JP3273631B2 - Terminal ion-modified ethylene-vinyl alcohol copolymer and aqueous dispersion thereof - Google Patents
Terminal ion-modified ethylene-vinyl alcohol copolymer and aqueous dispersion thereofInfo
- Publication number
- JP3273631B2 JP3273631B2 JP14316192A JP14316192A JP3273631B2 JP 3273631 B2 JP3273631 B2 JP 3273631B2 JP 14316192 A JP14316192 A JP 14316192A JP 14316192 A JP14316192 A JP 14316192A JP 3273631 B2 JP3273631 B2 JP 3273631B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- water
- aqueous dispersion
- mol
- evoh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000006185 dispersion Substances 0.000 title claims description 75
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 title claims description 53
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical group OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 38
- 239000005977 Ethylene Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 31
- 238000007127 saponification reaction Methods 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 20
- 125000003010 ionic group Chemical group 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012046 mixed solvent Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229920001567 vinyl ester resin Polymers 0.000 claims description 11
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 8
- 239000010419 fine particle Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 93
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 66
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 43
- 238000000034 method Methods 0.000 description 34
- 239000010408 film Substances 0.000 description 27
- 239000007789 gas Substances 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000004888 barrier function Effects 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 19
- 239000000839 emulsion Substances 0.000 description 18
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 150000003573 thiols Chemical class 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- -1 Butylhexyl Chemical group 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 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 8
- 239000000126 substance Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 4
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- ZJRRHXQQZBQOMB-UHFFFAOYSA-M sodium;3-sulfanylpropanoate Chemical compound [Na+].[O-]C(=O)CCS ZJRRHXQQZBQOMB-UHFFFAOYSA-M 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- VXVUDUCBEZFQGY-UHFFFAOYSA-N 4,4-dimethylpentanenitrile Chemical compound CC(C)(C)CCC#N VXVUDUCBEZFQGY-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
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- 125000003368 amide group Chemical group 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
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- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- KZLAYICWOGEOSV-UHFFFAOYSA-M sodium;2-sulfanylpropanoate Chemical compound [Na+].CC(S)C([O-])=O KZLAYICWOGEOSV-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000006177 thiolation reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、末端にイオン性基を有
するエチレン−ビニルアルコール系共重合体およびその
水性分散液に関し、特に分散性に優れたエチレン−ビニ
ルアルコール系共重合体の水性乳化分散液に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ethylene-vinyl alcohol copolymer having an ionic group at its terminal and an aqueous dispersion thereof, and more particularly to an aqueous emulsion of an ethylene-vinyl alcohol copolymer having excellent dispersibility. It relates to a dispersion.
【０００２】[0002]
【従来の技術】エチレン−ビニルエステル系共重合体、
特にエチレン−酢酸ビニル系共重合体をけん化したエチ
レン−ビニルアルコール系共重合体（以下ＥＶＯＨと略
記する）は、酸素等のガスバリヤー性や耐油・耐薬品性
に優れているため、包装材料やプラスチック成形物、金
属表面、紙、木材等の保護被覆用材料として注目されて
いる。2. Description of the Related Art Ethylene-vinyl ester copolymers,
In particular, an ethylene-vinyl alcohol-based copolymer (hereinafter abbreviated as EVOH) obtained by saponifying an ethylene-vinyl acetate-based copolymer is excellent in gas barrier properties of oxygen and the like, oil resistance, and chemical resistance, and is therefore used in packaging materials and the like. It is attracting attention as a protective coating material for plastic molded products, metal surfaces, paper, wood, and the like.
【０００３】特に内容物の酸化防止あるいは香りの保持
が重要とされる食品包装用のフィルム、シート、積層
物、中空容器等に於ては、高度のガスバリヤー性が要求
されている。また軟質塩化ビニルからなる塩ビ壁紙、塩
ビレザー、シート等では、可塑剤のブリードを防止する
被覆材が要求されている。そこでガスバリヤー性、保香
性および耐油・耐薬品性に優れたＥＶＯＨを内層、外層
あるいは中間層に設けることによって、これらの要求特
性を高度に満たすことが広く実施されている。[0003] In particular, high gas barrier properties are required for films, sheets, laminates, hollow containers, and the like for food packaging, for which it is important to prevent the contents from being oxidized or to maintain the flavor. In addition, for PVC wallpaper, PVC leather, sheets and the like made of soft vinyl chloride, a coating material for preventing bleeding of a plasticizer is required. Therefore, it has been widely practiced to meet these required properties to a high degree by providing EVOH having excellent gas barrier properties, fragrance retention properties and oil / chemical resistance in the inner layer, the outer layer or the intermediate layer.
【０００４】一般にＥＶＯＨ層を形成する方法として
は、溶融押出あるいは射出成形による方法やＥＶＯＨフ
ィルムをラミネートする方法等が広く実施されている。
一方、ＥＶＯＨの溶液や水性乳化分散液を塗布し、乾燥
する方法が提案されている。この方法は比較的膜厚の薄
い皮膜が形成できること、中空容器等の複雑な形状のも
のにも容易に皮膜が形成できること等から注目される。In general, as a method for forming an EVOH layer, a method by melt extrusion or injection molding, a method of laminating an EVOH film, and the like are widely practiced.
On the other hand, a method has been proposed in which an EVOH solution or an aqueous emulsion dispersion is applied and dried. This method attracts attention because a relatively thin film can be formed, and a film having a complicated shape such as a hollow container can be easily formed.
【０００５】しかしながら、ＥＶＯＨ溶液を塗布する方
法では基本的に高い濃度の溶液が粘度の関係から使用困
難なこと、溶剤がジメチルスルホキシド等の有機溶剤や
多量のアルコールと水の混合溶剤のため、皮膜形成過程
において有機溶剤の揮散による作業環境の悪化および有
機溶剤の回収のための装置が必要になる等、経済的にも
不利なこと等の問題がある。これに対し、ＥＶＯＨ水性
分散液を塗布する方法は、溶剤が水系で上記の作業環境
や経済性の点から有利と考えられ期待される。However, in the method of applying an EVOH solution, it is basically difficult to use a solution having a high concentration because of viscosity, and the solvent is an organic solvent such as dimethyl sulfoxide or a mixed solvent of a large amount of alcohol and water. In the formation process, there are problems such as deterioration of the working environment due to volatilization of the organic solvent and the necessity of an apparatus for collecting the organic solvent, which is economically disadvantageous. On the other hand, the method of applying the EVOH aqueous dispersion is considered to be advantageous from the viewpoint of the above working environment and economy because the solvent is water-based, and is expected.
【０００６】ＥＶＯＨの水性乳化分散液としては、通常
のＥＶＯＨを通常の界面活性剤あるいは通常の高分子コ
ロイド、例えばポリエチレンオキシド、カルボキシメチ
ルセルロース、ヒドロキシエチルセルロース、ポリビニ
ルアルコール等の共存下で乳化分散させたものが特開昭
５４−１０１８４４、特開昭５６−６１４３０等で提案
されている。しかしながら、本発明者等の検討による
と、これら公知の方法で得られたＥＶＯＨの水性乳化分
散液は、分散安定性が不十分で塗布用として実用が困難
である。[0006] The aqueous emulsified dispersion of EVOH is obtained by emulsifying and dispersing ordinary EVOH in the presence of an ordinary surfactant or an ordinary polymer colloid, for example, polyethylene oxide, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol and the like. Have been proposed in JP-A-54-101844 and JP-A-56-61430. However, according to the study of the present inventors, the aqueous emulsion dispersion of EVOH obtained by these known methods has insufficient dispersion stability and is difficult to be practically used for coating.
【０００７】また特開昭５４−１０１８４４には、アク
リル酸やアクリル酸アミド等のビニルモノマーをエチレ
ンおよび酢酸ビニルと三元共重合し、けん化して得た、
いわゆるランダムに共重合されたランダム共重合体のＥ
ＶＯＨ自体を通常の界面活性剤を分散安定剤として分散
させることが示されている。Japanese Patent Application Laid-Open No. 54-101844 discloses that a vinyl monomer such as acrylic acid or acrylamide is terpolymerized with ethylene and vinyl acetate and saponified.
So-called random copolymerized random copolymer E
It has been shown that VOH itself is dispersed with a conventional surfactant as a dispersion stabilizer.
【０００８】しかしながら、本発明者等の検討によると
単純な三元ランダム共重合によるＥＶＯＨでは乳化分散
安定性の向上は認められず、実用的な乳化分散液は得ら
れなかった。中ではイオン性基を有するアクリル酸を共
重合した場合は、そのイオン性基により乳化分散安定性
は改善されるが、イオン性基がランダムに含有されてい
るため、その含量を多くしないと乳化分散安定性が十分
に達成できず、そうするとＥＶＯＨの構造の乱れが大と
なって結晶性が低下し、ガスバリヤー性能が大幅に低下
する等の欠点があり実用的でない。However, according to the study by the present inventors, no improvement in emulsion dispersion stability was observed for EVOH obtained by simple ternary random copolymerization, and no practical emulsion dispersion was obtained. When acrylic acid having an ionic group is copolymerized in the emulsion, the emulsification dispersion stability is improved by the ionic group, but since the ionic group is contained at random, if the content is not increased, the emulsification is not improved. Dispersion stability cannot be sufficiently attained, and if this is the case, the structure of the EVOH becomes so disordered that crystallinity is reduced and gas barrier performance is significantly reduced, which is not practical.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、末端にイオ
ン性基を有する新規なＥＶＯＨおよびそれを用いた貯蔵
あるいは使用時の安定性が著しく改善され、分散安定性
の優れた、さらには造膜性に優れたＥＶＯＨ系水性分散
液、特に水性乳化分散液を提供するものである。DISCLOSURE OF THE INVENTION The present invention relates to a novel EVOH having an ionic group at the terminal, and a remarkably improved stability during storage or use using the same, and excellent dispersion stability. An object of the present invention is to provide an EVOH-based aqueous dispersion having excellent film properties, particularly an aqueous emulsion dispersion.
【００１０】[0010]
【課題を解決するための手段】上記目的は、ＥＶＯＨと
して末端にイオン性基を有し、かつ常温で水に不溶性の
特定のイオン変性ＥＶＯＨ系共重合体を自己乳化分散す
ることによって達成される。The above object can be attained by self-emulsifying and dispersing a specific ion-modified EVOH-based copolymer having an ionic group at an end as an EVOH and being insoluble in water at ordinary temperature. .
【００１１】本発明の最大の特徴は、そのＥＶＯＨ系水
性乳化分散液が貯蔵あるいは使用時の安定性において著
しく改善され、分散安定性に優れることである。元々粒
子径の小さいものが得られる上に、分散安定性が優れ、
貯蔵あるいは使用時の粒子の凝集による粒子径の顕著な
増大が殆どないため、粒子径の小さいことも大きな特徴
である。この特徴により本発明のＥＶＯＨ系水性乳化分
散液は造膜性が良好でより薄い均質な皮膜が塗布でき、
乾燥した皮膜がガスバリヤー性に優れる。ＥＶＯＨの分
子の末端にイオン性基が結合されているため、ＥＶＯＨ
成分の構造が殆ど乱されず、高ガスバリヤー性能が保持
できるものと考えられる。The most important feature of the present invention is that the EVOH-based aqueous emulsified dispersion is remarkably improved in storage or use stability and is excellent in dispersion stability. Originally small particle size can be obtained and excellent dispersion stability,
Since the particle size is not significantly increased due to aggregation of the particles during storage or use, the small particle size is also a major feature. Due to this feature, the EVOH-based aqueous emulsified dispersion of the present invention has good film-forming properties and can be applied to a thinner uniform film,
The dried film has excellent gas barrier properties. Since an ionic group is bonded to the terminal of the EVOH molecule, EVOH
It is considered that the structure of the components is hardly disturbed, and high gas barrier performance can be maintained.
【００１２】 本発明のＥＶＯＨは、末端にスルホン酸
基またはその塩、カルボン酸基またはその塩、アンモニ
ウム基の群から選択される少なくとも１種または２種以
上のイオン性基を有し、１モル／リットルのチオシアン
酸アンモニウムを含有する水／フェノール系混合溶剤
（重量比１５／８５）中３０℃で測定した固有粘度０．
４５デシリットル／ｇ以上、エチレン含量１５〜６５モ
ル％、けん化度９０モル％以上のエチレン−ビニルアル
コール系共重合体けん化物で、かつ常温で水の不溶解性
のもの（以下末端イオン変性ＥＶＯＨと略記する）を包
含する。末端にイオン性基を有することの認定は、ＮＭ
Ｒ（核磁気共鳴）分析により実施できる。また常温で水
に不溶解性とは濃度１％で３０℃の水に１日溶解したと
きの不溶解分が５０％以上のものを言う。水に対する不
溶解分は高いほうが好ましく、８０％以上さらに好まし
くは９０％以上である。The EVOH of the present invention has a sulfonic acid
Group or its salt, carboxylic acid group or its salt, ammonium
At least one or more selected from the group consisting of
Intrinsic viscosity measured at 30 ° C. in a water / phenol-based mixed solvent (15/85 by weight) containing the above ionic groups and containing 1 mol / l ammonium thiocyanate was used.
A saponified ethylene-vinyl alcohol copolymer having 45 deciliters / g or more, an ethylene content of 15 to 65 mol% and a saponification degree of 90 mol% or more, and insoluble in water at ordinary temperature (hereinafter referred to as terminal ion-modified EVOH) to include abbreviated). Certification of having an ionic group at the terminal is based on NM
It can be performed by R (nuclear magnetic resonance) analysis. The term "insoluble in water at normal temperature" refers to a substance having a concentration of 1% and an insoluble content of 50% or more when dissolved in water at 30 ° C for 1 day. The insoluble content in water is preferably higher, more preferably 80% or more, more preferably 90% or more.
【００１３】 本発明においてイオン性基とは、水中で
イオン性を示す基であり、スルホン酸基またはその塩、
カルボン酸基またはその塩、アンモニウム基である。イ
オン性基は1種でもよいし、２種以上の混合物でもよ
い。In the present invention, the ionic group is a group that exhibits ionicity in water, and includes a sulfonic acid group or a salt thereof,
It is a carboxylic acid group or a salt thereof, or an ammonium group . The ionic group may be one type or a mixture of two or more types.
【００１４】末端イオン変性ＥＶＯＨの組成は、エチレ
ン含量１５〜６５モル％、けん化度（本発明で言うけん
化度はビニルエステル単位のけん化度を示す）９０モル
％以上である必要がある。エチレン含量が１５モル％未
満では水性乳化分散液の安定性が不良となり、また６５
モル％を越えるものはポリマーのガスバリヤー性が不良
となり不適当である。水性乳化分散液の安定性とガスバ
リヤー性の点からエチレン含量のより好適な範囲は２０
〜５５モル％である。またけん化度は９０モル％未満で
はガスバリヤー性が不十分になるので９０モル％以上で
あることが必要で、より好適には９５モル％以上、さら
には９７モル％以上が好ましい。The composition of the terminal ion-modified EVOH must have an ethylene content of 15 to 65 mol% and a degree of saponification (the degree of saponification in the present invention indicates the degree of saponification of vinyl ester units) of at least 90 mol%. If the ethylene content is less than 15 mol%, the stability of the aqueous emulsion dispersion becomes poor, and
If the amount exceeds mol%, the gas barrier property of the polymer becomes poor and the polymer is unsuitable. From the viewpoint of the stability and gas barrier properties of the aqueous emulsion dispersion, a more preferable range of the ethylene content is 20.
~ 55 mol%. If the degree of saponification is less than 90 mol%, the gas barrier property becomes insufficient. Therefore, the saponification degree needs to be 90 mol% or more, more preferably 95 mol% or more, and further preferably 97 mol% or more.
【００１５】またＥＶＯＨ中にエチレンおよびビニルエ
ステルと共重合可能な単量体成分、例えばプロピレン、
イソブテン等のα−オレフィン類、ビニルトリメトキシ
シラン、ビニルトリエトキシシラン等のケイ素含有単量
体、アクリルアミド、Ｎ−メトキシメチルアクリルアミ
ド等のアクリルアミド類、アクリロニトリル、Ｎ−ビニ
ル−２−ピロリドン等が本発明の目的が阻害されない程
度の少量含まれていてもよい。Further, a monomer component copolymerizable with ethylene and vinyl ester in EVOH, for example, propylene,
Α-olefins such as isobutene; silicon-containing monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; acrylamides such as acrylamide and N-methoxymethylacrylamide; acrylonitrile; N-vinyl-2-pyrrolidone; May be contained in such a small amount that the object of the invention is not hindered.
【００１６】固有粘度は用途に応じて選択されるが、極
端に低いものは生成皮膜の強度が低く実用的でないの
で、０．４５デシリットル／ｇ以上、好ましくは０．６
０デシリットル／ｇ以上である。固有粘度の高いものほ
ど水性乳化分散液として塗布使用することは有利であ
り、通常３デシリットル／ｇ程度のものまで使用でき
る。The intrinsic viscosity is selected according to the application. However, an extremely low viscosity is 0.45 deciliter / g or more, preferably 0.6 mm or less, because the strength of the resulting film is low and not practical.
0 deciliter / g or more. The higher the intrinsic viscosity, the more advantageous it is to apply and use as an aqueous emulsified dispersion, and it can usually be used up to about 3 deciliter / g.
【００１７】 末端にスルホン酸基またはその塩、カル
ボン酸基またはその塩、アンモニウム基の群から選択さ
れる少なくとも１種または２種以上のイオン性基が導入
された、水性乳化分散液としての優れた安定性等を示す
ＥＶＯＨを得る方法としては、スルホン酸基またはその
塩、カルボン酸基またはその塩、アンモニウム基を含有
するチオールを連鎖移動剤として共存させて、エチレン
とビニルエステルとを共重合し、次いでけん化する方法
がある。[0017] The sulfonic acid group or a salt thereof at the end of the end, Cal
Selected from the group consisting of boronic acid groups or salts thereof and ammonium groups
At least one or two or more ionic groups are introduced
As a method for obtaining EVOH having excellent stability and the like as an aqueous emulsion dispersion, a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, and a thiol containing an ammonium group are coexistent as a chain transfer agent. Te, and copolymerizing ethylene and vinyl ester, then there is a method of saponification.
【００１８】エチレンとビニルエステルとの共重合は、
公知の方法、すなわち回分方式、半回分方式、あるいは
連続方式にて、重合開始剤の存在下、溶液重合、懸濁重
合、エマルジョン重合により実施されるが、アルコール
の存在下溶液重合で実施することが工業的に好ましい。
溶液重合の場合、溶剤濃度は０〜５０％、好適には３〜
３０％であり、重合率は通常２０〜８０％、好適には３
０〜６０％である。また重合温度は、通常２０〜１００
℃、好適には４０〜８０℃である。重合開始剤として
は、２，２’−アゾビスイソブチロニトリル、２，２’
−アゾビス−（２，４−ジメチルバレロニトリル）、
２，２’−アゾビス−（４−メトキシ−２，４−ジメチ
ルバレロニトリル）等のニトリル類、ジ−ノルマルプロ
ピルパ−オキシカ−ボネート、ビス−４−タ−シャリ−
ブチルヘキシルパ−オキシジカ−ボネート、ビス−２−
エチルヘキシルパ−オキシジカ−ボネート等のカ−ボネ
ート類、過酸化ベンゾイル、過酸化ラウロイル、アセチ
ルシクロヘキサンスルフォニルパ−オキシド等の過酸化
物類等の公知のラジカル重合開始剤が使用できる。また
アルコールとしては、メチルアルコール、エチルアルコ
ール、プロピルアルコール、ブチルアルコール等の低級
アルコールが用いられるが、経済的にみてメチルアルコ
ールが好ましい。The copolymerization of ethylene and vinyl ester is as follows:
In a known method, that is, in a batch system, a semi-batch system, or a continuous system, the polymerization is performed by solution polymerization, suspension polymerization, or emulsion polymerization in the presence of a polymerization initiator, but is performed by solution polymerization in the presence of an alcohol. Is industrially preferred.
In the case of solution polymerization, the solvent concentration is 0 to 50%, preferably 3 to 50%.
30%, and the polymerization rate is usually 20-80%, preferably 3
0 to 60%. The polymerization temperature is usually 20 to 100.
° C, preferably 40-80 ° C. As the polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2 ′
-Azobis- (2,4-dimethylvaleronitrile),
Nitriles such as 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), di-n-propylpropyl-oxycarbonate, bis-4-tert-phenyl
Butylhexyl par-oxydicarbonate, bis-2-
Known radical polymerization initiators such as carbonates such as ethylhexyl peroxycarbonyl carbonate and peroxides such as benzoyl peroxide, lauroyl peroxide and acetylcyclohexanesulfonyl peroxide can be used. As the alcohol, lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol are used, and methyl alcohol is preferable from the viewpoint of economy.
【００１９】スルホン酸基またはその塩、カルボン酸基
またはその塩、アンモニウム基等を含有するチオールの
存在下にエチレンとビニルエステルとを共重合するにあ
たって、チオールの重合系への添加量、添加方法は適宜
選択される。チオールは連鎖移動剤として働き、チオー
ルの重合系への添加量、添加方法は得られる重合体の重
合度、重合度分布等に影響するため、要求される末端イ
オン変性ＥＶＯＨの分散安定性、生成皮膜の強度等の面
から適宜決められるが、末端にイオン性基を効率よく導
入し、優れた品質のものを得るためには、重合系のビニ
ルエステルおよびエチレンの反応率に応じてチオールを
添加することにより、反応系のチオール量がビニルエス
テルおよびエチレンに対し、あまり変化しないようにす
ることが好ましい。When ethylene and vinyl ester are copolymerized in the presence of a thiol containing a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, an ammonium group, etc., the amount and method of addition of the thiol to the polymerization system Is appropriately selected. The thiol acts as a chain transfer agent, and the amount of the thiol added to the polymerization system and the method of addition affect the degree of polymerization and the degree of polymerization distribution of the resulting polymer. It is determined as appropriate from the viewpoint of the strength of the film, etc., but in order to efficiently introduce ionic groups at the terminals and obtain excellent quality, thiol is added according to the reaction rate of the polymerization vinyl ester and ethylene. By doing so, it is preferable that the amount of thiol in the reaction system does not change much with respect to vinyl ester and ethylene.
【００２０】スルホン酸基またはその塩、カルボン酸基
またはその塩、アンモニウム基等を含有するチオールと
しては種々のものが用いられる。Various thiols containing a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, and an ammonium group are used.
【００２１】スルホン酸基またはその塩を有するチオー
ルとして、次の一般式で表されるものがあげられる。こ
こで、ｎは１〜４、Ｒ1〜Ｒ8はメチル基または水素原
子、Ｍは水素原子またはアルカリ金属をそれぞれ示す。The thiol having a sulfonic acid group or a salt thereof includes those represented by the following general formula. Here, n respectively 1~4, R 1 ~R 8 are a methyl group or a hydrogen atom, M is a hydrogen atom or an alkali metal.
【００２２】[0022]
【化１】 Embedded image
【００２３】[0023]
【化２】 Embedded image
【００２４】[0024]
【化３】 Embedded image
【００２５】カルボン酸基またはその塩を有するチオー
ルとして、次の一般式で表されるものがあげられる。こ
こで、ｎは０〜４、Ｒ9〜Ｒ11は水素原子または低級ア
ルキル基（置換基を含んでいてもよい）、Ｍは水素原
子、アルカリ金属またはアンモニウム基をそれぞれ示
す。The thiol having a carboxylic acid group or a salt thereof includes those represented by the following general formula. Here, n represents 0 to 4, R 9 to R 11 represent a hydrogen atom or a lower alkyl group (which may have a substituent), and M represents a hydrogen atom, an alkali metal or an ammonium group.
【００２６】[0026]
【化４】 Embedded image
【００２７】[0027]
【化５】 Embedded image
【００２８】アンモニウム基を有するチオールとして、
次の一般式で表されるものがあげられる。ここでｎは０
〜３、ｍは１〜１０、Ｒ12、Ｒ13、Ｒ16、Ｒ17、Ｒ18は
水素原子またはメチル基、Ｒ14、Ｒ15は低級アルキル基
（置換基を含んでいてもよい）、Ａはアミンあるいはア
ンモニウム窒素原子と化６式中のアミド基の窒素原子あ
るいは化８式中の酸素原子とを連結する基をそれぞれ示
す。As a thiol having an ammonium group,
Examples include those represented by the following general formula. Where n is 0
And m are 1 to 10, R 12 , R 13 , R 16 , R 17 and R 18 are a hydrogen atom or a methyl group, R 14 and R 15 are a lower alkyl group (which may contain a substituent), A represents a group connecting an amine or ammonium nitrogen atom to a nitrogen atom of an amide group in the formula or an oxygen atom in the formula.
【００２９】[0029]
【化６】 Embedded image
【００３０】[0030]
【化７】 Embedded image
【００３１】[0031]
【化８】 Embedded image
【００３２】[0032]
【化９】 Embedded image
【００３３】ビニルエステルとしては蟻酸ビニル、酢酸
ビニル、プロピオン酸ビニル、安息香酸ビニル、三フッ
化酢酸ビニル、ピバリン酸ビニル等のエチレンと共重合
可能で該共重合体をけん化することによりビニルアルコ
ールに変換可能なモノマーの１種または２種以上が使用
できるが、酢酸ビニルが経済的にみて特に好ましい。The vinyl ester can be copolymerized with ethylene such as vinyl formate, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl trifluoroacetate, vinyl pivalate, and the like. One or more of the convertible monomers can be used, but vinyl acetate is particularly preferred from an economic standpoint.
【００３４】重合で得られた末端にイオン性基を有する
エチレン−ビニルエステル系共重合体は、ついでけん化
反応に供せられる。けん化反応はアルカリ性触媒を用い
て公知の方法、すなわち通常共重合体をアルコール溶液
としてアルコリシスにより反応を実施するのが有利であ
る。特に日本特許第５７５８８９号および同６１１５５
７号に開示された塔式反応器を用い、けん化反応中に副
生する酢酸メチルを、塔底にアルコール蒸気を吹き込ん
で塔頂から除去しながら行う方法が最も好適である。ア
ルカリ性触媒としては、水酸化ナトリウム、水酸化カリ
ウム等のアルカリ金属の水酸化物、ナトリウムメチラー
ト、カリウムメチラート等のアルコラートが用いられる
が、水酸化ナトリウムが経済的にみて特に好ましい。け
ん化反応温度は６０〜１７５℃の範囲から適宜選ばれ
る。特に前記塔式反応器を用いる場合には、共重合体の
組成にもよるが、反応時間の短縮、ＥＶＯＨのアルコー
ル類への溶解性等から１００℃以上が好ましい。The ethylene-vinyl ester copolymer having an ionic group at the terminal obtained by polymerization is then subjected to a saponification reaction. The saponification reaction is advantageously carried out by a known method using an alkaline catalyst, that is, the reaction is usually carried out by alcoholysis using a copolymer as an alcohol solution. In particular, Japanese Patent Nos. 575889 and 61155
The most preferred method is to use the column reactor disclosed in No. 7 and remove methyl acetate by-produced during the saponification reaction from the top of the column by blowing alcohol vapor from the bottom of the column. As the alkaline catalyst, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and alcoholates such as sodium methylate and potassium methylate are used, and sodium hydroxide is particularly preferable in view of economy. The saponification reaction temperature is appropriately selected from the range of 60 to 175 ° C. In particular, when the above-mentioned tower reactor is used, the temperature is preferably 100 ° C. or higher from the viewpoint of shortening the reaction time and solubility of EVOH in alcohols, although it depends on the composition of the copolymer.
【００３５】けん化反応後、末端イオン変性ＥＶＯＨを
単離するに当っては、公知の方法が適用され、特に日本
特許７２５５２０号に開示されたストランド状に析出さ
せる方法が好適である。析出単離された末端イオン変性
ＥＶＯＨは、公知の方法で水洗後必要に応じて酸処理等
の公知の熱安定化処理を行い、ついで乾燥される。For isolating the terminal ion-modified EVOH after the saponification reaction, a known method is applied, and a method of precipitating in the form of a strand disclosed in Japanese Patent No. 725520 is particularly preferable. The terminal ion-modified EVOH which has been isolated by precipitation is washed with water by a known method, and if necessary, subjected to a known heat stabilization treatment such as an acid treatment, and then dried.
【００３６】このようにして得られる本発明のＥＶＯＨ
は、分子の末端にイオン性基が結合されているため、Ｅ
ＶＯＨ成分の構造が殆ど乱されないため、融点の低下が
少なく、高バリヤー性能が保持できる特長を有する。ま
た水に分散しやすく、水性乳化分散液を製造するのに好
適であり、薄い均質な皮膜が塗布でき、乾燥した皮膜が
ガスバリヤー性に優れる。The thus obtained EVOH of the present invention
Has an ionic group attached to the end of the molecule,
Since the structure of the VOH component is hardly disturbed, there is a feature that a decrease in melting point is small and high barrier performance can be maintained. Further, it is easily dispersed in water and is suitable for producing an aqueous emulsified dispersion, a thin homogeneous film can be applied, and a dried film has excellent gas barrier properties.
【００３７】末端イオン変性ＥＶＯＨを乳化分散させる
方法には制限はなく、公知の方法が使用可能である。例
えば末端イオン変性ＥＶＯＨの溶液を該ＥＶＯＨの非溶
剤である水と撹拌下に接触させてＥＶＯＨ粒子を３μｍ
以下、好ましくは２μｍ以下、最適には１μｍ以下の微
粒子として析出させ、次いで溶剤を除去することにより
水性乳化分散液を得ることができる。なおここで微粒子
の径は数平均粒子径である。The method of emulsifying and dispersing the terminal ion-modified EVOH is not limited, and a known method can be used. For example, a solution of a terminal ion-modified EVOH is brought into contact with water, which is a non-solvent for the EVOH, with stirring to make the EVOH particles 3 μm.
The aqueous emulsified dispersion can be obtained by precipitating as fine particles having a particle size of 2 μm or less, optimally 1 μm or less, and then removing the solvent. Here, the diameter of the fine particles is a number average particle diameter.
【００３８】水性乳化分散液の固形分濃度は製造条件お
よび使用用途等により適宜決められるが、高濃度でしか
も安定な分散液の得られることが本発明の特徴である。
固形分濃度としては１０重量％以上、さらに好ましくは
１５重量％以上、最適には２０重量％以上である。固形
分濃度の上限には特に制限はないが、あまり高濃度にな
りすぎると水性分散液の放置安定性がやや不良になる場
合があるので、通常６０重量％以下が好ましく、さらに
好ましくは５０重量％以下、最適には４０重量％以下で
ある。The solid content concentration of the aqueous emulsion dispersion is appropriately determined depending on the production conditions, the intended use, and the like, and it is a feature of the present invention that a highly concentrated and stable dispersion can be obtained.
The solid content concentration is 10% by weight or more, more preferably 15% by weight or more, and most preferably 20% by weight or more. The upper limit of the solid content concentration is not particularly limited. However, if the concentration is too high, the storage stability of the aqueous dispersion may be slightly poor. Therefore, it is usually preferably 60% by weight or less, more preferably 50% by weight. %, Optimally up to 40% by weight.
【００３９】溶剤としては、例えばメチルアルコール、
エチルアルコール、プロピルアルコール、ブチルアルコ
ール等の１価アルコール、エチレングリコール、プロピ
レングリコール等の２価アルコール、グリセリン等の３
価アルコール、フェノール、クレゾール等のフェノール
類、エチレンジアミン、トリメチレンジアミン等のアミ
ン類、ジメチルスルホキシド、ジメチルアセトアミド、
Ｎ−メチルピロリドン等、あるいはこれらの含水物等が
単独あるいは２種以上混合されて使用できる。特に好ま
しい溶剤系はアルコール−水系の混合溶剤、例えば水−
メチルアルコール、水−ノルマルプロピルアルコール、
水−イソプロピルアルコール等である。As the solvent, for example, methyl alcohol,
Monohydric alcohols such as ethyl alcohol, propyl alcohol and butyl alcohol, dihydric alcohols such as ethylene glycol and propylene glycol, and trihydric alcohols such as glycerin
Polyhydric alcohols, phenols, phenols such as cresol, ethylenediamine, amines such as trimethylenediamine, dimethylsulfoxide, dimethylacetamide,
N-methylpyrrolidone or the like, or a hydrate thereof may be used alone or in combination of two or more. A particularly preferred solvent system is an alcohol-water mixed solvent such as water-
Methyl alcohol, water-normal propyl alcohol,
Water-isopropyl alcohol.
【００４０】溶剤系の有機溶剤は、蒸発法、抽出法ある
いは透析法等の適宜な方法で除去することができる。除
去の程度は高いことが望ましいが、経済性との兼ね合い
で小割合の有機溶剤を残存させることは可能である。The solvent-based organic solvent can be removed by an appropriate method such as an evaporation method, an extraction method or a dialysis method. It is desirable that the degree of removal be high, but it is possible to leave a small proportion of the organic solvent in view of economy.
【００４１】また別の方法として、高温では溶解するが
低温にすると不溶になる溶剤系に末端イオン変性ＥＶＯ
Ｈを加熱溶解した後、その溶液を冷却することにより微
粒子を析出分散させる方法も採用できる。しかる後その
溶剤を水と置換することにより水性乳化分散液とするこ
とができる。高温では溶解するが低温にすると不溶にな
る溶剤系としては、先に示した溶剤のうちアルコール類
の単独あるいは水との混合溶剤等が使用できる。As another method, a terminal ion-modified EVO is dissolved in a solvent system which dissolves at a high temperature but becomes insoluble at a low temperature.
After H is dissolved by heating, the solution may be cooled to precipitate and disperse the fine particles. Thereafter, by replacing the solvent with water, an aqueous emulsified dispersion can be obtained. As the solvent system which dissolves at a high temperature but becomes insoluble at a low temperature, any of the above-mentioned solvents alone or a mixed solvent with water can be used.
【００４２】さらに別の方法として、末端イオン変性Ｅ
ＶＯＨの溶液を非溶剤と接触させるか、あるいは冷却す
ることにより析出分散させた粒子を濾別し、その粒子を
水中に分散させる方法も可能である。As still another method, terminal ion-modified E
A method is also possible in which a VOH solution is brought into contact with a non-solvent or cooled, and the particles precipitated and dispersed by filtration are separated by filtration, and the particles are dispersed in water.
【００４３】また末端イオン変性ＥＶＯＨを水中に直接
分散させることも可能な場合がある。例えばイオン変性
ＥＶＯＨを水と混合し、撹拌機あるいはボールミル等で
撹拌することにより乳化分散させることも可能である。
ただし分散に時間を要する等の問題がある。In some cases, the terminal ion-modified EVOH can be directly dispersed in water. For example, it is also possible to emulsify and disperse by mixing ion-modified EVOH with water and stirring with a stirrer or a ball mill.
However, there is a problem that dispersion takes time.
【００４４】本発明において好適な水性分散液の製法と
しては、末端イオン変性ＥＶＯＨを、溶剤、例えば水−
アルコ−ルの混合溶剤に撹拌下、温度５０〜７５℃で溶
解して溶液とし次いで冷却（温度−１０〜３０℃）し、
ＥＶＯＨ粒子を析出して分散化（エマルジョン化）し、
次に減圧下（温度１０〜３０℃、圧力１０〜１５０ｍｍ
Ｈｇ）にアルコールを除去し、さらに水を所望量除去す
ることによって、所望の固形分濃度の水性分散液を得る
方法があげられる。本発明の水性分散液には粘度を低下
させる目的で水酸化ナトリウム、塩化ナトリウム、酢酸
ナトリウム、硫酸ナトリウム、硝酸ナトリウムなどのア
ルカリ金属化合物、水酸化カルシウム、塩化カルシウ
ム、酢酸カルシウム、硫酸カルシウム、硝酸カルシウム
などのアルカリ土類金属化合物、その他の電解質を０．
０１〜０．５重量％（対ポリマー）配合してもよい。配
合は、分散質の末端イオン変性ＥＶＯＨを微粒子化する
前でも後でもよい。In the present invention, a suitable aqueous dispersion is prepared by adding a terminal ion-modified EVOH to a solvent such as water-
The mixture was dissolved in a mixed solvent of alcohol at a temperature of 50 to 75 ° C under stirring to form a solution, and then cooled (temperature of -10 to 30 ° C).
EVOH particles are precipitated and dispersed (emulsified),
Next, under reduced pressure (temperature of 10 to 30 ° C., pressure of 10 to 150 mm
A method of obtaining an aqueous dispersion having a desired solid content concentration by removing the alcohol in Hg) and further removing a desired amount of water. Sodium hydroxide, sodium chloride, sodium acetate, sodium sulfate, alkali metal compounds such as sodium nitrate, calcium hydroxide, calcium chloride, calcium acetate, calcium sulfate, calcium nitrate for the purpose of reducing the viscosity of the aqueous dispersion of the present invention Alkaline earth metal compounds such as
You may mix | blend 01-0.5 weight% (with respect to a polymer). The compounding may be performed before or after the terminal ion-modified EVOH of the dispersoid is formed into fine particles.
【００４５】本発明の末端イオン変性ＥＶＯＨは、特に
水性分散液を製造するのに好適であるが、通常のＥＶＯ
Ｈと同様に溶融成形材料としても用いられ、押出成形、
射出成形等の各種方法で成形可能である。The terminal ion-modified EVOH of the present invention is particularly suitable for producing an aqueous dispersion,
Like H, it is also used as a melt molding material,
It can be molded by various methods such as injection molding.
【００４６】本発明の水性乳化分散液は優れたガスバリ
ヤー性の皮膜を形成する塗布材料として有用であるが、
その優れた力学的性能や化学的性能を生かして、他の用
途、例えば噴霧乾燥して微粒子粉末にしたり、また塗料
や接着剤のバインダーやビヒクル等の広範囲に利用でき
る。The aqueous emulsion dispersion of the present invention is useful as a coating material for forming a film having excellent gas barrier properties.
Utilizing its excellent mechanical performance and chemical performance, it can be used in a wide range of applications such as spray-drying to fine particle powder, and binders and vehicles for paints and adhesives.
【００４７】本発明の水性乳化分散液には、必要に応じ
て本発明の目的を妨げない範囲で通常の界面活性剤や保
護コロイドを添加することは自由である。また他の樹脂
の水性分散液、光あるいは熱等に対する安定剤、顔料、
滑剤、防黴剤あるいは造膜助剤等を添加することもでき
る。The aqueous emulsified dispersion of the present invention may be optionally added with a usual surfactant or protective colloid as long as the object of the present invention is not hindered. In addition, an aqueous dispersion of another resin, a stabilizer against light or heat, a pigment,
Lubricants, fungicides, film-forming auxiliaries and the like can also be added.
【００４８】以上に説明したように、本発明によれば貯
蔵あるいは使用時の安定性に優れた固形分濃度の水性分
散液が得られ、かつ水性であるため環境の汚染等の問題
もない利点があり、塗布乾燥により優れたガスバリヤー
性、保香性および耐油・耐薬品性を示す薄い皮膜を形成
できる有用な塗布剤として各種基材表面に塗布できる。
ここで基材としてはとくに熱可塑性樹脂｛ポリオレフィ
ン（ポリエチレン、ポリプロピレンなど）、ポリエステ
ル、ポリアミド、ポリ塩化ビニル、ポリ塩化ビニリデ
ン、ポリカーボネート、ポリスチレン、ポリビニルアル
コール、酢酸ビニル樹脂（エチレン−酢酸ビニル共重合
体など）など｝からなる各種成形品（フィルム、シー
ト、カップ、ボトルなど）が好適なものとしてあげら
れ、また繊維集合体（紙、不織布、織布、ファイブラス
ケーシングなど）、無機物（セメントなど）、金属、ポ
リ塩化ビニル樹脂製壁紙、写真印画紙などもあげられ
る。As described above, according to the present invention, an aqueous dispersion having a solid concentration excellent in stability during storage or use can be obtained, and since it is aqueous, there is no problem of environmental pollution. It can be applied to various substrate surfaces as a useful coating agent capable of forming a thin film having excellent gas barrier properties, fragrance retention properties, and oil and chemical resistance by coating and drying.
Here, the base material is, in particular, a thermoplastic resin ｛polyolefin (polyethylene, polypropylene, etc.), polyester, polyamide, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polystyrene, polyvinyl alcohol, vinyl acetate resin (ethylene-vinyl acetate copolymer, etc.) ), Etc. (films, sheets, cups, bottles, etc.) are suitable, and fiber aggregates (paper, nonwoven fabric, woven fabric, fibrous casing, etc.), inorganic substances (cement, etc.), Metal, polyvinyl chloride resin wallpaper, photographic paper and the like are also included.
【００４９】また本発明の水性分散液を基材表面に塗布
する方法としては、キャスティングヘッドからの吐出、
ロールコート、ドクターロールコート、ドクターナイフ
コート、カーテンフローコート、スプレー、浸漬、刷毛
塗りなど任意の手段が例示される。このように塗布され
た基材を乾燥・熱処理する方法としては乾熱処理法、た
とえば赤外線照射法、熱風乾燥法などが例示される。こ
れらの赤外線照射、熱風乾燥などはそれぞれ単独で使用
してもよいし、また併用することもできる。また乾燥・
熱処理の温度は３０〜１８０℃であることが好ましく、
下限値については５０℃以上が好ましく、最適には８０
℃以上である。また乾燥・熱処理の時間は５秒〜１０分
が好ましく、さらに好適には１〜５分である。乾燥・熱
処理中は条件、たとえば温度を増減させること、例えば
最初は低温で処理し、徐々に温度を上昇させることなど
は自由である。このよな乾燥・熱処理を施すことにより
ガスバリヤー性の優れた皮膜が基材表面に形成される。
また本発明の水性分散液を塗布、乾燥・熱処理したあと
の皮膜の厚さは０．５〜１５μｍであることが好まし
く、さらに好適には１〜１０μｍ、最適には２〜６μｍ
である。The method of applying the aqueous dispersion of the present invention to the surface of a substrate includes discharging from a casting head,
Any means such as roll coating, doctor roll coating, doctor knife coating, curtain flow coating, spraying, dipping, and brushing are exemplified. Examples of the method of drying and heat treating the substrate coated in this way include a dry heat treatment method, for example, an infrared irradiation method, a hot air drying method, and the like. These infrared irradiation, hot air drying and the like may be used alone or in combination. Also dry
The temperature of the heat treatment is preferably 30 to 180 ° C,
The lower limit is preferably 50 ° C. or higher, and optimally 80 ° C.
° C or higher. The drying and heat treatment time is preferably from 5 seconds to 10 minutes, more preferably from 1 to 5 minutes. During the drying and heat treatment, conditions such as increasing and decreasing the temperature, for example, treating at a low temperature at first and gradually increasing the temperature are free. By performing such drying and heat treatment, a film having excellent gas barrier properties is formed on the substrate surface.
Further, the thickness of the film after coating, drying and heat treatment of the aqueous dispersion of the present invention is preferably 0.5 to 15 μm, more preferably 1 to 10 μm, and most preferably 2 to 6 μm.
It is.
【００５０】以下、実施例により本発明をさらに詳細に
説明するが、これにより本発明は何ら限定されるもので
はない。実施例中の「部」あるいは「％」は、特に断り
のない限り重量基準で表したものである。また溶剤組成
も重量比で示す。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. “Parts” or “%” in the examples are expressed on a weight basis unless otherwise specified. The solvent composition is also shown by weight ratio.
【００５１】[0051]
実施例１ 酢酸ビニル１３４０部、メチルアルコール８４部、３−
メルカプトプロパン酸ナトリウム０．２３部を高圧重合
槽に仕込み、内部を十分窒素置換した後エチレンガスを
仕込んだ。内温６０℃、エチレン圧力４１Ｋｇ／ｃｍ2
Ｇに調節した後、重合開始剤２，２’−アゾビスイソブ
チロニトリル１．０７部を加え、さらに３−メルカプト
プロパン酸ナトリウムのメチルアルコール溶液（濃度
２．０％）を３８．４部／時間の速度で３．８時間連続
的に添加して重合を行った。酢酸ビニルの重合率は３９
％であった。Example 1 1340 parts of vinyl acetate, 84 parts of methyl alcohol, 3-
0.23 parts of sodium mercaptopropanoate was charged into a high-pressure polymerization tank, and the inside thereof was sufficiently purged with nitrogen, and then ethylene gas was charged. Internal temperature 60 ° C, ethylene pressure 41Kg / cm 2
After adjusting to G, 1.07 parts of a polymerization initiator 2,2'-azobisisobutyronitrile was added, and 38.4 parts of a methyl alcohol solution of sodium 3-mercaptopropanoate (concentration 2.0%) was further added. Per hour for 3.8 hours to carry out polymerization. The conversion of vinyl acetate is 39.
%Met.
【００５２】冷却後エチレンガスを分離除去し、さらに
減圧下メチルアルコールを添加しながら未反応の酢酸ビ
ニルを系外に追い出し、エチレン−酢酸ビニル系共重合
体のメチルアルコール溶液を得た。After cooling, ethylene gas was separated and removed, and unreacted vinyl acetate was driven out of the system while adding methyl alcohol under reduced pressure to obtain a methyl alcohol solution of an ethylene-vinyl acetate copolymer.
【００５３】次にこのメチルアルコール溶液を塔式けん
化反応器に供給し、さらに水酸化ナトリウムを共重合体
中の酢酸ビニル単位に対するモル比が０．０３となるよ
うに該反応器に添加し、塔下部よりメチルアルコール蒸
気を吹き込み、塔頂より副生する酢酸メチルを除去しな
がら、塔内温度１２０℃でけん化反応を行った。ついで
得られたＥＶＯＨのメチルアルコール溶液に水蒸気を吹
き込み、溶液の溶剤組成を水／メチルアルコール混合系
に変えた後、５℃のメチルアルコール１０％水溶液中に
ストランド状に吐出させ、凝固析出後、切断した。次に
蒸留水で十分に洗浄し、６０℃で５時間熱風乾燥、さら
に１００℃で１２時間真空乾燥した。Next, this methyl alcohol solution was fed to a tower type saponification reactor, and sodium hydroxide was further added to the reactor such that the molar ratio to vinyl acetate units in the copolymer was 0.03. Saponification reaction was carried out at a temperature in the tower of 120 ° C. while methyl alcohol vapor was blown in from the bottom of the tower to remove by-product methyl acetate from the top of the tower. Then, steam is blown into the obtained EVOH methyl alcohol solution to change the solvent composition of the solution to a water / methyl alcohol mixed system, and then discharged into a 10% aqueous solution of methyl alcohol at 5 ° C. in the form of a strand, and solidified and precipitated. Cut. Next, it was sufficiently washed with distilled water, dried with hot air at 60 ° C. for 5 hours, and further dried in vacuum at 100 ° C. for 12 hours.
【００５４】このＥＶＯＨをｄ6−ＤＭＳＯ（重水素化
ジメチルスルホキシド）とＣＤ3ＯＤ（重水素化メチル
アルコール）とからなる混合溶剤に溶解し、1Ｈ−ＮＭ
Ｒを測定したところ、図１のスペクトルが得られた。こ
れより分子の末端にカルボン酸ナトリウムを有するエチ
レン含量３２モル％、けん化度９９．９モル％の末端イ
オン変性ＥＶＯＨであることが分かる。このＥＶＯＨを
濃度１モル／リットルのチオシアン酸アンモニウムを含
有する水／フェノール系混合溶剤（重量比１５／８５）
に溶解し、３０℃で固有粘度（以下この条件で測定した
固有粘度を単に固有粘度と記す）を測定したところ０．
６２デシリットル／ｇであった。また濃度１％で３０℃
の水に１日溶解したときの水不溶解分（以下この条件で
測定した水不溶解分を単に水不溶解分と記す）は９９％
であった。またＤＳＣを用い、１０℃／分の昇温速度で
測定した融点（以下この条件で測定した融点を単に融点
と記す）は１８２℃であった。This EVOH was dissolved in a mixed solvent consisting of d 6 -DMSO (deuterated dimethyl sulfoxide) and CD 3 OD (deuterated methyl alcohol), and 1 H-NM
When R was measured, the spectrum of FIG. 1 was obtained. This shows that the terminal ion-modified EVOH having an ethylene content of 32 mol% having a sodium carboxylate at the terminal of the molecule and a saponification degree of 99.9 mol%. This EVOH is mixed with a water / phenol-based mixed solvent containing ammonium thiocyanate at a concentration of 1 mol / l (weight ratio 15/85).
Was dissolved at 30 ° C. and the intrinsic viscosity (hereinafter, the intrinsic viscosity measured under these conditions is simply referred to as the intrinsic viscosity) was measured.
It was 62 deciliters / g. 30% at 1% concentration
Water-insoluble matter when dissolved in water for 1 day (hereinafter, the water-insoluble matter measured under these conditions is simply referred to as water-insoluble matter) is 99%
Met. The melting point measured by a DSC at a rate of temperature rise of 10 ° C./min (hereinafter, the melting point measured under these conditions is simply referred to as melting point) was 182 ° C.
【００５５】この末端イオン変性ＥＶＯＨ５０部を水／
メチルアルコール３０／７０の混合溶剤６００部に６５
℃で加熱溶解した。ついで撹拌下に室温まで冷却したと
ころ粒子が析出し安定な分散液が得られた。平均粒子径
は０．９μｍであった。次いでこの分散液を撹拌下に２
０℃で減圧蒸発させてメチルアルコールを留去した。メ
チルアルコール留去過程でも粒子の凝集は殆ど認められ
ず、平均粒子径０．９μｍ、固形分濃度２４％の水性乳
化分散液を得た。放置安定性も良好で、４０℃で１０日
間放置しても凝集は殆ど認められなかった。50 parts of the terminal ion-modified EVOH was added to water /
65 in 600 parts of a mixed solvent of methyl alcohol 30/70
It melted by heating at ° C. Then, when the mixture was cooled to room temperature with stirring, particles were precipitated and a stable dispersion was obtained. The average particle size was 0.9 μm. The dispersion is then stirred for 2 hours.
Evaporation at 0 ° C. under reduced pressure removed methyl alcohol. Almost no aggregation of particles was observed in the process of distilling off methyl alcohol, and an aqueous emulsified dispersion having an average particle diameter of 0.9 μm and a solid content of 24% was obtained. The storage stability was also good, and almost no aggregation was observed even after being left at 40 ° C. for 10 days.
【００５６】一方、比較のため、固有粘度０．６３デシ
リットル／ｇ、エチレン含量３２モル％、けん化度９
９．５モル％、融点１８３℃、水不溶解分９９％の未変
性の通常のＥＶＯＨを用いて分散した場合、またこの通
常のＥＶＯＨに分散剤として公知のノニオン界面活性剤
のノニルフェノールエーテルのエチレンオキシド付加
物、アニオン界面活性剤のドデシルベンゼンスルホン酸
ナトリウム、あるいは高分子保護コロイドとしてけん化
度８０モル％、固有粘度０．７６デシリットル／ｇの部
分けん化ポリビニルアルコールを使用し、それ以外は実
施例１と同じ条件で分散を試みたが、いずれの場合も加
熱溶解した溶液を撹拌下に冷却する段階で粒子が凝集・
ブロック化してしまった。On the other hand, for comparison, an intrinsic viscosity of 0.63 deciliter / g, an ethylene content of 32 mol%, and a saponification degree of 9
When dispersed using unmodified ordinary EVOH having a melting point of 9.5 mol%, a melting point of 183 ° C., and a water-insoluble content of 99%, ethylene oxide of nonyl phenol ether, a nonionic surfactant known as a dispersant in this ordinary EVOH, An adduct, sodium dodecylbenzenesulfonate as an anionic surfactant, or partially saponified polyvinyl alcohol having a saponification degree of 80 mol% and an intrinsic viscosity of 0.76 deciliter / g was used as a polymer protective colloid. Attempts were made to disperse the particles under the same conditions.
It has been blocked.
【００５７】またエチレン、酢酸ビニルおよびアクリル
酸を共重合、けん化して得られた固有粘度０．６２デシ
リットル／ｇ、アクリル酸含量０．５モル％、エチレン
含量３２モル％、けん化度９９．５モル％、融点１７４
℃、水不溶解分９８％の三元ランダム共重合ＥＶＯＨを
用いたほかは実施例１と同じ条件で分散を試みたが、メ
チルアルコールを留去する過程で粒子が凝集して分散安
定性の良好な水性乳化分散液は得られなかった。An intrinsic viscosity obtained by copolymerizing and saponifying ethylene, vinyl acetate and acrylic acid is 0.62 deciliter / g, an acrylic acid content is 0.5 mol%, an ethylene content is 32 mol%, and a saponification degree is 99.5. Mol%, melting point 174
The dispersion was attempted under the same conditions as in Example 1 except that a ternary random copolymer EVOH having a water-insoluble content of 98% and a water insoluble content of 98% were used. A good aqueous emulsion dispersion was not obtained.
【００５８】このように本発明の末端イオン変性ＥＶＯ
Ｈを用いると、分子末端に結合したイオン性基が乳化分
散安定化に格別の効果を示し、安定な水性乳化分散液が
得られることが分かる。そして、この水性乳化分散液を
二軸延伸ポリプロピレンフィルム（膜厚２０μｍ）のプ
ライマー処理面に塗布して７０℃で５分間乾燥したとこ
ろきれいに造膜し、連続塗布膜が形成でき、造膜性に優
れることが分かった。さらに得られた形成皮膜を１５０
℃で３０秒間熱処理したフィルム（ＥＶＯＨ層の厚み５
μｍ）の酸素バリヤー性を測定したところ、酸素透過量
が３．４ｃｃ／ｍ2・ｄａｙ・ａｔｍ（２０℃、０％Ｒ
Ｈ）で食品包装材として良好な性能を示した。（以下、
酸素透過量の測定条件および単位は同一である。）As described above, the terminal ion-modified EVO of the present invention
It can be seen that when H is used, the ionic group bonded to the molecular terminal has a remarkable effect on the emulsification and dispersion stabilization, and a stable aqueous emulsion dispersion can be obtained. Then, this aqueous emulsified dispersion is applied to the primer-treated surface of a biaxially stretched polypropylene film (thickness: 20 μm) and dried at 70 ° C. for 5 minutes to form a clean film, and a continuous coating film can be formed. It turned out to be excellent. Further, the obtained formed film was subjected to 150
Film heat treated at 30 ° C. for 30 seconds (EVOH layer thickness 5
μm), the oxygen permeability was 3.4 cc / m 2 · day · atm (20 ° C., 0% R
H) showed good performance as a food packaging material. (Less than,
The measurement conditions and units for the amount of oxygen permeation are the same. )
【００５９】実施例２ ２−アクリルアミド−２−メチルプロパンスルホン酸９
１部、水酸化ナトリウム１６部、過酸化ベンゾイル０．
０６部をメチルアルコール２９０部に室温下で溶解し、
系内の酸素を窒素で置換した。ついで内温を１５〜２０
℃に保持しながらチオ酢酸を２部／分の速度で８０分間
連続的に添加した後、内温を６５℃とし４時間還流し
た。次に内温４０℃でチオ酢酸とメチルアルコールを減
圧下で留去した。得られた白色粉末１００部をメチルア
ルコール３００部に溶解した後、水酸化ナトリウム４部
を添加し、窒素気流下４０℃で３時間加熱した。ついで
この溶液に酢酸６部を添加後、内温３５℃でメチルアル
コールを減圧下で留去し、２−アクリルアミド−２−メ
チルプロパンスルホン酸のチオール化物を得た。なおチ
オール化が定量的に行われたことは、酸化還元滴定法に
より確認した。Example 2 2-acrylamido-2-methylpropanesulfonic acid 9
1 part, sodium hydroxide 16 parts, benzoyl peroxide 0.1 part
06 parts are dissolved in 290 parts of methyl alcohol at room temperature,
Oxygen in the system was replaced with nitrogen. Then the internal temperature is 15-20
After continuously adding thioacetic acid at a rate of 2 parts / minute for 80 minutes while maintaining the temperature at ℃, the internal temperature was brought to 65 ° C and refluxed for 4 hours. Next, thioacetic acid and methyl alcohol were distilled off under reduced pressure at an internal temperature of 40 ° C. After dissolving 100 parts of the obtained white powder in 300 parts of methyl alcohol, 4 parts of sodium hydroxide was added, and the mixture was heated at 40 ° C. for 3 hours under a nitrogen stream. Then, after adding 6 parts of acetic acid to this solution, methyl alcohol was distilled off under reduced pressure at an internal temperature of 35 ° C. to obtain a thiolated product of 2-acrylamido-2-methylpropanesulfonic acid. It was confirmed that the thiolation was performed quantitatively by a redox titration method.
【００６０】酢酸ビニル１０９０部、メチルアルコール
１０５部、２−アクリルアミド−２−メチルプロパンス
ルホン酸のチオール化物を水酸化ナトリウムで中和して
得られたナトリウム塩０．２５部を高圧重合槽に仕込
み、内部を十分窒素置換した後エチレンガスを仕込ん
だ。内温６０℃、エチレン圧力３０Ｋｇ／ｃｍ2Ｇに調
節した後、重合開始剤２，２’−アゾビスイソブチロニ
トリル１．５３部を加え、さらに上記２−アクリルアミ
ド−２−メチルプロパンスルホン酸ナトリウムのチオー
ル化物のメチルアルコール溶液（濃度１８％）を１４．
４部／時間の速度で３．４時間連続的に添加して重合を
行った。酢酸ビニルの重合率は４０％であった。1090 parts of vinyl acetate, 105 parts of methyl alcohol, and 0.25 part of a sodium salt obtained by neutralizing a thiolated product of 2-acrylamido-2-methylpropanesulfonic acid with sodium hydroxide were charged into a high-pressure polymerization tank. After the inside was sufficiently purged with nitrogen, ethylene gas was charged. After adjusting the internal temperature to 60 ° C. and the ethylene pressure to 30 kg / cm 2 G, 1.53 parts of a polymerization initiator 2,2′-azobisisobutyronitrile was added, and the above 2-acrylamido-2-methylpropanesulfonic acid was further added. 13. A solution of sodium thiol in methyl alcohol (18% concentration)
Polymerization was carried out by continuously adding at a rate of 4 parts / hour for 3.4 hours. The polymerization rate of vinyl acetate was 40%.
【００６１】実施例１と同様に未反応のエチレンおよび
酢酸ビニルを除去、けん化、凝固析出、切断、蒸留水で
洗浄、さらに０．５ｇ／リットルの酢酸水溶液で洗浄、
ついで乾燥して分子の末端にスルホン酸基を有する固有
粘度０．８７デシリットル／ｇ、エチレン含量２５モル
％、けん化度９９．３モル％、融点１９３℃、水不溶解
分９７％の末端イオン変性ＥＶＯＨを得た。In the same manner as in Example 1, unreacted ethylene and vinyl acetate were removed, saponified, coagulated and precipitated, cut, washed with distilled water, and further washed with a 0.5 g / liter aqueous acetic acid solution.
Then, it is dried and modified with terminal ions having an intrinsic viscosity of 0.87 deciliter / g having a sulfonic acid group at the terminal of the molecule, an ethylene content of 25 mol%, a saponification degree of 99.3 mol%, a melting point of 193 ° C. and a water-insoluble content of 97%. EVOH was obtained.
【００６２】この末端イオン変性ＥＶＯＨ５０部を水／
メチルアルコール＝４０／６０の混合溶剤５００部に７
０℃で加熱溶解した。この溶液を撹拌下に室温まで冷却
したところ、粒子が析出し安定な分散液が得られた。平
均粒子径０．８μｍであった。ついでこの分散液を撹拌
下に２５℃で減圧蒸発させてメチルアルコールを留去し
た。メチルアルコール留去過程でも粒子の凝集は殆ど認
められず、平均粒子径０．８μｍ、固形分濃度２６％の
水性乳化分散液を得た。この水性乳化分散液を実施例１
と同様に塗布、乾燥・熱処理したフィルム（ＥＶＯＨ層
厚み５μｍ）の酸素透過量は２．６でガスバリヤー性が
非常に良好であった。The terminal ion-modified EVOH (50 parts) was mixed with water /
7 in 500 parts of a mixed solvent of methyl alcohol = 40/60
The mixture was heated and dissolved at 0 ° C. When this solution was cooled to room temperature with stirring, particles were precipitated and a stable dispersion was obtained. The average particle size was 0.8 μm. The dispersion was then evaporated under reduced pressure at 25 ° C. with stirring to distill off the methyl alcohol. Almost no particle aggregation was observed during the methyl alcohol distillation process, and an aqueous emulsified dispersion having an average particle size of 0.8 μm and a solid content of 26% was obtained. This aqueous emulsion dispersion was prepared in Example 1.
The oxygen permeation amount of the film (EVOH layer thickness 5 μm) coated, dried and heat-treated in the same manner as described above was 2.6, and the gas barrier property was very good.
【００６３】比較のため、けん化度が８７．６モル％で
あるほかは実施例２と同じ末端イオン変性ＥＶＯＨ（水
不溶解分９５％）を用い、実施例２と同様に水性分散液
を得ようとしたが粒子の凝集が目立ち、また塗布、乾燥
・熱処理した皮膜（膜厚４μｍ）の酸素透過量は１００
０以上でガスバリヤー性が著しく不良であった。For comparison, an aqueous dispersion was obtained in the same manner as in Example 2 by using the same terminal ion-modified EVOH (water-insoluble content: 95%) as in Example 2 except that the saponification degree was 87.6 mol%. However, the aggregation of particles was conspicuous, and the oxygen permeation amount of the coated (dried and heat-treated) film (film thickness 4 μm) was 100 μm.
At 0 or more, the gas barrier properties were extremely poor.
【００６４】また、実施例２と同様にして、分子の末端
にスルホン酸基を有する固有粘度０．３５デシリットル
／ｇ、エチレン含量２５モル％、けん化度９９．４モル
％、融点１９３℃、水不溶解分９７％の末端イオン変性
ＥＶＯＨを合成し、その水性分散液を作り、これを塗
布、乾燥したところヒビ割れが生じ、強度の十分な皮膜
は形成できなかった。In the same manner as in Example 2, an intrinsic viscosity having a sulfonic acid group at the terminal of the molecule was 0.35 dL / g, an ethylene content was 25 mol%, a saponification degree was 99.4 mol%, a melting point was 193 ° C., and water was A terminal ion-modified EVOH having an insoluble content of 97% was synthesized, an aqueous dispersion was prepared, and this was applied and dried. When this was applied and cracked, cracks occurred and a film having sufficient strength could not be formed.
【００６５】実施例３ 実施例２と同様にしてトリメチル−（３−メタクリルア
ミド）アンモニウムクロリドとチオ酢酸とを過酸化ベン
ゾイルの存在下に付加反応させ、ついで水酸化ナトリウ
ムでけん化することによりアンモニウムクロリド基を含
有するチオールを得た。Example 3 In the same manner as in Example 2, trimethyl- (3-methacrylamido) ammonium chloride was subjected to an addition reaction with thioacetic acid in the presence of benzoyl peroxide, followed by saponification with sodium hydroxide to obtain ammonium chloride. A thiol containing groups was obtained.
【００６６】酢酸ビニル９９０部、メチルアルコール１
２０部、トリメチル−（３−メタクリルアミド）アンモ
ニウムクロリドのチオール化物０．１７部を高圧重合槽
に仕込み、内部を十分窒素置換した後エチレンガスを仕
込んだ。内温６０℃、エチレン圧力６１Ｋｇ／ｃｍ2Ｇ
に調節した後、重合開始剤２，２’−アゾビス−（２，
４−ジメチルバレロニトリル）６．２部を加え、さらに
上記アンモニウムクロリド基含有チオールのメチルアル
コール溶液（濃度５％）を３９．４部／時間の速度で
３．３時間連続的に添加して重合を行った。酢酸ビニル
の重合率は３８％であった。990 parts of vinyl acetate, methyl alcohol 1
20 parts and 0.17 part of a thiolated product of trimethyl- (3-methacrylamide) ammonium chloride were charged into a high-pressure polymerization tank, and the inside thereof was sufficiently purged with nitrogen, and then ethylene gas was charged. Internal temperature 60 ° C, ethylene pressure 61Kg / cm 2 G
After adjusting to 2, the polymerization initiator 2,2'-azobis- (2,
Then, 6.2 parts of 4-dimethylvaleronitrile) were added, and further, the above-mentioned ammonium chloride group-containing thiol methyl alcohol solution (concentration: 5%) was continuously added at a rate of 39.4 parts / hour for 3.3 hours to carry out polymerization. Was done. The conversion of vinyl acetate was 38%.
【００６７】実施例１と同様に未反応のエチレンおよび
酢酸ビニルを除去、けん化、凝固析出、切断、蒸留水で
洗浄、ついで乾燥して分子の末端にアンモニウムクロリ
ド基を有する固有粘度０．５４デシリットル／ｇ、エチ
レン含量４８モル％、けん化度９９．２モル％、融点１
５７℃、水不溶解分９８％の末端イオン変性ＥＶＯＨを
得た。In the same manner as in Example 1, unreacted ethylene and vinyl acetate were removed, saponified, coagulated and precipitated, cut, washed with distilled water, and dried to obtain an intrinsic viscosity of 0.54 deciliter having an ammonium chloride group at the terminal of the molecule. / G, ethylene content 48 mol%, degree of saponification 99.2 mol%, melting point 1
There was obtained a terminal ion-modified EVOH having a water-insoluble content of 98% at 57 ° C.
【００６８】この末端イオン変性ＥＶＯＨ５０部を水／
イソプロピルアルコール＝２０／８０の混合溶剤１００
０部に６５℃で加熱溶解し、次いで溶液を撹拌下に室温
まで冷却したところ、平均粒子径０．８μｍの安定な分
散液が得られた。ついでこの分散液を撹拌下に３０℃で
減圧蒸発させてイソプロピルアルコールを留去し、平均
粒子径０．８μｍ、固形分濃度２２％の安定な水性分散
液を得た。この水性乳化分散液を実施例１と同様に塗
布、乾燥・熱処理したフィルム（ＥＶＯＨ厚み５μｍ）
の酸素透過量は８．０でガスバリヤー性が良好であっ
た。The terminal ion-modified EVOH (50 parts) was mixed with water /
Isopropyl alcohol = 20/80 mixed solvent 100
In 0 part, the mixture was heated and dissolved at 65 ° C., and then the solution was cooled to room temperature with stirring to obtain a stable dispersion having an average particle diameter of 0.8 μm. Then, this dispersion was evaporated under reduced pressure at 30 ° C. under stirring to distill off isopropyl alcohol, thereby obtaining a stable aqueous dispersion having an average particle diameter of 0.8 μm and a solid content of 22%. A film obtained by applying, drying and heat-treating this aqueous emulsion dispersion in the same manner as in Example 1 (EVOH thickness: 5 μm)
Had an oxygen permeation of 8.0 and good gas barrier properties.
【００６９】比較のため、実施例３と同様にして、固有
粘度０．７５デシリットル／ｇ、エチレン含量１３モル
％、けん化度９８．１モル％、融点２１２℃、水不溶解
分３０％の末端にアンモニウムクロリド基を有するＥＶ
ＯＨを合成し、このＥＶＯＨ５０部を水／イソプロピル
アルコール＝９０／１０の混合溶剤１０００部に６０℃
で加熱溶解、ついで冷却、さらにイソプロピルアルコー
ルの留去を行ったが、水不溶解分が小さすぎるためか微
粒子として析出しがたく、また安定性が不良で実用に耐
える水分散体は得られなかった。For comparison, in the same manner as in Example 3, the terminal having an intrinsic viscosity of 0.75 deciliter / g, an ethylene content of 13 mol%, a saponification degree of 98.1 mol%, a melting point of 212 ° C. and a water insoluble content of 30% was used. Having ammonium chloride group
OH was synthesized, and 50 parts of this EVOH was added to 1000 parts of a mixed solvent of water / isopropyl alcohol = 90/10 at 60 ° C.
The solution was heated and melted, then cooled, and isopropyl alcohol was distilled off.However, because the water-insoluble matter was too small, it was difficult to precipitate as fine particles, and a water dispersion having poor stability and practical use was not obtained. Was.
【００７０】また実施例３と同様にして、固有粘度０．
４６デシリットル／ｇ、エチレン含量６８モル％、けん
化度９９．０モル％、融点１２３℃、水不溶解分９９％
の末端にアンモニウムクロリド基を有するＥＶＯＨを合
成し、このＥＶＯＨ５０部を水／イソプロピルアルコー
ル＝１０／９０の混合溶剤１０００部に６５℃で加熱溶
解、ついで冷却、イソプロピルアルコールの留去を行っ
て固形分濃度２４％の水性分散液を得た。しかしなが
ら、この水性乳化分散液を実施例１と同様に塗布、乾燥
・熱処理したフィルム（ＥＶＯＨ厚み５μｍ）の酸素透
過量は１０００以上でガスバリヤー性が著しく不良であ
った。Further, in the same manner as in Example 3, the intrinsic viscosity was set to 0.1.
46 deciliter / g, ethylene content 68 mol%, degree of saponification 99.0 mol%, melting point 123 ° C., water insoluble content 99%
Was synthesized by heating 50 parts of this EVOH in 1000 parts of a mixed solvent of water / isopropyl alcohol = 10/90 at 65 ° C., followed by cooling and distilling off isopropyl alcohol to obtain a solid content. An aqueous dispersion having a concentration of 24% was obtained. However, a film (EVOH thickness: 5 μm) obtained by applying, drying and heat-treating this aqueous emulsified dispersion in the same manner as in Example 1 had an oxygen permeation of 1000 or more, and the gas barrier properties were extremely poor.
【００７１】実施例４ ピバリン酸ビニル１０００部、メチルアルコール３００
部、３−メルカプトプロパン酸ナトリウム０．１１部を
高圧重合槽に仕込み、内部を十分窒素置換した後エチレ
ンガスを仕込んだ。内温６０℃、エチレン圧力２４Ｋｇ
／ｃｍ2Ｇに調節した後、重合開始剤２，２’−アゾビ
スイソブチロニトリル０．６５部を加え、さらに３−メ
ルカプトプロパン酸ナトリウムのメチルアルコール溶液
（濃度２．０％）を１９．０部／時間の速度で５．０時
間連続的に添加して重合を行った。ピバリン酸ビニルの
重合率は５１％であった。Example 4 1000 parts of vinyl pivalate, 300 parts of methyl alcohol
Parts and sodium 3-mercaptopropanoate (0.11 part) were charged into a high-pressure polymerization tank, and the inside thereof was sufficiently purged with nitrogen, and then ethylene gas was charged. Inner temperature 60 ° C, ethylene pressure 24Kg
/ Cm 2 G, 0.65 parts of a polymerization initiator 2,2′-azobisisobutyronitrile was added, and a solution of sodium 3-mercaptopropanoate in methyl alcohol (concentration: 2.0%) was further added to the solution. Polymerization was carried out by continuously adding at a rate of 0.0 parts / hour for 5.0 hours. The polymerization rate of vinyl pivalate was 51%.
【００７２】冷却後エチレンガスを分離除去し、さらに
減圧下ノルマルプロピルアルコールを添加しながら未反
応の酢酸ビニルを系外に追い出し、エチレン−ピバリン
酸ビニル系共重合体のノルマルプロピルアルコール溶液
を得た。After cooling, ethylene gas was separated and removed, and unreacted vinyl acetate was driven out of the system while adding normal propyl alcohol under reduced pressure to obtain a normal propyl alcohol solution of an ethylene-vinyl pivalate copolymer. .
【００７３】次にこのノルマルプロピルアルコール溶液
に、水酸化カリウムを共重合体中のピバリン酸ビニル単
位に対するモル比が３．２となるように水酸化カリウム
のメチルアルコール溶液を添加し、窒素雰囲気下９０℃
で１．５時間けん化反応を行った。ついで反応液を２０
℃まで冷却してけん化物を析出させ、遠心脱液後、蒸留
水で繰り返し洗浄し、７０℃で３時間熱風乾燥、さらに
１０５℃で１２時間真空乾燥した。Next, to this normal propyl alcohol solution was added potassium hydroxide in a methyl alcohol solution such that the molar ratio of potassium hydroxide to vinyl pivalate units in the copolymer was 3.2, and the mixture was added under a nitrogen atmosphere. 90 ° C
For 1.5 hours. Then, add 20
After cooling to ℃ to precipitate a saponified substance, and after centrifugal elimination, it was repeatedly washed with distilled water, dried at 70 ° C. for 3 hours with hot air, and further dried at 105 ° C. for 12 hours under vacuum.
【００７４】得られたエチレン−ピバリン酸ビニル系共
重合体けん化物は、分子の末端にカルボン酸ナトリウム
を有する固有粘度０．８１デシリットル／ｇ、エチレン
含量３２モル％、けん化度９９．２モル％、融点１８３
℃、水不溶解分９８％の末端イオン変性ＥＶＯＨであっ
た。The saponified ethylene-vinyl pivalate copolymer had an intrinsic viscosity of 0.81 deciliter / g having sodium carboxylate at the terminal of the molecule, an ethylene content of 32 mol%, and a saponification degree of 99.2 mol%. Melting point 183
It was a terminal ion-modified EVOH having a water-insoluble content of 98% at ℃.
【００７５】この末端イオン変性ＥＶＯＨを実施例１と
同一条件で水とメチルアルコールの混合溶剤に溶解し、
冷却、ついでメチルアルコールの留去を行い、平均粒子
径１．０μｍ、固形分濃度２３％の水性分散液を得た。
また実施例１と同様に塗布、乾燥・熱処理したフィルム
（ＥＶＯＨ層厚み５μｍ）の酸素透過量は２．５でガス
バリヤー性が非常に良好であった。The terminal ion-modified EVOH was dissolved in a mixed solvent of water and methyl alcohol under the same conditions as in Example 1,
After cooling, the methyl alcohol was distilled off to obtain an aqueous dispersion having an average particle diameter of 1.0 μm and a solid concentration of 23%.
The oxygen permeation amount of the film (EVOH layer thickness: 5 μm) coated, dried and heat-treated in the same manner as in Example 1 was 2.5, and the gas barrier property was very good.
【００７６】実施例５ 実施例４記載の末端イオン変性ＥＶＯＨ５０部を水／エ
チルアルコール＝３０／７０の混合溶剤５００部に添加
混合し７０℃で加熱溶解した。ついでこの溶液をドデシ
ルベンゼンスルホン酸ナトリウムを０．５％含有する１
５℃の水１００部中５０００ｒｐｍの高速撹拌下に滴下
したところ、平均粒子径０．８μｍの安定な分散液が得
られた。次いでこの分散液を撹拌下に１５℃で減圧蒸発
させてエチルアルコールを留去し、平均粒子径０．８μ
ｍ、固形分濃度２０％の安定な水性分散液を得た。この
水性乳化分散液を実施例１と同様に塗布、乾燥・熱処理
したフィルム（ＥＶＯＨ厚み５μｍ）の酸素透過量は
２．５でガスバリヤー性が非常に良好であった。Example 5 50 parts of the terminal ion-modified EVOH described in Example 4 was added to and mixed with 500 parts of a mixed solvent of water / ethyl alcohol = 30/70, and dissolved by heating at 70 ° C. The solution was then added to a solution containing 0.5% sodium dodecylbenzenesulfonate.
When the mixture was added dropwise to 100 parts of water at 5 ° C. under high-speed stirring at 5000 rpm, a stable dispersion having an average particle diameter of 0.8 μm was obtained. Subsequently, this dispersion was evaporated under reduced pressure at 15 ° C. with stirring to remove ethyl alcohol, and the average particle diameter was 0.8 μm.
m, a stable aqueous dispersion having a solid content of 20% was obtained. A film (EVOH thickness 5 μm) obtained by applying, drying and heat-treating this aqueous emulsion dispersion in the same manner as in Example 1 had an oxygen permeation amount of 2.5 and an extremely good gas barrier property.
【００７７】[0077]
【発明の効果】本発明の末端イオン変性ＥＶＯＨを用い
て自己乳化分散した水性乳化分散液は貯蔵あるいは使用
時の安定性に優れた高固形分濃度の水性分散液で、環境
汚染等の問題のない利点があり、塗布乾燥により優れた
ガスバリヤー性、保香性および耐油・耐薬品性を示す薄
い皮膜を形成できる有用な塗布剤として利用できる工業
的価値の高いものである。The aqueous emulsion dispersion which is self-emulsified and dispersed using the terminal ion-modified EVOH of the present invention is an aqueous dispersion having a high solid content and excellent in stability during storage or use. It has high industrial value and can be used as a useful coating agent capable of forming a thin film showing excellent gas barrier properties, fragrance retention properties, and oil and chemical resistance by coating and drying.
【図１】実施例１記載の分子の末端にカルボン酸ナトリ
ウムを有するエチレン含量３２モル％、けん化度９９．
９モル％の末端イオン変性ＥＶＯＨをｄ6−ＤＭＳＯ
（重水素化ジメチルスルホキシド）とＣＤ3ＯＤ（重水
素化メチルアルコール）とからなる混合溶剤に溶解して
測定した1Ｈ−ＮＭＲスペクトルである。FIG. 1 shows an ethylene content having sodium carboxylate at the end of the molecule described in Example 1, an ethylene content of 32 mol%, and a degree of saponification of 99.
9 mol% of the terminally ion-modified EVOH was converted to d 6 -DMSO
1 is a 1 H-NMR spectrum measured by dissolving in a mixed solvent consisting of (deuterated dimethyl sulfoxide) and CD 3 OD (deuterated methyl alcohol).
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｌ 23/26 Ｃ０８Ｌ 23/26 (72)発明者 廣藤 俐 岡山県倉敷市酒津1621番地 株式会社ク ラレ内 審査官 佐藤 邦彦 (56)参考文献 特開 昭61−81403（ＪＰ，Ａ) 特開 昭61−81405（ＪＰ，Ａ) 特開 昭63−301206（ＪＰ，Ａ) 特開 昭63−46202（ＪＰ，Ａ) 特開 昭59−187003（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 8/00 - 8/50 Continuation of the front page (51) Int.Cl. 7 Identification code FI C08L 23/26 C08L 23/26 (72) Inventor Li Li Hiroto 1621 Sakurazu, Kurashiki-shi, Okayama Pref. Document JP-A-61-81403 (JP, A) JP-A-61-81405 (JP, A) JP-A-63-301206 (JP, A) JP-A-63-46202 (JP, A) 187003 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) C08F 8/00-8/50
Claims (7)
基またはその塩、アンモニウム基の群から選択される少
なくとも１種または２種以上のイオン性基を含有するチ
オールの存在下にエチレンとビニルエステルを共重合
し、次いでけん化して得られる、末端にスルホン酸基ま
たはその塩、カルボン酸基またはその塩、アンモニウム
基の群から選択される少なくとも１種または２種以上の
イオン性基を有し、１モル／リットルのチオシアン酸ア
ンモニウムを含有する水／フェノール系混合溶剤（重量
比１５／８５）中３０℃で測定した固有粘度０．４５デ
シリットル／ｇ以上、エチレン含量１５〜６５モル％、
けん化度９０モル％以上で、かつ濃度１％で３０℃の水
に１日溶解したときの不溶解分が５０％以上のエチレン
−ビニルアルコール系共重合体。1. A sulfonic acid group or a salt thereof, a carboxylic acid
Group or a salt thereof, or a small group selected from the group of ammonium groups.
Thiol groups containing at least one or more ionic groups
Copolymerization of ethylene and vinyl ester in the presence of all
Was then obtained by saponification, sulfone terminated Sanmotoma
Or its salt, carboxylic acid group or its salt, ammonium
Water / phenolic mixed solvent containing at least one or more ionic groups selected from the group of groups and containing 1 mol / l ammonium thiocyanate (weight ratio 15/85) Intrinsic viscosity 0.45 deciliter / g or more measured at 30 ° C., ethylene content 15 to 65 mol%,
An ethylene-vinyl alcohol copolymer having a saponification degree of 90 mol% or more and an insoluble content of 50% or more when dissolved in water at 30 ° C. for 1 day at a concentration of 1%.
ール系共重合体の水性分散液。2. An aqueous dispersion of the ethylene-vinyl alcohol copolymer according to claim 1 .
してなる積層体。3. A laminate obtained by applying the aqueous dispersion according to claim 2 to a substrate.
ール系共重合体の溶液を水と接触させて微粒子として析
出させ、次いで溶剤を除去することを特徴とする水性分
散液の製造法。4. A method for producing an aqueous dispersion, comprising: bringing a solution of the ethylene-vinyl alcohol copolymer according to claim 1 into contact with water to precipitate fine particles, and then removing the solvent.
ール系共重合体を高温では溶解するが低温にすると不溶
になる溶剤に加熱溶解した後、その溶液を冷却し、次い
で溶剤を水と置換することを特徴とする水性分散液の製
造法。5. The ethylene-vinyl alcohol copolymer according to claim 1 is dissolved by heating in a solvent which dissolves at a high temperature but becomes insoluble at a low temperature, cools the solution, and then replaces the solvent with water. A method for producing an aqueous dispersion, comprising:
ール系共重合体の溶液を非溶剤と接触させるか、又は冷
却することにより析出させた粒子を水中に分散させるこ
とを特徴とする水性分散液の製造法。6. An aqueous dispersion characterized by dispersing particles precipitated by bringing the solution of the ethylene-vinyl alcohol copolymer according to claim 1 into contact with a non-solvent or cooling the solution. Manufacturing method.
ール系共重合体の水−アルコール混合溶液を冷却して、
析出させ、次いでアルコールを除去し、必要に応じて水
を除去することを特徴とする水性分散液の製造法。 7. A water-alcohol mixed solution of the ethylene-vinyl alcohol copolymer according to claim 1 is cooled,
A method for producing an aqueous dispersion, comprising precipitating, then removing alcohol and, if necessary, removing water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14316192A JP3273631B2 (en) | 1991-05-10 | 1992-05-08 | Terminal ion-modified ethylene-vinyl alcohol copolymer and aqueous dispersion thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13569491 | 1991-05-10 | ||
| JP3-135694 | 1991-05-10 | ||
| JP14316192A JP3273631B2 (en) | 1991-05-10 | 1992-05-08 | Terminal ion-modified ethylene-vinyl alcohol copolymer and aqueous dispersion thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05155919A JPH05155919A (en) | 1993-06-22 |
| JP3273631B2 true JP3273631B2 (en) | 2002-04-08 |
Family
ID=26469474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14316192A Expired - Fee Related JP3273631B2 (en) | 1991-05-10 | 1992-05-08 | Terminal ion-modified ethylene-vinyl alcohol copolymer and aqueous dispersion thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3273631B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4230007B2 (en) * | 1997-05-09 | 2009-02-25 | 株式会社クラレ | Molded product comprising ethylene-vinyl alcohol copolymer |
| JP4953528B2 (en) * | 2000-08-07 | 2012-06-13 | 株式会社クラレ | Process for producing water-containing composition of ethylene-vinyl alcohol copolymer |
| JP3639831B2 (en) | 2002-02-28 | 2005-04-20 | キヤノン株式会社 | NOVEL POLYHYDROXYALKANOATE AND METHOD FOR PRODUCING THE SAME, CHARGE CONTROL AGENT CONTAINING THE SAME, TONER BINDER, TONER, IMAGE FORMING METHOD USING THE TONER |
| CA2578024C (en) | 2004-09-03 | 2012-04-17 | Kuraray Co., Ltd. | Multilayered pellet comprising ethylene-vinyl alcohol copolymer resin composition |
-
1992
- 1992-05-08 JP JP14316192A patent/JP3273631B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05155919A (en) | 1993-06-22 |
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