JP4996180B2 - Coating agent composition for vapor deposition film - Google Patents
Coating agent composition for vapor deposition film Download PDFInfo
- Publication number
- JP4996180B2 JP4996180B2 JP2006237296A JP2006237296A JP4996180B2 JP 4996180 B2 JP4996180 B2 JP 4996180B2 JP 2006237296 A JP2006237296 A JP 2006237296A JP 2006237296 A JP2006237296 A JP 2006237296A JP 4996180 B2 JP4996180 B2 JP 4996180B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- agent
- vapor
- containing acrylic
- coating
- 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.)
- Active
Links
- 239000011248 coating agent Substances 0.000 title claims description 59
- 239000000203 mixture Substances 0.000 title claims description 28
- 238000007740 vapor deposition Methods 0.000 title claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- 229920000178 Acrylic resin Polymers 0.000 claims description 38
- 239000004925 Acrylic resin Substances 0.000 claims description 38
- 125000002560 nitrile group Chemical group 0.000 claims description 36
- 230000004888 barrier function Effects 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 26
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000012948 isocyanate Substances 0.000 claims description 15
- -1 isocyanate compound Chemical class 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 12
- 239000008199 coating composition Substances 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 239000005001 laminate film Substances 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 239000007789 gas Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010410 layer Substances 0.000 description 13
- 239000005022 packaging material Substances 0.000 description 12
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 8
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 238000007756 gravure coating Methods 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 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
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 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
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-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
- 229920006284 nylon film Polymers 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Description
本発明は、蒸着フィルム用コート剤組成物に関し、詳細にはコート剤がガスバリヤー性をもつことにより、蒸着フィルムの蒸着層を保護するだけでなく、さらに良好なガスバリヤー性フィルム用コート剤に使用する蒸着フィルム用コート剤組成物に関する。 The present invention relates to a coating composition for a vapor deposition film, and in particular, the coating agent has a gas barrier property, so that not only the vapor deposition layer of the vapor deposition film is protected but also a better coating agent for a gas barrier film. It is related with the coating agent composition for vapor deposition films to be used.
透明蒸着フィルムは、シリカやアルミナの蒸気を付着させたもので、酸素ガス遮断性に優れ、防湿性、耐熱性も良くレトルトにも対応し、電子レンジにも使用できる資材である。しかしながら、歪みや屈曲により蒸着被膜にひび割れを起こしやすくバリヤー性が低下しやすい。フィルム加工中、過度のテンションをかけたり、印刷時の白インキ中の酸化チタンなどとの擦れによってバリヤー劣化を引き起こす。そのため、ポリビニルアルコール樹脂、エチレン−ビニルアルコール樹脂などのバリヤー性のある樹脂やポリエステル樹脂、ウレタン樹脂、ポリエステル樹脂、塩ビ・酢ビ共重合体、アクリル樹脂などを蒸着層の上に塗工し、蒸着層を印刷時やラミネート時などのフィルム加工時のフィルムの歪みや圧力などから保護する手法が用いられている。 The transparent vapor-deposited film is a material to which silica or alumina vapor is attached, is excellent in oxygen gas barrier properties, has good moisture resistance and heat resistance, is compatible with retort, and can be used in a microwave oven. However, the deposited film tends to crack due to distortion or bending, and the barrier property tends to be lowered. Barrier deterioration is caused by applying excessive tension during film processing or rubbing with titanium oxide in white ink during printing. Therefore, barrier resin such as polyvinyl alcohol resin and ethylene-vinyl alcohol resin, polyester resin, urethane resin, polyester resin, vinyl chloride / vinyl acetate copolymer, acrylic resin, etc. are coated on the vapor deposition layer and vapor deposition is performed. A technique for protecting a layer from film distortion or pressure during film processing such as printing or laminating is used.
ポリビニルアルコールやエチレン−ビニルアルコール樹脂などのポリアルコール樹脂系などのバリヤー性樹脂は保護機能とともにさらなるバリヤー性向上効果を得ることができる。しかし、水溶性であり、乾燥性に難があり、塗工適性が良くない。また、耐水性に乏しく、耐ボイル性や耐レトルト性に難がある。 A barrier resin such as a polyalcohol resin such as polyvinyl alcohol or ethylene-vinyl alcohol resin can provide a further barrier property improving effect as well as a protective function. However, it is water-soluble, has difficulty in drying, and has poor coating suitability. In addition, the water resistance is poor, and the boil resistance and retort resistance are difficult.
一方、ポリエステル樹脂、ウレタン樹脂、ポリエステル樹脂、塩ビ・酢ビ共重合体、アクリル樹脂などの油性樹脂は乾燥性に優位性があり、塗工は比較的容易である。さらには蒸着膜の上に塗工することにより、蒸着層を保護する機能を付与することができる。しかし、これらの樹脂はバリヤー性に乏しく、保護膜として使用した場合、ガスバリヤー性向上効果はない。
例えば、特許文献１には、ポリウレタン系樹脂とポリエステル系樹脂と接着強化剤とを有機溶媒中に含有するコーティング液が、特許文献２には、特定のポリエステル樹脂を含有するコーティング液が開示されている。これらの方法により、蒸着層面を保護しガスバリヤー性を維持することが可能となっている。
On the other hand, oil-based resins such as polyester resins, urethane resins, polyester resins, vinyl chloride / vinyl acetate copolymers, and acrylic resins have superior drying properties and are relatively easy to apply. Furthermore, the function which protects a vapor deposition layer can be provided by coating on a vapor deposition film. However, these resins are poor in barrier properties, and when used as a protective film, there is no effect of improving gas barrier properties.
For example, Patent Document 1 discloses a coating liquid containing a polyurethane resin, a polyester resin, and an adhesion enhancer in an organic solvent, and Patent Document 2 discloses a coating liquid containing a specific polyester resin. Yes. By these methods, it is possible to protect the vapor deposition layer surface and maintain gas barrier properties.
本発明の目的は、透明蒸着フィルムの蒸着面にコート剤を塗工することにより、蒸着層面を保護し、かつ、コート剤にもガスバリヤー性をもたせることにより更にガスバリヤー性を向上させ、耐水性にも優れたコート剤組成物を提供することである。 The object of the present invention is to protect the vapor deposition layer surface by applying a coating agent to the vapor deposition surface of the transparent vapor deposition film, and to further improve the gas barrier property by providing the coating agent with a gas barrier property. It is providing the coating agent composition excellent also in the property.
上記の課題を達成する本発明に係わる蒸着無機酸化物フィルム用コート剤組成物は、
（１）蒸着無機酸化物フィルムのガスバリヤー性を保護し向上させるための主剤と硬化剤とからなる２液混合型コート剤であって、主剤は、ニトリル基含有アクリル樹脂（Ａ）とシランカップリング剤（Ｂ）とを主たる構成成分としてなり、前記ニトリル基含有アクリル樹脂（Ａ）が、（Ａ）を構成するモノマーとして、ニトリル基含有アクリルモノマーと水酸基含有アクリルモノマーとを必須とし、該ニトリル基含有アクリルモノマーは（Ａ）中に３〜７０質量％で構成され、（Ａ）の水酸基価は２０〜２００ｍｇＫＯＨ／ｇであり、
硬化剤が、イソシアネート化合物（Ｃ）を主たる構成成分とすることを特徴とする蒸着無機酸化物フィルム用コート剤組成物、
（２）さらに、ニトリル基含有アクリル樹脂（Ａ）の重量平均分子量が１０，０００〜１００，０００であることを特徴とする上記（１）記載の蒸着無機酸化物フィルム用コート剤組成物、
（３）ニトリル基含有アクリル樹脂（Ａ）のガラス転移点（Ｔｇ）が５０〜２００℃であることを特徴とする上記（１）または（２）に記載の蒸着無機酸化物フィルム用コート剤組成物、
（４）主剤中ニトリル基含有アクリル樹脂（Ａ）のＯＨ基と硬化剤中のＮＣＯ基の比率が［ＮＣＯ］／［ＯＨ］＝０．３〜３．０であることを特徴とする上記（１）〜（３）の何れかに記載の蒸着無機酸化物フィルム用コート剤組成物、
（５）シランカップリング剤（Ｂ）が、イソシアネート基、アミノ基、エポキシ基、メルカプト基から選ばれる有機官能基を少なくとも１種を含有していることを特徴とする上記（１）〜（４）の何れかに記載の蒸着無機酸化物フィルム用コート剤組成物、
（６）ニトリル基含有アクリル樹脂（Ａ）のガラス転移点（Ｔｇ）が５０〜２００℃であることを特徴とする上記（１）〜（５）の何れかに記載の蒸着無機酸化物フィルム用コート剤組成物、
（７）主剤中のニトリル基含有アクリル樹脂（Ａ）とシランカップリング剤（Ｂ）との質量比が、（Ａ）／（Ｂ）＝１００／３〜１００／８０であることを特徴とする上記（１）〜（６）の何れかに記載の蒸着無機酸化物フィルム用コート剤組成物、
（８）上記（１）〜（７）の何れかに記載の蒸着無機酸化物フィルム用コート剤組成物を蒸着無機酸化物フィルムの蒸着層面に塗工したことを特徴とするガスバリヤー性積層フィルム、である。
The coating composition for a vapor-deposited inorganic oxide film according to the present invention that achieves the above-described problems is as follows.
(1) A two-component mixed coating agent comprising a main agent and a curing agent for protecting and improving the gas barrier properties of a vapor-deposited inorganic oxide film, the main agents being a nitrile group-containing acrylic resin (A) and a silane cup The nitrile group-containing acrylic resin (A) is essentially composed of a nitrile group-containing acrylic monomer and a hydroxyl group-containing acrylic monomer as a monomer constituting the ring component (B). The group-containing acrylic monomer is composed of 3 to 70% by mass in (A), the hydroxyl value of (A) is 20 to 200 mgKOH / g,
A coating agent composition for a vapor-deposited inorganic oxide film, wherein the curing agent comprises an isocyanate compound (C) as a main constituent;
(2) Furthermore, the weight average molecular weight of the nitrile group-containing acrylic resin (A) is 10,000 to 100,000, The coating composition for vapor-deposited inorganic oxide film according to (1) above,
(3) The glass transition point (Tg) of the nitrile group-containing acrylic resin (A) is 50 to 200 ° C. The coating composition for a vapor-deposited inorganic oxide film as described in (1) or (2) above object,
(4) The above characterized in that the ratio of the OH group of the nitrile group-containing acrylic resin (A) in the main agent to the NCO group in the curing agent is [NCO] / [OH] = 0.3 to 3.0 ( 1) -Coating agent composition for vapor deposition inorganic oxide film in any one of (3),
(5) The above (1) to (4), wherein the silane coupling agent (B) contains at least one organic functional group selected from an isocyanate group, an amino group, an epoxy group, and a mercapto group. ) The coating agent composition for vapor-deposited inorganic oxide film according to any one of
(6) The glass transition point (Tg) of the nitrile group-containing acrylic resin (A) is 50 to 200 ° C. The vapor-deposited inorganic oxide film according to any one of (1) to (5) above Coating agent composition,
(7) The mass ratio of the nitrile group-containing acrylic resin (A) and the silane coupling agent (B) in the main agent is (A) / (B) = 100/3 to 100/80. The coating agent composition for vapor-deposited inorganic oxide film according to any one of (1) to (6) above,
(8) A gas barrier laminate film, characterized in that the coating composition for a vapor-deposited inorganic oxide film according to any one of (1) to (7) above is applied to the vapor-deposited layer surface of the vapor-deposited inorganic oxide film. , it is.
本発明によれば、上記のコート剤組成物を透明蒸着フィルムの蒸着面にコートすることにより、その透明性を損なうことなく、蒸着層を保護してガスバリヤー性の劣化を防止し、コート層のガスバリヤー性により更にガスバリヤー性が向上した積層フィルムを得ることができるコート剤組成物が提供される。 According to the present invention, by coating the above-described coating agent composition on the vapor deposition surface of the transparent vapor deposition film, the vapor deposition layer is protected without impairing its transparency, and the deterioration of the gas barrier property is prevented. A coating agent composition capable of obtaining a laminated film having further improved gas barrier properties due to the gas barrier properties is provided.
発明を実施するための最良の形態を挙げて本発明をさらに詳しく説明する。 The present invention will be described in more detail with reference to the best mode for carrying out the invention.
本発明で使用するニトリル基含有アクリル樹脂を構成するニトリル基含有モノマーとして、アクリロニトリル、メタクリロニトリル等が挙げられる。また、当該ニトリル基含有アクリル樹脂を構成する他のモノマーとしては必須成分である水酸基含有モノマーの他、中性モノマー、カルボキシル基含有モノマー、エポキシ基含有モノマー、および含窒素モノマー等が挙げられる。本発明で使用するニトリル基含有アクリル樹脂はこれらから選択されたモノマーの組み合わせで合成される。水酸基含有モノマーとしては、メタクリル酸２−ヒドロキシエチル、メタクリル酸ヒドロキシプロピル、アクリル酸２−ヒドロキシエチル、アクリル酸ヒドロキシプロピルなどが挙げられる。中性モノマーとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ｎ−ヘキシル、メタクリル酸ラウリル、スチレン、ビニルトルエン、酢酸ビニルなどが挙げられる。カルボキシル基含有モノマーとしては、アクリル酸、メタクリル酸、マレイン酸、イタコン酸などが挙げられる。エポキシ基含有モノマーとしては、アクリル酸グリシジル、メタクリル酸グリシジルなどが挙げられる。含窒素モノマーとしては、アクリルアミド、Ｎ−メチロールアクリルアミド、ジアセトンアクリルアミド、メタクリル酸ジメチルアミノエチルなどが挙げられる。 Examples of the nitrile group-containing monomer constituting the nitrile group-containing acrylic resin used in the present invention include acrylonitrile and methacrylonitrile. In addition to the hydroxyl group-containing monomer, which is an essential component, other monomers that constitute the nitrile group-containing acrylic resin include neutral monomers, carboxyl group-containing monomers, epoxy group-containing monomers, and nitrogen-containing monomers. The nitrile group-containing acrylic resin used in the present invention is synthesized with a combination of monomers selected from these. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, and hydroxypropyl acrylate. Neutral monomers include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid Examples include isobutyl, n-hexyl methacrylate, lauryl methacrylate, styrene, vinyl toluene, and vinyl acetate. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, and itaconic acid. Examples of the epoxy group-containing monomer include glycidyl acrylate and glycidyl methacrylate. Examples of the nitrogen-containing monomer include acrylamide, N-methylol acrylamide, diacetone acrylamide, and dimethylaminoethyl methacrylate.
アクリル樹脂中の官能基としてはカルボキシル基、水酸基、エポキシ基、アミノ基等が挙げられ、硬化剤中のイソシアネート化合物と反応せしめることにより、レトルト殺菌等に耐えうる耐熱性、耐油性に優れる皮膜を形成させる。中でも反応速度のコントロールの容易さから水酸基が好適に用いられる。 Examples of the functional group in the acrylic resin include a carboxyl group, a hydroxyl group, an epoxy group, and an amino group. By reacting with an isocyanate compound in the curing agent, a film excellent in heat resistance and oil resistance that can withstand retort sterilization, etc. Let it form. Among these, a hydroxyl group is preferably used because of easy control of the reaction rate.
本発明のニトリル基含有アクリル樹脂の合成は公知のラジカル重合開始剤を用いた溶液法で製造することができる。ラジカル開始剤としてはアゾビスイソブチロニトリル、アゾビス−２−メチルブチロニトリル等のアゾ系開始剤、クメンヒドロペルオキシド、ジ−ｔ−ブチルペルオキシド、過酸化ベンゾイル等の過酸化物系開始剤、過硫酸アンモニウムなどの過硫酸系開始剤などが好適に用いられ、特に限定されるものではない。 The synthesis of the nitrile group-containing acrylic resin of the present invention can be produced by a solution method using a known radical polymerization initiator. As radical initiators, azo initiators such as azobisisobutyronitrile, azobis-2-methylbutyronitrile, peroxide initiators such as cumene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, A persulfate-based initiator such as ammonium persulfate is preferably used and is not particularly limited.
ニトリル基含有アクリル樹脂の重量平均分子量は１０，０００以下では塗工した後にブロッキングしやすくなる。１００，０００以上では硬化剤との相溶性が不良となる。そのため、１０，０００〜１００，０００が好ましく、特に２０，０００〜７０，０００が好ましい。 When the weight average molecular weight of the nitrile group-containing acrylic resin is 10,000 or less, blocking tends to occur after coating. If it is 100,000 or more, the compatibility with the curing agent becomes poor. Therefore, 10,000 to 100,000 is preferable, and 20,000 to 70,000 is particularly preferable.
ニトリル基含有アクリル樹脂のガラス転移点（Ｔｇ）は５０℃以下であると、ブロッキングしやすくなり、２００℃以上ではニトリル基含有アクリル樹脂の分子運動が少なく、アクリルの官能基とイソシアネート化合物との反応速度が遅くなり、硬化不良となりやすい。そのため、５０〜２００℃の範囲が好ましく、特に７０〜１５０℃の範囲が好適に用いられる。 When the glass transition point (Tg) of the nitrile group-containing acrylic resin is 50 ° C. or lower, blocking tends to occur, and at 200 ° C. or higher, the molecular motion of the nitrile group-containing acrylic resin is small, and the reaction between the acrylic functional group and the isocyanate compound. The speed is slow, and poor curing is likely. Therefore, the range of 50-200 degreeC is preferable, and the range of 70-150 degreeC is used suitably especially.
ニトリル基含有アクリル樹脂は、原料としてニトリル基含有モノマーを合成時の配合組成中３質量％以下ではガスバリヤー性向上効果が発現せず、また、７０質量％以上では樹脂の凝集力が強くなり、合成および溶液化が困難となる。そのため、ニトリル基含有アクリル樹脂は、原料としてニトリル基含有モノマーを合成時の配合組成中に３〜７０質量％の範囲が好ましく、特に５〜６０質量％の範囲が好適に用いられる。 The nitrile group-containing acrylic resin does not exhibit a gas barrier property improving effect at 3% by mass or less in the composition of the nitrile group-containing monomer as a raw material, and the cohesive strength of the resin is strong at 70% by mass or more. Synthesis and solution are difficult. Therefore, the nitrile group-containing acrylic resin preferably has a range of 3 to 70% by mass, and particularly preferably a range of 5 to 60% by mass in the composition of the nitrile group-containing monomer as a raw material.
ニトリル基含有アクリル樹脂の水酸基価は２０ｍｇＫＯＨ／ｇ以下であると、イソシアネート化合物との反応性に乏しく、レトルトに耐えうるコート層を得ることができない。２００ｍｇＫＯＨ／ｇ以上であると、対応する硬化剤量も増加し、ブロッキングの問題及びコストの問題があり、好ましくない。そのため、水酸基価は２０〜２００ｍｇＫＯＨ／ｇの範囲が好ましく、特に３０〜１５０ｍｇＫＯＨ／ｇの範囲が好適に用いられる。 When the hydroxyl value of the nitrile group-containing acrylic resin is 20 mgKOH / g or less, the reactivity with the isocyanate compound is poor, and a coat layer that can withstand retort cannot be obtained. When it is 200 mgKOH / g or more, the amount of the corresponding curing agent increases, and there are problems of blocking and cost, which is not preferable. Therefore, the hydroxyl value is preferably in the range of 20 to 200 mgKOH / g, and particularly preferably in the range of 30 to 150 mgKOH / g.
本発明で使用するシランカップリング剤は、無機物と反応する加水分解基と有機物と相溶し易くする官能基を一分子中にもつ有機ケイ素化合物である。加水分解基はメトキシ基、エトキシ基、などが挙げられる。また、有機物と相溶し易くする官能基はビニル基、エポキシ基、アミノ基、メタクリロキシ基、メルカプト基、イソシアネート基などが挙げられる。また、これらと官能基をもたないメチル基、フェニル基、さらには全て加水分解基であるアルコキシシランを混合しても問題はない。また、これらの官能基含有カップリング剤は１種類または２種類以上の混合物であっても良い。 The silane coupling agent used in the present invention is an organosilicon compound having a hydrolyzable group that reacts with an inorganic substance and a functional group that facilitates compatibility with an organic substance in one molecule. Examples of the hydrolyzable group include a methoxy group and an ethoxy group. Examples of functional groups that are easily compatible with organic substances include vinyl groups, epoxy groups, amino groups, methacryloxy groups, mercapto groups, and isocyanate groups. Moreover, there is no problem even if these are mixed with a methyl group having no functional group, a phenyl group, or an alkoxysilane which is a hydrolyzable group. These functional group-containing coupling agents may be one kind or a mixture of two or more kinds.
また、シランカップリング剤は有機官能基がアクリルポリオールもしくはイソシアネート化合物と反応または相溶し、加水分解基がシラノール基を形成し、シリカもしくはアルミナと強固な密着性を示し、その結果フィルムとシリカもしくはアルミナの密着性が向上する。有機官能基を有するカップリング剤として、Ｎ−２（アミノエチル）３−アミノプロピルメチルジメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランなどのアミノ基含有カップリング剤、２−（３，４エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシランなどのエポキシ基含有カップリング剤、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシランなどのメルカプト基含有カップリング剤、３−イソシアネートプロピルトリエトキシシラン、３−イソシアネートプロピルトリメトキシシランなどのイソシアネート基含有カップリング剤等が挙げられる。 In addition, the silane coupling agent has an organic functional group that reacts or is compatible with an acrylic polyol or an isocyanate compound, a hydrolyzable group forms a silanol group, and exhibits strong adhesion to silica or alumina. The adhesiveness of alumina is improved. As a coupling agent having an organic functional group, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-amino Amino group-containing coupling agents such as propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 2- (3,4 epoxycyclohexyl) Epoxy group-containing coupling agents such as ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropylmethyldimethoxy Silane, 3- Mercapto group-containing coupling agents such as Le mercaptopropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. isocyanate group-containing coupling agents such as 3-isocyanate propyl trimethoxysilane.
主剤中のシランカップリング剤は有機官能基としてイソシアネート基、アミノ基、エポキシ基、メルカプト基を少なくとも１個含有することが好ましく、この有機官能基がアクリル樹脂やイソシアネート化合物と反応、相溶作用を示す。また、加水分解成分は蒸着フィルムの蒸着層との密着性向上に寄与する The silane coupling agent in the main agent preferably contains at least one isocyanate group, amino group, epoxy group, or mercapto group as an organic functional group. This organic functional group reacts with an acrylic resin or an isocyanate compound and has a compatible action. Show. In addition, the hydrolysis component contributes to improving the adhesion of the deposited film to the deposited layer.
アクリル樹脂に対するシランカップリング剤添加量は質量比において、１００／３よりシランカップリング剤が少ないと、蒸着層の保持力が十分でない。１００／８０より多いと、ブロッキングの問題が発現し、コスト的にも不利となる。そのため、１００／３〜１００／８０が好ましく、特に１００／５〜１００／５０の範囲が好ましい When the amount of the silane coupling agent added to the acrylic resin is less than 100/3 in terms of mass ratio, the deposition layer does not have sufficient holding power. When the ratio is more than 100/80, the problem of blocking appears, which is disadvantageous in terms of cost. Therefore, 100/3 to 100/80 is preferable, and the range of 100/5 to 100/50 is particularly preferable.
本発明では硬化剤として、イソシアネート化合物を使用する。本発明に使用するイソシアネート化合物は、トリレンジイソシアネート、４４’−ジフェニルメタンジイソシアネート等の芳香族系ジイソシアネートモノマー、キシリレンジイソシアネート、ヘキサメチレンジイソシアネート等の脂肪族系ジイソシアネートモノマー、イソホロンジイソシアネート等の脂環族系ジイソシアネートモノマーもしくはこれらの重合体、誘導体またはこれらの混合物が挙げられる。硬化剤には、イソシアネート化合物を流動性・貯蔵安定性の観点で取扱い易くするため、溶剤を添加することができる。主剤の各成分と相溶性良い溶剤が選択できる。 In the present invention, an isocyanate compound is used as a curing agent. Isocyanate compounds used in the present invention are aromatic diisocyanate monomers such as tolylene diisocyanate and 44'-diphenylmethane diisocyanate, aliphatic diisocyanate monomers such as xylylene diisocyanate and hexamethylene diisocyanate, and alicyclic diisocyanates such as isophorone diisocyanate. Monomers or their polymers, derivatives, or mixtures thereof. In order to make the isocyanate compound easy to handle from the viewpoint of fluidity and storage stability, a solvent can be added to the curing agent. A solvent having good compatibility with each component of the main agent can be selected.
本発明の蒸着フィルム用コート剤組成物は、有機溶剤に均一に溶解分散した溶液として使用することができる。 The coating composition for a vapor deposition film of the present invention can be used as a solution that is uniformly dissolved and dispersed in an organic solvent.
主剤中の溶剤組成はコート剤の塗工時の流動性を保ち、コート層の平滑性を得るよう決定される。主剤中に使用される溶剤はメタノール、エタノール、イソプロピルアルコール、ノルマルプロピルアルコール、イソブチルアルコール、ノルマルブチルアルコールなどのアルコール系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、アノンなどのケトン系溶剤、酢酸エチル、酢酸ｎ−プロピル、酢酸ｎ−ブチル、酢酸イソブチルなどのエステル系溶剤、ブチルセルソルブ、プロピレングリコールモノメチルエーテルなどのグリコール系溶剤、トルエン、キシレン、ノルマルヘキサン、メチルシクロヘキサンなどの炭化水素系溶剤、などが好適に用いられる。 The solvent composition in the main agent is determined so as to maintain the fluidity when the coating agent is applied and to obtain the smoothness of the coating layer. Solvents used in the main agent are alcohol solvents such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, isobutyl alcohol and normal butyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and anone, ethyl acetate, acetic acid Preferred are ester solvents such as n-propyl, n-butyl acetate and isobutyl acetate, glycol solvents such as butyl cellosolve and propylene glycol monomethyl ether, and hydrocarbon solvents such as toluene, xylene, normal hexane and methylcyclohexane. Used for.
主剤と硬化剤との混合割合は、主剤中ニトリル基含有アクリル樹脂のＯＨ基と硬化剤中イソシアネートのＮＣＯ基との比率により決められる。ニトリル基含有アクリル樹脂のＯＨ基とイソシアネートのＮＣＯ基の比率は［ＮＣＯ］／［ＯＨ］＝０．３〜３．０とすることが好ましく、特に０．５〜２．５であることが好適である。０．３より低いと、アクリル樹脂中の水酸基と反応するイソシアネートが不足し、硬化不良となり、レトルト時にラミネート不良（浮き）が発生する。また、２．５より高いとブロッキングの問題が発生する。 The mixing ratio of the main agent and the curing agent is determined by the ratio of the OH group of the nitrile group-containing acrylic resin in the main agent to the NCO group of the isocyanate in the curing agent. The ratio of the OH group of the nitrile group-containing acrylic resin to the NCO group of the isocyanate is preferably [NCO] / [OH] = 0.3 to 3.0, particularly preferably 0.5 to 2.5. It is. If it is lower than 0.3, the isocyanate that reacts with the hydroxyl group in the acrylic resin is insufficient, resulting in poor curing, resulting in poor lamination (floating) during retorting. On the other hand, if it is higher than 2.5, a blocking problem occurs.
本発明に使用される透明蒸着フィルムは、ガスバリヤー層を形成する蒸着膜が無機酸化物であり、酸化アルミニウム、酸化ケイ素、酸化マグネシウム、酸化スズあるいはこれらの混合物であり、透明性、酸素や水蒸気などのガスバリヤー性を有するものであれば良い。なかでも、コスト的にも耐性においても酸化アルミニウムや酸化ケイ素もしくはこれらの混合物が好ましい。また、蒸着層の厚みは１０〜３００ｎｍの範囲が好ましい。 In the transparent vapor-deposited film used in the present invention, the vapor-deposited film forming the gas barrier layer is an inorganic oxide, and is an aluminum oxide, silicon oxide, magnesium oxide, tin oxide or a mixture thereof. Any gas barrier property may be used. Of these, aluminum oxide, silicon oxide or a mixture thereof is preferable in terms of cost and resistance. Moreover, the thickness of a vapor deposition layer has the preferable range of 10-300 nm.
塗工方法は公知の方法で良いが、グラビア塗工が膜厚の調整などが容易で好適である。コート層の厚みは特に限定されないが、０．０５μｍ（乾燥厚さ）より薄いと均一な塗膜が得られにくく、コート層が均一な厚さになり難く、バリヤー性が低下する場合があり、好ましくない。また、２μｍより厚いとコスト的な問題及びブロッキングを起こしやすくなる問題がある。乾燥状態で、厚さ０．０５〜２μｍの範囲が好ましく、特に０．１〜１μの範囲が好ましい。 The coating method may be a known method, but gravure coating is preferable because the adjustment of the film thickness is easy. The thickness of the coating layer is not particularly limited, but if it is less than 0.05 μm (dry thickness), it is difficult to obtain a uniform coating film, the coating layer is difficult to have a uniform thickness, and the barrier property may be lowered. It is not preferable. On the other hand, if it is thicker than 2 μm, there are problems of cost and blocking. In the dry state, the thickness is preferably in the range of 0.05 to 2 μm, particularly preferably in the range of 0.1 to 1 μm.
コート剤塗工後、加熱エージングすることにより、コート層を安定かつ短時間で硬化皮膜とすることができる。３０℃より低いとアクリル樹脂中の水酸基と硬化剤中のイソシアネート基の反応が不安定で、硬化不良となることがある。１００℃以上でエージングするとブロッキングを起こしやすくなる問題がある。エージング条件はアクリル樹脂のＴｇにもよるが、３０〜１００℃が好ましい。特に、４０〜７０℃の範囲が好ましい。また、エージングの時間は少なくとも１２時間以上行うことが好ましく、特に２４時間以上が好適である。 By applying heat aging after coating the coating agent, the coating layer can be formed into a cured film stably and in a short time. If it is lower than 30 ° C., the reaction between the hydroxyl group in the acrylic resin and the isocyanate group in the curing agent may be unstable, resulting in poor curing. When aging is performed at 100 ° C. or higher, there is a problem that blocking tends to occur. Aging conditions depend on Tg of the acrylic resin, but are preferably 30 to 100 ° C. The range of 40-70 degreeC is especially preferable. The aging time is preferably at least 12 hours or more, and particularly preferably 24 hours or more.
上記のコート剤が塗工された蒸着フィルムのコート層面に、公知の方法により包装材料に適したドライラミネート用接着剤を塗布し他のプラスチックフィルムをラミネート加工する、または、オレフィン系ポリマーを押出加工して積層フィルムとすることができる。 Apply a dry laminating adhesive suitable for packaging materials to the coating layer surface of the vapor-deposited film coated with the above coating agent to laminate other plastic films, or extrude olefin polymers. Thus, a laminated film can be obtained.
上記の積層フィルムは、ガスバリヤー性に優れたフィルム資材として使用でき、特にレトルト用包装資材に好適である。 The above laminated film can be used as a film material having excellent gas barrier properties, and is particularly suitable as a packaging material for retort.
次に、本発明の蒸着フィルム用コート剤組成物について、具体的に述べる。なお、文中の「部」および「％」とあるのは質量基準である。本発明は下記の実施例に限定されるものではない。 Next, the coating agent composition for a vapor deposition film of the present invention will be specifically described. In the text, “part” and “%” are based on mass. The present invention is not limited to the following examples.
（ニトリル基含有アクリル樹脂の調製）
還流冷却管、窒素導入管、温度計、攪拌機を備えた反応容器に酢酸エチル１５０部、ＭＥＫ１００部を仕込み９０℃となるまで加温して保持する。メタクリル酸メチル１９５部、メタクリル酸２−ヒドロキシエチル６０部、アクリロニトリル４５部の混合溶液中に、重合開始剤として、ベンゾイルパーオキサイドを４．５部入れ撹拌し、この混合液を先の酢酸エチルとＭＥＫ混合溶媒へ９０℃にて均一に２時間掛けて撹拌しながら滴下し、さらに１時間保持する。
(Preparation of nitrile group-containing acrylic resin)
In a reaction vessel equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 150 parts of ethyl acetate and 100 parts of MEK are charged and heated to 90 ° C. and held. In a mixed solution of 195 parts of methyl methacrylate, 60 parts of 2-hydroxyethyl methacrylate, and 45 parts of acrylonitrile, 4.5 parts of benzoyl peroxide as a polymerization initiator was added and stirred, and this mixture was mixed with the above ethyl acetate. The mixture is added dropwise to the MEK mixed solvent at 90 ° C. with stirring over 2 hours, and the mixture is further maintained for 1 hour.
（主剤の調製）
その後、前記ニトリル基含有アクリル樹脂溶液にベンゾイルパーオキサイド１．５部を酢酸エチル１２０部に溶解した開始剤溶液を９０℃にて３時間掛けて均一に滴下した後、さらに２時間保持後７０℃まで冷却し、酢酸ｎ−プロピル、トルエン、イソプロピルアルコール、ＭＥＫをそれぞれ９００部、９００部、２００部、３００部、次いで１５部の３−イソシアネートプロピルトリエトキシシラン、１５部のＮ−２（アミノエチル）３−アミノプロピルメチルジメトキシシランを添加して均一となるように撹拌して、本発明のコート剤の主剤を調製した。
(Preparation of main agent)
Thereafter, an initiator solution in which 1.5 parts of benzoyl peroxide was dissolved in 120 parts of ethyl acetate in the nitrile group-containing acrylic resin solution was uniformly added dropwise at 90 ° C. over 3 hours, and then maintained for 2 hours and then 70 ° C. To 900 parts, 900 parts, 200 parts, 300 parts, then 15 parts of 3-isocyanatopropyltriethoxysilane, 15 parts of N-2 (aminoethyl). ) 3-Aminopropylmethyldimethoxysilane was added and stirred uniformly to prepare the main agent of the coating agent of the present invention.
得られた主剤は固形分１０％、重量平均分子量３５，０００（昭和電工社製ＳＨＯＤＥＸ ＫＦ−８０ＭによりＧＰＣ法で測定）、水酸基価８６ｍｇＫＯＨ／ｇ（ＪＩＳ Ｋ００７０）、Ｔｇ９４℃（ＪＩＳ Ｋ７１２１）、ニトリル含有量１５％（計算値）であった。 The obtained main agent has a solid content of 10%, a weight average molecular weight of 35,000 (measured by GPC method using SHODEX KF-80M manufactured by Showa Denko KK), a hydroxyl value of 86 mgKOH / g (JIS K0070), Tg94 ° C. (JIS K7121), and nitrile. The content was 15% (calculated value).
（コート剤組成物の作製）
硬化剤として、ヘキサメチレンジイソシアネート３量体の固形分７５％酢酸エチル溶液（日本ポリウレタン工業社製：商品名コロネートＨＬ）を用い、前記主剤１００部に対して硬化剤３．３部を添加混合して本発明のコート剤１を作製した。
(Preparation of coating agent composition)
As a curing agent, a solid content 75% ethyl acetate solution of hexamethylene diisocyanate trimer (manufactured by Nippon Polyurethane Industry Co., Ltd .: trade name Coronate HL) was used, and 3.3 parts of the curing agent was added and mixed with 100 parts of the main agent. Thus, the coating agent 1 of the present invention was produced.
（実施例１）
アルミナ蒸着ＰＥＴであるＴＬ−ＰＥＴ Ｈ（東セロ社製）に本発明のコート剤１を厚さ０．３μｍとなるようにグラビア塗工し、５０℃にて２４時間エージングして、蒸着膜を保護したフィルムを得た。これにレトルト用接着剤タケラック（商標）Ａ−５２５／タケネート（商標）Ａ−５２（三井化学ポリウレタン社製）で両面処理ナイロンフィルムをドライラミネート法により、貼り合わせ、さらにレトルト用未延伸ポリプロピレンフィルムをドライラミネート法により張り合わせ、レトルト用ラミネート物を得た。また、このラミネート物を用い、熱溶融により製袋し、レトルト用包材を作製した。
Example 1
The coating agent 1 of the present invention is gravure-coated to a thickness of 0.3 μm on TL-PET H (manufactured by Tosero), which is an alumina-deposited PET, and aged at 50 ° C. for 24 hours to protect the deposited film. Film was obtained. To this, a double-sided nylon film was bonded by a dry laminating method with a retort adhesive Takelac (trademark) A-525 / Takenate (trademark) A-52 (manufactured by Mitsui Chemicals Polyurethanes), and an unstretched polypropylene film for retort was further bonded. Lamination was performed by a dry laminating method to obtain a laminate for retort. In addition, this laminate was used to form a bag by heat melting to produce a retort packaging material.
（実施例２）
アルミナ蒸着ＰＥＴであるファインバリヤー（商標）Ａ（麗光社製）に本発明のコート剤１を厚さ０．３μｍとなるようにグラビア塗工し、５０℃にて２４時間エージングして、蒸着膜を保護したフィルムを得た。これにノンボイル用接着剤タケラックＡ−９６９Ｖ／タケネートＡ−５（三井化学ポリウレタン社製）で未延伸ポリプロピレンフィルムをドライラミネート法により、貼り合わせ、ノンボイル用ラミネート物を得た。また、このラミネート物を用い、熱溶融により製袋し、ノンボイル用包材を作製した。
(Example 2)
The coating agent 1 of the present invention is applied to fine barrier (trademark) A (made by Reiko Co., Ltd.), an alumina-deposited PET, with a gravure coating to a thickness of 0.3 μm, and aged for 24 hours at 50 ° C. A film with the membrane protected was obtained. Non-boiled adhesive Takelac A-969V / Takenate A-5 (manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was bonded to the unstretched polypropylene film by a dry laminating method to obtain a non-boiled laminate. In addition, this laminate was used to make a bag by heat melting to produce a non-boiled packaging material.
（比較例１）
本発明のコート剤を塗工しない以外は実施例１と同様に、レトルト用包材を作製した。
(Comparative Example 1)
A packaging material for retort was produced in the same manner as in Example 1 except that the coating agent of the present invention was not applied.
（比較例２）
本発明のコート剤を塗工しない以外は実施例２と同様に、ノンボイル用包材を作製した。
(Comparative Example 2)
A non-boil packaging material was prepared in the same manner as in Example 2 except that the coating agent of the present invention was not applied.
（比較例３）
完全けん化ポリビニルアルコール樹脂（けん化度９９％以上）を水に溶解させた後、これをコート剤として、実施例１と同様にグラビア塗工したが、乾燥不良によりブロッキングしたので、塗工速度を落としてレトルト用包材を作製した。
(Comparative Example 3)
After completely saponified polyvinyl alcohol resin (saponification degree 99% or more) was dissolved in water, it was coated as a coating agent in the same manner as in Example 1, but blocked due to poor drying, so the coating speed was reduced. A retort packaging was prepared.
（比較例４）
完全けん化ポリビニルアルコール樹脂（けん化度９９％以上）を水に溶解させた後、これをコート剤として、実施例２と同様にグラビア塗工したが、乾燥不良によりブロッキングしたので、塗工速度を落としてノンボイル用包材を作製した。
(Comparative Example 4)
After completely saponified polyvinyl alcohol resin (saponification degree 99% or more) was dissolved in water, this was used as a coating agent and applied to gravure in the same manner as in Example 2, but blocked due to poor drying, so the coating speed was reduced. A non-boiled packaging material was prepared.
（比較例５）
（過少ニトリル基含有アクリル樹脂の調製）
還流冷却管、窒素導入管、温度計、攪拌機を備えた反応容器に酢酸エチル１５０ｇ、ＭＥＫ１００ｇを仕込み９０℃となるまで加温して保持する。メタクリル酸メチル２３４部、メタクリル酸２−ヒドロキシエチル６０部、アクリロニトリル６部の混合溶液中に、重合開始剤として、ベンゾイルパーオキサイドを４．５部入れ撹拌し、この混合液を先の酢酸エチルとＭＥＫ混合溶媒へ９０℃にて均一に２時間掛けて撹拌しながら滴下し、さらに１時間保持する。
(Comparative Example 5)
(Preparation of acrylic resin containing too little nitrile group)
In a reaction vessel equipped with a reflux condenser, a nitrogen inlet tube, a thermometer, and a stirrer, 150 g of ethyl acetate and 100 g of MEK are charged and heated to 90 ° C. and held. In a mixed solution of 234 parts of methyl methacrylate, 60 parts of 2-hydroxyethyl methacrylate and 6 parts of acrylonitrile, 4.5 parts of benzoyl peroxide as a polymerization initiator was added and stirred, and this mixed solution was mixed with the above ethyl acetate. The mixture is added dropwise to the MEK mixed solvent at 90 ° C. with stirring over 2 hours, and the mixture is further maintained for 1 hour.
（比較例５、主剤の調製）
その後、前記ニトリル基含有アクリル樹脂溶液にベンゾイルパーオキサイド１．５部を酢酸エチル１２０部に溶解した開始剤溶液を９０℃にて３時間掛けて均一に滴下した後、さらに２時間保持後７０℃まで冷却し、酢酸ｎ−プロピル、トルエン、イソプロピルアルコール、ＭＥＫをそれぞれ９００部、９００部、２００部、３００部、次いで１５部の３−イソシアネートプロピルトリエトキシシラン、１５部のＮ−２（アミノエチル）３−アミノプロピルメチルジメトキシシランを添加して均一となるように撹拌して、コート剤の主剤（比較例５）を調製した。
(Comparative Example 5, preparation of main agent)
Thereafter, an initiator solution in which 1.5 parts of benzoyl peroxide was dissolved in 120 parts of ethyl acetate in the nitrile group-containing acrylic resin solution was uniformly added dropwise at 90 ° C. over 3 hours, and then maintained for 2 hours and then 70 ° C. To 900 parts, 900 parts, 200 parts, 300 parts, then 15 parts of 3-isocyanatopropyltriethoxysilane, 15 parts of N-2 (aminoethyl). ) 3-Aminopropylmethyldimethoxysilane was added and stirred uniformly to prepare a main agent of the coating agent (Comparative Example 5).
得られた主剤（比較例５）は固形分１０％、重量平均分子量３８，０００（昭和電工社製ＳＨＯＤＥＸ ＫＦ−８０ＭによりＧＰＣ法で測定）、水酸基価８６ｍｇＫＯＨ／ｇ（ＪＩＳ
Ｋ００７０）、Ｔｇ９５℃（ＪＩＳ Ｋ７１２１）、ニトリル含有量２％（計算値）であった。
さらに、硬化剤として、実施例１で用いたヘキサメチレンジイソシアネート３量体の固形分７５％酢酸エチル溶液を用い、上記主剤（比較例５）１００部に対して硬化剤３．３部を添加混合して、コート剤２（比較例５）を作製した。
コート剤２（比較例５）を用いて実施例１と同様に、レトルト用包材を作製した。
The obtained main agent (Comparative Example 5) has a solid content of 10%, a weight average molecular weight of 38,000 (measured by GPC method using SHODEX KF-80M manufactured by Showa Denko KK), and a hydroxyl value of 86 mgKOH / g (JIS).
K0070), Tg 95 ° C. (JIS K7121), and nitrile content 2% (calculated value).
Further, as the curing agent, the hexamethylene diisocyanate trimer solid content 75% ethyl acetate solution used in Example 1 was used, and 3.3 parts of the curing agent was added and mixed with 100 parts of the above main agent (Comparative Example 5). Thus, a coating agent 2 (Comparative Example 5) was produced.
A packaging material for retort was produced in the same manner as in Example 1 using the coating agent 2 (Comparative Example 5).
（比較例６）
（ポリエステル樹脂系コート剤）
数平均分子量１７，０００、Ｔｇ６７℃、固形分中の水酸基価６ｍｇＫＯＨ／ｇであるポリエステル樹脂、バイロン（商標）２０ＳＳ（東洋紡績社製、固形分３０％）１０００部をトルエン／ＭＥＫ＝８／２の混合溶剤１９７０部で希釈してから、１５部の３−イソシアネートプロピルトリエトキシシラン、１５部のＮ−２（アミノエチル）３−アミノプロピルメチルジメトキシシランを添加して均一となるように撹拌して、コート剤主剤（比較例６）を作製後、硬化剤として、実施例１で用いたヘキサメチレンジイソシアネート３量体の固形分７５％酢酸エチル溶液を用い、上記主剤（比較例６）１００部に対して硬化剤０．５部を添加混合して、コート剤３（比較例６）を作製した。
コート剤３（比較例６）を用いて実施例１と同様に、レトルト用包材を作製した。
(Comparative Example 6)
(Polyester resin coating)
A polyester resin having a number average molecular weight of 17,000, Tg of 67 ° C., and a hydroxyl value of 6 mgKOH / g in the solid content, 1000 parts of Byron (trademark) 20SS (manufactured by Toyobo Co., Ltd., solid content of 30%) is toluene / MEK = 8/2. Then, 15 parts of 3-isocyanatopropyltriethoxysilane and 15 parts of N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane were added and stirred uniformly. Then, after preparing the coating agent main agent (Comparative Example 6), the solid component 75% ethyl acetate solution of hexamethylene diisocyanate trimer used in Example 1 was used as the curing agent, and the main agent (Comparative Example 6) 100 parts. The coating agent 3 (Comparative Example 6) was prepared by adding and mixing 0.5 parts of the curing agent.
A packaging material for retort was produced in the same manner as in Example 1 using the coating agent 3 (Comparative Example 6).
＜評価方法＞
上記、実施例、比較例についてそれぞれ下記要領で評価を行い、性能評価した。
<Evaluation method>
The above-mentioned Examples and Comparative Examples were evaluated in the following manner to evaluate the performance.
＜ガスバリヤー性＞
作製した包材（１０×１５ｃｍ２）に酸素バリヤー性を検査するＬＧ−ＯＸ検査液（東京インキ社製）を投入後、熱溶融により密封する。３０℃、９０％ＲＨ条件で１週間保存し、検査液の色により評価する。なお、ＬＧ−ＯＸ検査液は、検査開始時に脱酸素処理した時点で白色を呈しているが、酸素バリヤー性が不良であると検査液が青く変色し、良好であると白色のまま変色しない。
１週間保存後白色のまま…○
１週間保存後青色に着色…×
<Gas barrier properties>
An LG-OX test solution (manufactured by Tokyo Ink Co., Ltd.) for inspecting oxygen barrier properties is added to the produced packaging material (10 × 15 cm 2 ) and then sealed by heat melting. Store at 30 ° C. and 90% RH for 1 week and evaluate by the color of the test solution. Note that the LG-OX test solution is white when deoxygenated at the start of the test, but the test solution turns blue when the oxygen barrier property is poor, and does not change white when it is good.
It remains white after 1 week storage ... ○
Colored blue after 1 week storage ... ×
＜レトルト適性＞
レトルト殺菌（１２１℃×３０分）を施した後の包材の状態を観察した。
サンプル数：各３
試料：包材（１０×１５ｃｍ２）、充填物（ケチャップ／食酢／サラダ油＝１／１／１）
観察結果：浮きなし…○、浮きあり…×
<Retort suitability>
The state of the packaging material after retort sterilization (121 ° C. × 30 minutes) was observed.
Number of samples: 3 each
Sample: packaging material (10 × 15 cm 2 ), filling (ketchup / vinegar / salad oil = 1/1/1)
Observation result: No floating ... ○, with floating ... ×
＜塗工適性（乾燥性）＞
コート剤を厚さ０．３μｍとなるように、１５０ｍ／ｍｉｎの塗工速度でグラビア塗工したときの、塗工状態を観察した。
コート面は乾燥していて問題なく塗工できる…○
乾燥不良でブロッキングを発生し塗工できない…×
<Coating suitability (dryness)>
The coating state was observed when gravure coating was applied at a coating speed of 150 m / min so that the coating agent had a thickness of 0.3 μm.
The coated surface is dry and can be applied without any problem ...
Can not be coated due to blocking due to poor drying. ×
評価結果を表１に示した。表中、−は評価実施していないことを表している。実施例においては、いずれもガスバリヤー性、レトルト適性、塗工適性に優れている。
本発明では、コート剤としてニトリル基含有アクリル樹脂を使用することにより、課題を解決した。本発明のコート剤は油性タイプであるため、乾燥性などの塗工適性は良好であり、蒸着フィルムの保護膜として使用した場合、蒸着膜保護機能と同時にバリヤー性向上効果を付与できた。また、レトルト適性にも対応していることを確認できた。
The evaluation results are shown in Table 1. In the table,-indicates that evaluation is not performed. In Examples, all are excellent in gas barrier properties, retort suitability, and coating suitability.
In this invention, the subject was solved by using a nitrile group containing acrylic resin as a coating agent. Since the coating agent of the present invention is an oily type, the coating suitability such as drying property is good, and when used as a protective film of a vapor deposition film, the barrier property improving effect can be imparted simultaneously with the vapor deposition film protection function. Moreover, it has confirmed that it corresponds also to retort aptitude.
本発明のコート剤組成物は、透明蒸着フィルムの蒸着面に塗工することにより、蒸着フィルムのガスバリヤー性を保護・向上する目的で使用でき、ガスバリヤー性を向上した複合フィルムに好適に使用することができる。 The coating composition of the present invention can be used for the purpose of protecting and improving the gas barrier property of the vapor deposited film by coating on the vapor deposition surface of the transparent vapor deposited film, and is suitably used for the composite film having improved gas barrier property. can do.
Claims (7)
主剤は、ニトリル基含有アクリル樹脂（Ａ）とシランカップリング剤（Ｂ）とを主たる構成成分としてなり、
前記ニトリル基含有アクリル樹脂（Ａ）が、（Ａ）を構成するモノマーとして、ニトリル基含有アクリルモノマーと水酸基含有アクリルモノマーとを必須とし、該ニトリル基含有アクリルモノマーは（Ａ）中に３〜７０質量％で構成され、（Ａ）の水酸基価は２０〜２００ｍｇＫＯＨ／ｇであり、
硬化剤が、イソシアネート化合物（Ｃ）を主たる構成成分とする
ことを特徴とする蒸着無機酸化物フィルム用コート剤組成物。 A two-component mixed coating agent comprising a main agent and a curing agent for protecting and improving the gas barrier property of a vapor-deposited inorganic oxide film,
The main agent is composed mainly of the nitrile group-containing acrylic resin (A) and the silane coupling agent (B),
The nitrile group-containing acrylic resin (A) essentially comprises a nitrile group-containing acrylic monomer and a hydroxyl group-containing acrylic monomer as monomers constituting (A), and the nitrile group-containing acrylic monomer is 3 to 70 in (A). The hydroxyl value of (A) is 20 to 200 mg KOH / g.
A coating agent composition for a vapor-deposited inorganic oxide film, wherein the curing agent comprises an isocyanate compound (C) as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006237296A JP4996180B2 (en) | 2006-09-01 | 2006-09-01 | Coating agent composition for vapor deposition film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006237296A JP4996180B2 (en) | 2006-09-01 | 2006-09-01 | Coating agent composition for vapor deposition film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008056835A JP2008056835A (en) | 2008-03-13 |
| JP4996180B2 true JP4996180B2 (en) | 2012-08-08 |
Family
ID=39239960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006237296A Active JP4996180B2 (en) | 2006-09-01 | 2006-09-01 | Coating agent composition for vapor deposition film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4996180B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2332724B1 (en) * | 2008-10-01 | 2014-05-07 | Toray Industries, Inc. | Gas barrier film |
| DE102009003221A1 (en) * | 2009-05-19 | 2010-11-25 | Evonik Degussa Gmbh | Barrier film, useful e.g. in packaging industry and for organic light-emitting diodes, comprises a weather-resistant carrier layer, a lacquer layer and a barrier layer, where the lacquer layer improves adhesion of the carrier layer |
| JP5705006B2 (en) * | 2011-04-15 | 2015-04-22 | 積水化学工業株式会社 | Gas barrier film and method for producing the same |
| JP6411707B2 (en) * | 2011-10-07 | 2018-10-24 | 東京インキ株式会社 | Gas barrier laminate |
| JP5870834B2 (en) * | 2012-04-27 | 2016-03-01 | 大日本印刷株式会社 | Method for producing gas barrier film |
| JP6272389B2 (en) * | 2016-05-02 | 2018-01-31 | 東京インキ株式会社 | Gas barrier laminate |
| CN111971168B (en) * | 2018-02-02 | 2023-09-05 | 凸版印刷株式会社 | Gas barrier film and method for producing same |
| JP7398892B2 (en) * | 2019-07-08 | 2023-12-15 | 三井化学株式会社 | Two-component polyurethane coating agent |
| JP7439504B2 (en) | 2019-12-26 | 2024-02-28 | Ｔｏｐｐａｎホールディングス株式会社 | Laminates, packages and packaged articles |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57107834A (en) * | 1980-12-26 | 1982-07-05 | Teijin Ltd | Selective beam transmitting laminate |
| JP2533035Y2 (en) * | 1990-08-13 | 1997-04-16 | 凸版印刷株式会社 | Packaging material |
| JP3441594B2 (en) * | 1995-03-14 | 2003-09-02 | ダイセル化学工業株式会社 | Barrier composite film and method for producing the same |
| JP2000007978A (en) * | 1998-06-22 | 2000-01-11 | Toyo Ink Mfg Co Ltd | Coating agent and laminate |
-
2006
- 2006-09-01 JP JP2006237296A patent/JP4996180B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008056835A (en) | 2008-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4996180B2 (en) | Coating agent composition for vapor deposition film | |
| KR102008180B1 (en) | Adhesive for optical film, adhesive layer, optical element, and image display device | |
| TWI485213B (en) | Ultraviolet curing adhesive composition | |
| KR101077064B1 (en) | Inorganic-organic hybrid composition and use thereof | |
| JP5828196B1 (en) | Coating agents and their use | |
| JP6564695B2 (en) | Adhesive composition, method for producing the same, adhesive sheet and image display device | |
| JP6688054B2 (en) | Adhesive composition, optical member and adhesive sheet | |
| JP4292634B2 (en) | Method for manufacturing antireflection laminate | |
| JP5085904B2 (en) | Decorative film | |
| EP2848663B1 (en) | Coating composition with excellent tactile characteristics, preparation method thereof, and transfer sheet using same | |
| TW201336682A (en) | Laminate for window sheet, window sheet comprising the same and display apparatus comprising the same | |
| WO2010038643A1 (en) | Primer and laminate including resin film formed from the primer | |
| JP6967999B2 (en) | Adhesive composition | |
| JP6545407B2 (en) | Resin composition, molded article, laminate, gas barrier material, coating material and adhesive | |
| CN104099046B (en) | Silane primer for improving the adhesiveness of adhesive tape on hydrophilic surfaces, especially on the glass surface | |
| JP5151209B2 (en) | Laminate having a primer and a resin coating film comprising the primer | |
| JP5114923B2 (en) | Adhesive composition | |
| CN101528846A (en) | Inorganic-organic hybrid composition and use thereof | |
| JP4759780B2 (en) | Low refractive index composition, low refractive index film, optical multilayer film and antireflection film | |
| JP6206553B1 (en) | Non-aqueous printing ink composition | |
| JP6152720B2 (en) | Fluorine-based graft copolymer and coating agent using the same | |
| JP2010241991A (en) | Acrylonitrile copolymer composition and method for producing acrylonitrile copolymer | |
| JP3919391B2 (en) | Primer composition | |
| JP6814454B2 (en) | Composition, gas barrier material, coating material, adhesive, molded product, laminate, and method for producing the molded product. | |
| JP5633146B2 (en) | Film or sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090827 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120125 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120131 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120326 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120417 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120511 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150518 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4996180 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |