JP6148500B2 - Gas barrier coating composition - Google Patents
Gas barrier coating composition Download PDFInfo
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- JP6148500B2 JP6148500B2 JP2013040651A JP2013040651A JP6148500B2 JP 6148500 B2 JP6148500 B2 JP 6148500B2 JP 2013040651 A JP2013040651 A JP 2013040651A JP 2013040651 A JP2013040651 A JP 2013040651A JP 6148500 B2 JP6148500 B2 JP 6148500B2
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- Prior art keywords
- meth
- gas barrier
- acrylic acid
- coating composition
- acrylate
- Prior art date
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- 230000004888 barrier function Effects 0.000 title claims description 38
- 239000008199 coating composition Substances 0.000 title claims description 18
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 15
- -1 alkylene glycol Chemical compound 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010408 film Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 29
- 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 16
- 229920000178 Acrylic resin Polymers 0.000 description 12
- 239000004925 Acrylic resin Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- MUBQKSBEWRYKES-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO MUBQKSBEWRYKES-UHFFFAOYSA-N 0.000 description 1
- LCANECIWPMDASZ-UHFFFAOYSA-N 2-isocyanatoethanol Chemical compound OCCN=C=O LCANECIWPMDASZ-UHFFFAOYSA-N 0.000 description 1
- WGKYSFRFMQHMOF-UHFFFAOYSA-N 3-bromo-5-methylpyridine-2-carbonitrile Chemical compound CC1=CN=C(C#N)C(Br)=C1 WGKYSFRFMQHMOF-UHFFFAOYSA-N 0.000 description 1
- YHFGMFYKZBWPRW-UHFFFAOYSA-N 3-methylpentane-1,1-diol Chemical compound CCC(C)CC(O)O YHFGMFYKZBWPRW-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- XFOFBPRPOAWWPA-UHFFFAOYSA-N 6-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCO XFOFBPRPOAWWPA-UHFFFAOYSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 241001601804 Margites Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920006122 polyamide resin 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
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Paints Or Removers (AREA)
Description
本発明は、ガスバリア性塗料組成物に関する。 The present invention relates to a gas barrier coating composition.
包装用樹脂フィルムに、特に食品包装分野においては内容物の長期保存性のためにガスバリア性が重要な要求特性となる。ガスバリア性に優れた樹脂としてポリビニルアルコール(PVA)が使用されているが、吸湿時にガスバリア性が低下し、とくに水分を多く含む食品の包装には適していない。 In the packaging resin film, particularly in the food packaging field, gas barrier properties are an important required characteristic for long-term storage of contents. Polyvinyl alcohol (PVA) is used as a resin having an excellent gas barrier property, but the gas barrier property is lowered at the time of moisture absorption and is not particularly suitable for packaging of foods containing a large amount of moisture.
高湿度下で樹脂フィルムを包装材として用いる場合、ガスバリア性だけでなく耐水性(非水溶性)も要求される。PVAの耐水性を向上させガスバリア性の湿度依存性を改善するために、PVAの水酸基とポリ(メタ)アクリル酸のカルボキシル基をエステル化反応により架橋させる方法が知られている(たとえば特許文献1)。しかしながら、十分なガスバリア性と耐水性のために200℃程度の高温での熱処理が必要であり、樹脂が着色し外観を損ねるなどの問題もあった。 When using a resin film as a packaging material under high humidity, not only gas barrier properties but also water resistance (water-insoluble) is required. In order to improve the water resistance of PVA and improve the humidity dependency of gas barrier properties, a method is known in which a hydroxyl group of PVA and a carboxyl group of poly (meth) acrylic acid are crosslinked by an esterification reaction (for example, Patent Document 1). ). However, heat treatment at a high temperature of about 200 ° C. is necessary for sufficient gas barrier properties and water resistance, and there is a problem that the resin is colored and the appearance is impaired.
さらに、食品包装用途の中でも、レトルト処理される用途においては、単なる酸素透過性の湿度依存性の改善だけでは充分ではなく、レトルト処理後の表面状態や密着性(耐レトルト性)が大きな課題となる。これまでに知られていたポリビニルアルコールおよびポリ(メタ)アクリル酸を含むガスバリア性塗料組成物では、耐レトルト性は充分に改善することができなかった。 Furthermore, among food packaging applications, in applications where retort processing is performed, it is not sufficient to simply improve the humidity dependency of oxygen permeability, and surface conditions and adhesion (retort resistance) after retort processing are major issues. Become. In the gas barrier coating composition containing polyvinyl alcohol and poly (meth) acrylic acid known so far, the retort resistance could not be sufficiently improved.
本発明は、上記のような問題点を改善し、比較的簡便な製造方法で、高温での焼付によるガスバリア性や着色の問題もなく、酸素透過度の湿度依存性も小さく、さらに耐レトルト性が向上したガスバリアフィルムを与える塗料組成物を提供することを目的とする。 The present invention improves the above-mentioned problems, is a relatively simple production method, has no gas barrier property or coloring problem due to baking at high temperature, has low humidity dependency of oxygen permeability, and is also resistant to retort. An object of the present invention is to provide a coating composition that gives a gas barrier film with improved slag.
本発明者らは上記課題を解決するために鋭意検討を重ねた結果、ポリビニルアルコール、および、ポリ(メタ)アクリル酸を含むガスバリア性塗料組成物において、ポリ(メタ)アクリル酸に分岐構造を導入することで、とくに耐レトルト性を改善できることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have introduced a branched structure into poly (meth) acrylic acid in a gas barrier coating composition containing polyvinyl alcohol and poly (meth) acrylic acid. As a result, it was found that the retort resistance can be improved, and the present invention has been completed.
すなわち、本発明は、ポリビニルアルコール、および、分岐したポリ(メタ)アクリル酸を含むガスバリア性塗料組成物に関する。 That is, the present invention relates to a gas barrier coating composition containing polyvinyl alcohol and branched poly (meth) acrylic acid.
分岐したポリ(メタ)アクリル酸は、アルキレングリコールジ(メタ)アクリレートを共重合したポリ(メタ)アクリル酸であることが好ましい。 The branched poly (meth) acrylic acid is preferably poly (meth) acrylic acid obtained by copolymerizing alkylene glycol di (meth) acrylate.
また、本発明は、前記ガスバリア性塗料組成物を塗布し、熱処理する工程を含むガスバリア性フィルムの製造方法、および該製造方法により製造されたガスバリア性フィルムに関する。 Moreover, this invention relates to the manufacturing method of the gas barrier film including the process of apply | coating the said gas barrier coating composition and heat-processing, and the gas barrier film manufactured by this manufacturing method.
本発明では、分岐したポリ(メタ)アクリル酸を使用するため、ポリビニルアルコールに起因するガスバリア性の湿度による変化を改善するとともに、耐レトルト性にも優れたガスバリアフィルムを得ることができる。 In this invention, since the branched poly (meth) acrylic acid is used, while improving the change by the humidity of the gas barrier property resulting from polyvinyl alcohol, the gas barrier film excellent also in retort resistance can be obtained.
本発明のガスバリア性塗料組成物は、ポリビニルアルコール、および、分岐したポリ(メタ)アクリル酸を含むことを特徴とする。 The gas barrier coating composition of the present invention includes polyvinyl alcohol and branched poly (meth) acrylic acid.
本発明で使用するポリビニルアルコールは、分子内に少なくとも2個以上のビニルアルコール単位を有するものであれば、特に限定されず、他のモノマー単位を含む共重合体も使用できる。共重合モノマーとしては、たとえばエチレン、プロピレン、1−ブテンなどの炭素数2〜10のオレフィン類、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸などの炭素数3〜30の不飽和カルボン酸類、アクリロニトリル、メタアクリロニトリルなどの炭素数3〜10の不飽和ニトリル類、メチルビニルエーテル、エチルビニルエーテルなどの炭素数3〜10のビニルエーテル類などが挙げられる。なかでも、ポリビニルアルコール(PVA)またはエチレン−ビニルアルコール共重合体が好ましい。 The polyvinyl alcohol used in the present invention is not particularly limited as long as it has at least two vinyl alcohol units in the molecule, and a copolymer containing other monomer units can also be used. Examples of the copolymerizable monomer include olefins having 2 to 10 carbon atoms such as ethylene, propylene and 1-butene, and unsaturated carboxylic acids having 3 to 30 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid. Examples thereof include unsaturated nitriles having 3 to 10 carbon atoms such as acids, acrylonitrile and methacrylonitrile, and vinyl ethers having 3 to 10 carbon atoms such as methyl vinyl ether and ethyl vinyl ether. Among these, polyvinyl alcohol (PVA) or ethylene-vinyl alcohol copolymer is preferable.
ポリビニルアルコールのケン化度はとくに限定されないが、90〜100%が好ましく、95〜100%がより好ましい。90%未満では、バリア性、耐水性が低下する傾向にある。 The degree of saponification of polyvinyl alcohol is not particularly limited, but is preferably 90 to 100%, more preferably 95 to 100%. If it is less than 90%, the barrier properties and water resistance tend to be lowered.
ポリビニルアルコールの数平均重合度はとくに限定されないが、50〜5000が好ましく、300〜2000がより好ましい。50未満では、機械的強度が劣り、5000を超えると、液粘度が高くなって作業性が低下する傾向がある。 The number average polymerization degree of polyvinyl alcohol is not particularly limited, but is preferably 50 to 5000, and more preferably 300 to 2000. If it is less than 50, mechanical strength is inferior, and if it exceeds 5000, the liquid viscosity tends to be high and workability tends to be lowered.
本発明で使用するポリ(メタ)アクリル酸とは、分子内に少なくも2個以上のアクリル酸またはメタアクリル酸単位を有するポリマーであればとくに限定されず、アクリル酸またはメタアクリル酸のホモポリマーだけでなく、アクリル酸とメタアクリル酸の共重合体や、また他のモノマー単位を含む共重合体も使用できる。共重合モノマーとしては、たとえばエチレン、プロピレン、1−ブテンなどの炭素数2〜10のオレフィン類、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸などの炭素数3〜10の不飽和カルボン酸類、アクリロニトリル、メタアクリロニトリルなどの炭素数3〜10の不飽和ニトリル類、メチルビニルエーテル、エチルビニルエーテルなどの炭素数3〜10のビニルエーテル類などが挙げられる。また、ポリ(メタ)アクリル酸をアルカリまたはアルカリ土類金属の水酸化物や水酸化アンモニウム、水酸化有機アンモニウムなどでカルボン酸基の全部または一部を中和したものも使用できる。これらのポリ(メタ)アクリル酸のうち、ポリ(メタ)アクリル酸またはその部分中和物が好ましく、ポリアクリル酸(PAA)またはその部分中和物が特に好ましい。ここで、ポリ(メタ)アクリル酸とは、ポリメタクリル酸およびポリアクリル酸を意味する。 The poly (meth) acrylic acid used in the present invention is not particularly limited as long as it is a polymer having at least two acrylic acid or methacrylic acid units in the molecule. A homopolymer of acrylic acid or methacrylic acid In addition, copolymers of acrylic acid and methacrylic acid, and copolymers containing other monomer units can also be used. Examples of the copolymerizable monomer include olefins having 2 to 10 carbon atoms such as ethylene, propylene, and 1-butene, and unsaturated carboxylic acids having 3 to 10 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and fumaric acid. Examples thereof include unsaturated nitriles having 3 to 10 carbon atoms such as acids, acrylonitrile and methacrylonitrile, and vinyl ethers having 3 to 10 carbon atoms such as methyl vinyl ether and ethyl vinyl ether. In addition, poly (meth) acrylic acid obtained by neutralizing all or part of carboxylic acid groups with an alkali or alkaline earth metal hydroxide, ammonium hydroxide, organic ammonium hydroxide, or the like can also be used. Among these poly (meth) acrylic acids, poly (meth) acrylic acid or a partially neutralized product thereof is preferable, and polyacrylic acid (PAA) or a partially neutralized product thereof is particularly preferable. Here, poly (meth) acrylic acid means polymethacrylic acid and polyacrylic acid.
なかでも、ポリビニルアルコールとの相溶性が高く、透明性に優れた乾燥被膜が得られる点で、アクリル酸またはメタアクリル酸のホモポリマー、もしくはその部分中和物が好ましい。 Especially, the homopolymer of acrylic acid or methacrylic acid, or its partial neutralization thing is preferable at the point from which the compatibility with polyvinyl alcohol is high and the dry film excellent in transparency is obtained.
ポリ(メタ)アクリル酸に分岐構造を導入する方法はとくに限定されないが、たとえば、溶液重合、乳化重合、ソープフリー乳化重合、懸濁重合などの重合途中で、多官能(メタ)アクリレートを導入する方法が挙げられる。なかでも、微小なソフトゲルを生成できるという点で、多官能(メタ)アクリレートを溶液重合途中で導入する方法が好ましい。 The method for introducing a branched structure into poly (meth) acrylic acid is not particularly limited. For example, polyfunctional (meth) acrylate is introduced during polymerization such as solution polymerization, emulsion polymerization, soap-free emulsion polymerization, suspension polymerization. A method is mentioned. Among them, a method of introducing polyfunctional (meth) acrylate during solution polymerization is preferable in that a fine soft gel can be generated.
多官能(メタ)アクリレートとしては、たとえば1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、3−メチルペンタンジオールジ(メタ)アクリレートなどのアルキレングリコールジ(メタ)アクリレート、ジエチレングリコールビスβ―(メタ)アクリロイルオキシプロピネート、トリメチロールエタントリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリ(2-ヒドロキシエチル)イソシアネートジ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、2,3−ビス(メタ)アクリロイルオキシエチルオキシメチル[2.2.1]ヘプタン、ポリー1,2−ブタジエンジ(メタ)アクリレート、1,2−ビス(メタ)アクリロイルオキシメチルヘキサン、ノナエチレングリコールジ(メタ)アクリレート、テトラデカンエチレングリコールジ(メタ)アクリレート、10−デカンジオール(メタ)アクリレート、3,8−ビス(メタ)アクリロイルオキシメチルトリシクロ[5.2.10]デカンなどがあげられる。これらの化合物は1種または2種以上を組み合わせて使用できる。なかでも、アルキレングリコールジ(メタ)アクリレートが好ましい。このような分岐したポリ(メタ)アクリレートは、塗料組成物中において粒子として存在する。 Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and ethylene glycol di (meth) acrylate. , Alkylene glycol di (meth) acrylate such as triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- (Meth) acryloyloxypropinate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Dipentaerythritol hexa (meth) acrylate, tri (2-hydroxyethyl) isocyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2 .1] Heptane, poly-1,2-butadiene di (meth) acrylate, 1,2-bis (meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecanethylene glycol di (meth) acrylate, 10- Examples include decanediol (meth) acrylate and 3,8-bis (meth) acryloyloxymethyltricyclo [5.2.10.] Decane. These compounds can be used alone or in combination of two or more. Of these, alkylene glycol di (meth) acrylate is preferable. Such branched poly (meth) acrylates are present as particles in the coating composition.
多官能(メタ)アクリレートの共重合量はとくに限定されないが、0.5〜20重量%が好ましく、1〜10重量%がより好ましい。0.5重量%未満では、粒子化が起こらなくなり、20重量%を超えると、ポリビニルアルコールと混合しにくくなる傾向がある。 The copolymerization amount of the polyfunctional (meth) acrylate is not particularly limited, but is preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight. If it is less than 0.5% by weight, particle formation does not occur, and if it exceeds 20% by weight, it tends to be difficult to mix with polyvinyl alcohol.
分岐したポリ(メタ)アクリル酸の数平均分子量はとくに限定されないが、3000〜50000が好ましく、5000〜20000がより好ましい。3000未満では、機械的強度が低下し、50000を超えると、粘度が上昇し、作業性が低下する傾向がある。 The number average molecular weight of the branched poly (meth) acrylic acid is not particularly limited, but is preferably 3000 to 50000, more preferably 5000 to 20000. If it is less than 3000, mechanical strength will fall, and if it exceeds 50000, a viscosity will rise and there exists a tendency for workability | operativity to fall.
ポリビニルアルコール、および、分岐したポリ(メタ)アクリル酸の配合量もとくに限定されないが、分岐したポリ(メタ)アクリル酸の配合量は、ポリビニルアルコール100重量部に対して、5〜400重量部が好ましく、50〜100重量部がより好ましい。5重量部未満では、耐水性が低下し、400重量部を超えると、バリア性および耐水性が低下する傾向がある。 The blending amount of polyvinyl alcohol and branched poly (meth) acrylic acid is not particularly limited, but the blending amount of branched poly (meth) acrylic acid is 5 to 400 parts by weight with respect to 100 parts by weight of polyvinyl alcohol. Preferably, 50-100 weight part is more preferable. If it is less than 5 parts by weight, the water resistance is lowered, and if it exceeds 400 parts by weight, the barrier properties and the water resistance tend to be lowered.
ポリビニルアルコールおよび分岐したポリ(メタ)アクリル酸を混合する際、両者の間でエステル化反応を起こさせるために、触媒を添加することができる。エステル化触媒としては、酸、アルカリ、金属触媒などを使用することができる。なかでも、ポリ(メタ)アクリル酸を中和させるという点から、アルカリが好ましい。アルカリとしてはとくに限定されず、水酸化ナトリウム、水酸化カリウム、アンモニアなどが挙げられる。アルカリの添加量もとくに限定されないが、酸に対して1〜20%を中和するように添加すれば良い。 When mixing polyvinyl alcohol and branched poly (meth) acrylic acid, a catalyst can be added to cause an esterification reaction between them. As the esterification catalyst, an acid, an alkali, a metal catalyst, or the like can be used. Of these, alkali is preferable from the viewpoint of neutralizing poly (meth) acrylic acid. It does not specifically limit as an alkali, Sodium hydroxide, potassium hydroxide, ammonia etc. are mentioned. The addition amount of the alkali is not particularly limited, but may be added so as to neutralize 1 to 20% with respect to the acid.
本発明のガスバリア性塗料組成物には、無機層状化合物などを添加することができる。無機層状化合物は極薄の単位結晶層が重なって一つの層状粒子を形成している無機化合物のことであり、溶媒に膨潤・へき開するものが好ましい。これらの中でも特に溶媒への膨潤性を持つ粘度化合物が好ましく用いられる。代表的なものとしては、たとえばカオリナイト、ハロイサイト、モンモリロナイト、バーキュライト、ディッカイト、ナクライト、アンチゴライト、パイロフィライト、ヘクトライト、バイデライト、マーガタイト、タルク、テトラシリリックマイカ、白雲母、金雲母緑泥石等が挙げられる。なかでも、バリア性の点で、モンモリロナイトが好ましい。 An inorganic layered compound or the like can be added to the gas barrier coating composition of the present invention. The inorganic layered compound is an inorganic compound in which ultrathin unit crystal layers overlap to form one layered particle, and those that swell and cleave in a solvent are preferable. Among these, a viscosity compound having a swelling property to a solvent is particularly preferably used. Typical examples are kaolinite, halloysite, montmorillonite, verculite, dickite, nacrite, antigolite, pyrophyllite, hectorite, beidellite, margite, talc, tetrasilic mica, muscovite, phlogopite. Chlorite and the like. Of these, montmorillonite is preferable in terms of barrier properties.
無機層状化合物の配合量としては、ポリビニルアルコールおよび分岐したポリ(メタ)アクリル酸の合計100重量部に対して、5〜100重量部が好ましく、20〜50重量部がより好ましい。5重量部未満では、バリア性を充分に発現せず、100重量部を超えると、塗膜が白濁する傾向がある。 As a compounding quantity of an inorganic layered compound, 5-100 weight part is preferable with respect to a total of 100 weight part of polyvinyl alcohol and branched poly (meth) acrylic acid, and 20-50 weight part is more preferable. If the amount is less than 5 parts by weight, the barrier property is not sufficiently exhibited, and if it exceeds 100 parts by weight, the coating tends to become cloudy.
本発明のガスバリア性塗料組成物には、溶媒を添加することができる。溶媒としてはとくに限定されないが、たとえば水、メタノール、エタノール、プロパノールなどの炭素数1以上30以下のアルコール類;n−ヘキサン、n−ヘプタン、トルエン、キシレンなどの炭素数4以上30以下の脂肪族または芳香族炭化水素;ジクロロメタン、クロロホルム、クロロベンゼン、o−ジブロモベンゼンなどの炭素数1以上30以下の含ハロゲン脂肪族または芳香族炭化水素;ジエチルエーテル、ジフェニルエーテルなどの炭素数2以上30以下の脂肪族または芳香族エーテル類;酢酸エチル、プロピオン酸ブチルなどの炭素数2以上30以下の脂肪族または芳香族エステル類;ジメチルホルムアミド、ジメチルアセトアミドなどの炭素数2から30の脂肪族または芳香族アミド化合物;アセトニトリル、ベンゾニトリルなどの炭素数2以上30以下の脂肪族または芳香族ニトリル類などが挙げられる。これらの溶媒は1種または2種以上を組み合わせて使用できる。 A solvent can be added to the gas barrier coating composition of the present invention. Although it does not specifically limit as a solvent, For example, C1-C30 alcohols, such as water, methanol, ethanol, and propanol; C4-C30 aliphatic, such as n-hexane, n-heptane, toluene, and xylene Or aromatic hydrocarbons; halogen-containing aliphatic or aromatic hydrocarbons having 1 to 30 carbon atoms such as dichloromethane, chloroform, chlorobenzene, o-dibromobenzene; aliphatics having 2 to 30 carbon atoms such as diethyl ether and diphenyl ether Or aromatic ethers; aliphatic or aromatic esters having 2 to 30 carbon atoms such as ethyl acetate and butyl propionate; aliphatic or aromatic amide compounds having 2 to 30 carbon atoms such as dimethylformamide and dimethylacetamide; Acetonitrile, benzonitrile Like aliphatic or aromatic nitriles having 2 to 30 carbons such. These solvents can be used alone or in combination of two or more.
溶媒の使用量は特に限定されないが、ポリビニルアルコールおよび分岐したポリ(メタ)アクリル酸の混合物100重量部に対し、1〜10000重量部が好ましく、10〜1000重量部がより好ましい。 Although the usage-amount of a solvent is not specifically limited, 1-10000 weight part is preferable with respect to 100 weight part of the mixture of polyvinyl alcohol and branched poly (meth) acrylic acid, and 10-1000 weight part is more preferable.
本発明のガスバリア性フィルムの製造方法は、前記ガスバリア性塗料組成物を基材に塗布し、熱処理する工程を含む。基材はとくに限定されないが、たとえばガラス板、金属板、熱可塑性樹脂フィルム、熱硬化性樹脂フィルムなどが挙げられる。次いで、支持体上にフィルムを形成した後、熱処理を行う。熱処理温度はとくに限定されないが、150〜250℃が好ましく、150〜200℃がより好ましい。150℃未満では、反応が充分に進行しないために、耐水性の低い膜が得られやすくなり、250℃を超えると、密着性の低い膜が得られやすくなる傾向がある。 The method for producing a gas barrier film of the present invention includes a step of applying the gas barrier coating composition to a substrate and heat-treating it. Although a base material is not specifically limited, For example, a glass plate, a metal plate, a thermoplastic resin film, a thermosetting resin film etc. are mentioned. Subsequently, after forming a film on a support body, it heat-processes. Although heat processing temperature is not specifically limited, 150-250 degreeC is preferable and 150-200 degreeC is more preferable. If the temperature is lower than 150 ° C., the reaction does not proceed sufficiently, so that a film having low water resistance is likely to be obtained. If the temperature exceeds 250 ° C., a film having low adhesion tends to be obtained.
ガスバリア性フィルムの膜厚もとくに限定されないが、0.5〜20μmが好ましく、1〜5μmがより好ましい。0.5μm未満では、欠陥のない薄膜が得られにくくなる傾向がある。 The film thickness of the gas barrier film is not particularly limited, but is preferably 0.5 to 20 μm, and more preferably 1 to 5 μm. If the thickness is less than 0.5 μm, it tends to be difficult to obtain a defect-free thin film.
ガスバリア性フィルムは、他の熱可塑性樹脂フィルムと積層することができる。熱可塑性樹脂フィルムは特に制限されないが、たとえばポリエチレン、ポリプロピレンなどのポリオレフィン樹脂フィルム、ナイロン6、ナイロン66などのポリアミド樹脂フィルム、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などのポリエステル樹脂フィルムなどが挙げられる。 The gas barrier film can be laminated with other thermoplastic resin films. The thermoplastic resin film is not particularly limited, and examples thereof include polyolefin resin films such as polyethylene and polypropylene, polyamide resin films such as nylon 6 and nylon 66, and polyester resin films such as polyethylene terephthalate and polyethylene naphthalate.
本発明のガスバリア性塗料組成物の用途はとくに限定されず、従来のガスバリア性材料が使用されていた用途に適用できる。とくに、フィルム(深絞袋、製袋)、ボトル、チューブ、スタンディングパウチ、レトルト用袋、紙容器、バックインボックス、樹脂袋のような重袋用フィルム容器、缶詰などのような食品、工業材料などの包装材料やフロアーヒーティングパイプ及びその構造素材の一部として使用することができる。 The application of the gas barrier coating composition of the present invention is not particularly limited, and can be applied to applications where conventional gas barrier materials have been used. In particular, films (deep-drawn bags, bag making), bottles, tubes, standing pouches, retort bags, paper containers, back-in boxes, film containers for heavy bags such as resin bags, foods such as cans, and industrial materials It can be used as a packaging material such as a floor heating pipe and a part of its structural material.
つぎに、本発明の塗料を、実施例にもとづいて説明するが、本発明はこれらに限定されるものではない。 Next, the paint of the present invention will be described based on examples, but the present invention is not limited thereto.
製造例1
メタクリル酸19部、エタノール80部、および触媒としてアゾビスイソブチロニトリル(AIBN)を用い、窒素気流下で70℃1時間かけて、攪拌しながら重合した。その後、エチレングリコールジメタクリレートEG(ライトエステルEG、共栄社化学株式会社製)1部を加えて同温度で5時間攪拌しアクリル樹脂溶液を得た。得られたアクリル樹脂溶液は、固形分20.3%、粘度400cpsであった。なお、粘度は、B型粘度計およびローターNo.2を用い、25±0.5℃下にて測定した。得られたアクリル樹脂の数平均分子量は、18000であった。
Production Example 1
Polymerization was conducted with stirring for 19 hours under a nitrogen stream using 19 parts of methacrylic acid, 80 parts of ethanol, and azobisisobutyronitrile (AIBN) as a catalyst. Then, 1 part of ethylene glycol dimethacrylate EG (light ester EG, manufactured by Kyoeisha Chemical Co., Ltd.) was added and stirred at the same temperature for 5 hours to obtain an acrylic resin solution. The obtained acrylic resin solution had a solid content of 20.3% and a viscosity of 400 cps. The viscosity was measured using a B-type viscometer and a rotor No. 2 was measured at 25 ± 0.5 ° C. The number average molecular weight of the obtained acrylic resin was 18000.
製造例2
メタクリル酸19部、エタノール80部、および触媒としてアゾビスイソブチロニトリル(AIBN)を用い、窒素気流下で70℃1時間かけて、攪拌しながら重合した。その後、ポリエチレングリコールジメタクリレート(ライトエステル4EG−A、PEG#200(EG4量体)、共栄社化学株式会社製)1部を加えて同温度で5時間攪拌しアクリル樹脂溶液を得た。得られたアクリル樹脂溶液は、固形分20.1%、粘度250cpsであった。得られたアクリル樹脂の数平均分子量は、13000であった。
Production Example 2
Polymerization was conducted with stirring for 19 hours under a nitrogen stream using 19 parts of methacrylic acid, 80 parts of ethanol, and azobisisobutyronitrile (AIBN) as a catalyst. Thereafter, 1 part of polyethylene glycol dimethacrylate (light ester 4EG-A, PEG # 200 (EG tetramer), manufactured by Kyoeisha Chemical Co., Ltd.) was added and stirred at the same temperature for 5 hours to obtain an acrylic resin solution. The obtained acrylic resin solution had a solid content of 20.1% and a viscosity of 250 cps. The number average molecular weight of the obtained acrylic resin was 13000.
製造例3
メタクリル酸19部、エタノール80部、および触媒としてアゾビスイソブチロニトリル(AIBN)を用い、窒素気流下で70℃1時間かけて、攪拌しながら重合した。その後、1,6−ヘキサンジオールメタクリレート(ライトエステル1.6HX、共栄社化学株式会社製)1部を加えて同温度で5時間攪拌しアクリル樹脂溶液を得た。得られたアクリル樹脂溶液は、固形分20.0%、粘度350cpsであった。得られたアクリル樹脂の数平均分子量は、15000であった。
Production Example 3
Polymerization was conducted with stirring for 19 hours under a nitrogen stream using 19 parts of methacrylic acid, 80 parts of ethanol, and azobisisobutyronitrile (AIBN) as a catalyst. Thereafter, 1 part of 1,6-hexanediol methacrylate (light ester 1.6HX, manufactured by Kyoeisha Chemical Co., Ltd.) was added and stirred at the same temperature for 5 hours to obtain an acrylic resin solution. The obtained acrylic resin solution had a solid content of 20.0% and a viscosity of 350 cps. The number average molecular weight of the obtained acrylic resin was 15000.
製造例4
メタクリル酸20部、エタノール80部、および触媒としてアゾビスイソブチロニトリル(AIBN)を用い、窒素気流下で70℃6時間かけて、攪拌しながら重合した。得られたアクリル樹脂溶液は、固形分20.4%、粘度200cpsであった。得られたアクリル樹脂の数平均分子量は、10000であった。
Production Example 4
Using 20 parts of methacrylic acid, 80 parts of ethanol, and azobisisobutyronitrile (AIBN) as a catalyst, polymerization was conducted with stirring at 70 ° C. for 6 hours under a nitrogen stream. The obtained acrylic resin solution had a solid content of 20.4% and a viscosity of 200 cps. The number average molecular weight of the obtained acrylic resin was 10,000.
実施例1〜3および比較例1
ポリビニルアルコール(OKS−8049、日本合成株式会社製)の20%水溶液50gに、製造例1〜4で重合したアクリル樹脂50g(固形分20%)、水酸化ナトリウム0.44gを加え良く攪拌して、それぞれ実施例1〜3および比較例1の塗料を調製した。
Examples 1 to 3 and Comparative Example 1
Add 50 g of acrylic resin polymerized in Production Examples 1 to 4 (solid content 20%) and 0.44 g of sodium hydroxide to 50 g of 20% aqueous solution of polyvinyl alcohol (OKS-8049, Nihon Gosei Co., Ltd.) and stir well. The paints of Examples 1 to 3 and Comparative Example 1 were prepared.
実施例4
実施例2で得られた塗料の固形分100重量部に対して、マイカ水膨潤スラリー(濃度8%、ソマシフMEB−3、平均粒子径2〜3μ、コープケミカル株式会社製)を250重量部(固形分で20部)混合して良く攪拌し塗料を調製した。
Example 4
250 parts by weight of mica water swelling slurry (concentration 8%, Somasif MEB-3, average particle diameter of 2 to 3 μ, manufactured by Coop Chemical Co., Ltd.) with respect to 100 parts by weight of the solid content of the paint obtained in Example 2 The mixture was mixed and mixed well to prepare a paint.
比較例2
ポリビニルアルコール(OKS−8049、日本合成株式会社製)の20%水溶液50gに、固形分20%のポリアクリル酸水溶液(アクアリックHL−415,日本触媒株式会社製)50g、水酸化ナトリウム0.44gを加え良く攪拌して、比較例2の塗料を調製した。
Comparative Example 2
50 g of 20% aqueous solution of polyvinyl alcohol (OKS-8049, manufactured by Nihon Gosei Co., Ltd.), 50 g of polyacrylic acid aqueous solution (Aquaric HL-415, manufactured by Nippon Shokubai Co., Ltd.) with a solid content of 20%, 0.44 g of sodium hydroxide Was added and stirred well to prepare a coating material of Comparative Example 2.
実施例1〜3および比較例1〜2で得られた塗料を0.29mm厚のA5052アルミ材(神戸製鋼株式会社製)の基材上に塗布し、200℃で3分間焼付した。得られた塗装板を用いて、以下に示す方法で鉛筆硬度と耐水性を評価した。評価結果を表1に示す。 The paints obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were applied on a base material of 0.250 mm thick A5052 aluminum material (manufactured by Kobe Steel) and baked at 200 ° C. for 3 minutes. Using the obtained coated plate, pencil hardness and water resistance were evaluated by the following methods. The evaluation results are shown in Table 1.
実施例2および比較例2で得られた塗料を二軸延伸ポリエステルフィルム(25μ、E5107,東洋紡績株式会社製)のコロナ面上に乾燥膜厚3μで塗布し、200℃で3分間焼付および200℃で10分間焼付した。得られたそれぞれのフィルムを用いて、目視により着色を確認するとともに、以下に示す方法で酸素透過度を測定した。評価結果を表2に示す。 The paint obtained in Example 2 and Comparative Example 2 was applied on the corona surface of a biaxially stretched polyester film (25 μ, E5107, manufactured by Toyobo Co., Ltd.) with a dry film thickness of 3 μ, baked at 200 ° C. for 3 minutes, and 200 Bake at 10 ° C. for 10 minutes. Each of the obtained films was visually checked for coloration, and the oxygen permeability was measured by the method described below. The evaluation results are shown in Table 2.
実施例2および4で得られた塗料を二軸延伸ポリエステルフィルム(25μ、E5107,東洋紡績株式会社製)のコロナ面上に乾燥膜厚3μで塗布し、200℃で3分間焼付した。得られたそれぞれのフィルムを用いて、23℃において、湿度65%と80%の条件下で、以下に示す方法で酸素透過度を測定した。評価結果を表3に示す。 The paints obtained in Examples 2 and 4 were applied at a dry film thickness of 3 μm on the corona surface of a biaxially stretched polyester film (25 μm, E5107, manufactured by Toyobo Co., Ltd.) and baked at 200 ° C. for 3 minutes. Using each of the obtained films, the oxygen transmission rate was measured at 23 ° C. under the conditions of 65% and 80% humidity by the following method. The evaluation results are shown in Table 3.
<鉛筆硬度>
JIS K−5400(1990)に記載の方法に準拠し、三菱鉛筆株式会社製ユニ(商品名)を用いて測定した。
<密着性>
JIS K−5400(1990)に記載の方法に準拠し、塗装板上をカッターナイフで塗膜を貫通して素地に達するように1mm間隔で切り傷をつけ、碁盤目100個(10×10)を作る。これにニチバン製セロテープ(登録商標)を完全に密着させ、塗面に対して90°の方向に急激に剥離し、塗膜の状態を目視にて観察し、以下の基準に基づいて評価した。
<Pencil hardness>
Based on the method described in JIS K-5400 (1990), the measurement was performed using Uni (trade name) manufactured by Mitsubishi Pencil Co., Ltd.
<Adhesion>
In accordance with the method described in JIS K-5400 (1990), the coated plate was cut with a cutter knife on the painted plate at intervals of 1 mm so as to reach the substrate, and 100 grids (10 × 10) were cut create. Nichiban cello tape (registered trademark) was completely adhered to this, and it peeled off rapidly in the direction of 90 ° with respect to the coating surface. The state of the coating film was visually observed and evaluated based on the following criteria.
<耐水性>
80℃30分処理については、80℃のウォーターバスに30分間浸漬処理を施した後、表面状態と密着性を以下の基準で評価した。レトルト処理30分については、125℃で30分間レトルト処理を施した後、表面状態と密着性を以下の基準で評価した。評価結果を表1に示す。
表面状態
○・・・変化なし。
○△・・少し白化したり、表面状態に変化がある。
△・・・塗膜が白化あるいは少し溶けたような表面をしている。
×・・・処理により塗膜が溶解した。
<Water resistance>
About 80 degreeC 30 minute process, after performing immersion process for 30 minutes to a 80 degreeC water bath, the surface condition and adhesiveness were evaluated on the following references | standards. About 30 minutes of retort processing, after performing the retort processing for 30 minutes at 125 degreeC, the surface condition and adhesiveness were evaluated on the following references | standards. The evaluation results are shown in Table 1.
Surface condition ○ ・ ・ ・ No change.
○ △ ・ ・ Slightly whitening or change in surface condition.
Δ: The surface is whitened or slightly melted.
X: The coating film was dissolved by the treatment.
密着性
○・・・変化なし。
○△・・1〜10個の升目が剥離した。
△・・・半分程度の升目が剥離した。
×・・・全体が剥離した。
Adhesion ○ ・ ・ ・ No change.
○ Δ ························································································ −
Δ: Half of the squares peeled off.
X: The whole peeled off.
<酸素透過度>
JIS K 7126Bに記載の方法に準拠し、23℃×65%RHの条件下で、サンプル表面から裏面への酸素の透過率を、2回測定し、その平均値を算出した。
<Oxygen permeability>
Based on the method described in JIS K 7126B, the oxygen permeability from the sample surface to the back surface was measured twice under the condition of 23 ° C. × 65% RH, and the average value was calculated.
表1の結果から、分岐していないポリ(メタ)アクリル酸を使用すると、比較例1に示すように、密着性が大きく低下する。一方、分岐したポリ(メタ)アクリル酸を使用すると、実施例1〜3に示すように、30分のレトルト処理を行った後でも、表面状態と密着性を維持している。 From the results in Table 1, when unbranched poly (meth) acrylic acid is used, as shown in Comparative Example 1, the adhesion is greatly reduced. On the other hand, when branched poly (meth) acrylic acid is used, as shown in Examples 1 to 3, the surface state and adhesion are maintained even after 30 minutes of retorting.
表2の結果から、分岐構造を導入していないポリ(メタ)アクリル酸を含むガスバリア性塗料組成物では、比較例2に示すように200℃で10分間焼付を行うと、黄変した。一方、分岐構造を導入したポリ(メタ)アクリル酸を含むガスバリア性塗料組成物では、実施例2に示すように200℃で10分間焼付を行っても、着色は見られなかった。 From the results shown in Table 2, the gas barrier coating composition containing poly (meth) acrylic acid into which no branched structure was introduced was yellowed when baked at 200 ° C. for 10 minutes as shown in Comparative Example 2. On the other hand, in the gas barrier coating composition containing poly (meth) acrylic acid into which a branched structure was introduced, as shown in Example 2, no coloring was observed even after baking at 200 ° C. for 10 minutes.
表3の結果から、マイカを配合すると、酸素透過度の湿度依存性が大きく改善された。 From the results in Table 3, when mica was blended, the humidity dependency of oxygen permeability was greatly improved.
耐レトルト性に優れたガスバリア性フィルムが得られ、食品包装、とくにレトルト食品などの用途に好適に適用できる。 A gas barrier film excellent in retort resistance can be obtained, and can be suitably applied to food packaging, particularly retort foods.
Claims (2)
分岐したポリ(メタ)アクリル酸が、アルキレングリコールジ(メタ)アクリレートを共重合したポリ(メタ)アクリル酸であるガスバリア性塗料組成物。 A gas barrier coating composition comprising polyvinyl alcohol and branched poly (meth) acrylic acid ,
A gas barrier coating composition in which the branched poly (meth) acrylic acid is poly (meth) acrylic acid obtained by copolymerizing alkylene glycol di (meth) acrylate .
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