (en) * | 1998-03-10 | 1999-09-21 | Nippon Shokubai Co Ltd | Surface-treated resin molded item |
| JP2002138109A (en) * | 2000-07-28 | 2002-05-14 | Kuraray Co Ltd | Method of producing vinylalcoholic polymer composition |
| JP2003205582A (en) * | 2002-01-11 | 2003-07-22 | Rengo Co Ltd | Gas barrier film |
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| JP2005060621A (en) | 2005-03-10 |
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