JP5009302B2 - Process for producing carbon monoxide-vinyl alcohol copolymer, carbon monoxide-vinyl alcohol copolymer and water-resistant composition using the same - Google Patents
Process for producing carbon monoxide-vinyl alcohol copolymer, carbon monoxide-vinyl alcohol copolymer and water-resistant composition using the same Download PDFInfo
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- JP5009302B2 JP5009302B2 JP2008544120A JP2008544120A JP5009302B2 JP 5009302 B2 JP5009302 B2 JP 5009302B2 JP 2008544120 A JP2008544120 A JP 2008544120A JP 2008544120 A JP2008544120 A JP 2008544120A JP 5009302 B2 JP5009302 B2 JP 5009302B2
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- Prior art keywords
- carbon monoxide
- water
- vinyl alcohol
- pva
- viscosity
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 83
- 239000000203 mixture Substances 0.000 title claims description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 28
- 229910052799 carbon Inorganic materials 0.000 title claims description 28
- 229920001577 copolymer Polymers 0.000 title claims description 27
- 238000000034 method Methods 0.000 title description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 74
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 71
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 238000007127 saponification reaction Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 18
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 10
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 117
- 229920002451 polyvinyl alcohol Polymers 0.000 description 48
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- 238000012986 modification Methods 0.000 description 25
- 230000004048 modification Effects 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 21
- 229920001567 vinyl ester resin Polymers 0.000 description 21
- 238000007334 copolymerization reaction Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 15
- 239000000178 monomer Substances 0.000 description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 11
- -1 methylol compound Chemical class 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 229920002689 polyvinyl acetate Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 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 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
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- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical group CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
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- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
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- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
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- DBUPOCYLUHVFHU-UHFFFAOYSA-N carboxyoxy 2,2-diethoxyethyl carbonate Chemical compound CCOC(OCC)COC(=O)OOC(O)=O DBUPOCYLUHVFHU-UHFFFAOYSA-N 0.000 description 1
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- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- MFOBKQAGVZYMON-UHFFFAOYSA-N cyanoformohydrazide Chemical compound NNC(=O)C#N MFOBKQAGVZYMON-UHFFFAOYSA-N 0.000 description 1
- FOAFCAUCIZMBJM-UHFFFAOYSA-N cyclohexane-1,1,2-tricarbohydrazide Chemical compound NNC(=O)C1CCCCC1(C(=O)NN)C(=O)NN FOAFCAUCIZMBJM-UHFFFAOYSA-N 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- LPUZTLKYAOOFDX-QXMHVHEDSA-N ethenyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC=C LPUZTLKYAOOFDX-QXMHVHEDSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- WNMORWGTPVWAIB-UHFFFAOYSA-N ethenyl 2-methylpropanoate Chemical compound CC(C)C(=O)OC=C WNMORWGTPVWAIB-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UJRIYYLGNDXVTA-UHFFFAOYSA-N ethenyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC=C UJRIYYLGNDXVTA-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- OXAGUPFRAIIDLT-UHFFFAOYSA-N heptanedihydrazide Chemical compound NNC(=O)CCCCCC(=O)NN OXAGUPFRAIIDLT-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical class CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- ADTJPOBHAXXXFS-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 description 1
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- HATIEXJZXOLRAO-UHFFFAOYSA-N octanedihydrazide Chemical compound NNC(=O)CCCCCCC(=O)NN HATIEXJZXOLRAO-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical class [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- WKEWCYHGACEYTR-UHFFFAOYSA-N tert-butyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(C)(C)C WKEWCYHGACEYTR-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 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
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
Description
本発明は、一酸化炭素に基づく単位とビニルアルコール単位とを含む一酸化炭素−ビニルアルコール系共重合体の製造方法、ならびに一酸化炭素−ビニルアルコール系共重合体とこれを用いた耐水性組成物に関する。より詳細には、一酸化炭素とビニルエステル系単量体とを共重合して得た一酸化炭素−ビニルエステル系共重合体をけん化する、一酸化炭素−ビニルアルコール系共重合体の製造方法、ならびに、上記一酸化炭素−ビニルエステル系共重合体をけん化して得た一酸化炭素−ビニルアルコール系共重合体と、これを用いた耐水性組成物に関する。 The present invention relates to a method for producing a carbon monoxide-vinyl alcohol copolymer comprising units based on carbon monoxide and vinyl alcohol units, and a carbon monoxide-vinyl alcohol copolymer and a water-resistant composition using the same. Related to things. More specifically, a method for producing a carbon monoxide-vinyl alcohol copolymer that saponifies a carbon monoxide-vinyl ester copolymer obtained by copolymerizing carbon monoxide and a vinyl ester monomer. And a carbon monoxide-vinyl alcohol copolymer obtained by saponifying the carbon monoxide-vinyl ester copolymer and a water-resistant composition using the same.
ビニルアルコール系重合体（ＰＶＡ）は、皮膜の形成性（造膜性）および形成された皮膜の強度において、他の水溶性樹脂の追随を許さぬ性能を有することが知られており、各種のバインダー、接着剤、表面処理剤などに広く使用されている。しかし、ＰＶＡは水溶性であるため、形成された皮膜の耐水性（以下、ＰＶＡあるいはＰＶＡを含む水性組成物から形成された皮膜の耐水性を、単に「ＰＶＡの耐水性」あるいは「水性組成物の耐水性」ともいう）が低いという欠点を有し、特に低温で乾燥させた場合に、形成される皮膜の耐水性が低くなる。この欠点を改良するために、種々の方法が検討されてきた。 Vinyl alcohol polymers (PVA) are known to have performances that do not allow other water-soluble resins to follow in terms of film formability (film forming properties) and strength of the formed film. Widely used in binders, adhesives, surface treatment agents, etc. However, since PVA is water-soluble, the water resistance of the formed film (hereinafter, the water resistance of the film formed from PVA or an aqueous composition containing PVA is simply referred to as “water resistance of PVA” or “aqueous composition”. The water resistance of the formed film is lowered particularly when dried at a low temperature. Various methods have been investigated to remedy this drawback.
例えば、ＰＶＡを、グリオキザール、グルタルアルデヒド、ジアルデヒド澱粉、水溶性エポキシ化合物、メチロール化合物などで架橋する方法が知られている。しかし、この方法によりＰＶＡを十分に耐水化するためには、１００℃以上、特に１２０℃以上、の高温による長時間の熱処理が必要である。また例えば、特に低温乾燥時のＰＶＡの耐水化を図るために、強酸性（例えばｐＨ２以下）の水性組成物とする方法が知られているが、この方法では、水性組成物の粘度安定性が低下して使用中にゲル化するなどの問題がある他、耐水性の点においても、十分な耐水性を得ることができない。カルボン酸含有ＰＶＡをポリアミドエピクロルヒドリン樹脂で架橋する方法、アセトアセチル基含有ＰＶＡをグリオキザールなどの多価アルデヒド化合物で架橋する方法も知られているが、これらの方法においても、架橋後のＰＶＡの耐水性が不十分である、水性組成物としての粘度安定性が低下する、などの問題を有している。 For example, a method for crosslinking PVA with glyoxal, glutaraldehyde, dialdehyde starch, a water-soluble epoxy compound, a methylol compound, or the like is known. However, long-term heat treatment at a high temperature of 100 ° C. or higher, particularly 120 ° C. or higher, is necessary to make the PVA sufficiently water resistant by this method. In addition, for example, a method of preparing a strongly acidic (for example, pH 2 or less) aqueous composition for achieving water resistance of PVA particularly at low temperature drying is known, but in this method, the viscosity stability of the aqueous composition is improved. In addition to problems such as lowering and gelation during use, sufficient water resistance cannot be obtained in terms of water resistance. A method of crosslinking a carboxylic acid-containing PVA with a polyamide epichlorohydrin resin and a method of crosslinking an acetoacetyl group-containing PVA with a polyvalent aldehyde compound such as glyoxal are also known, but in these methods, the water resistance of the PVA after crosslinking is also known. Is insufficient, viscosity stability as an aqueous composition is lowered, and the like.
また、カルボニル基とヒドラジン化合物との反応性を利用して、カルボニル基が側鎖に導入されたジアセトン基含有ＰＶＡを、ヒドラジンまたはヒドラジド化合物により架橋する方法が知られている。この方法によれば、熱処理や強酸の添加などの特別な処理をしなくても、得られた変性ＰＶＡは優れた耐水性を示す。また、架橋に用いられるヒドラジン化合物は、アルデヒド類やイソシアネート類などの他の架橋剤に比べて、安全性に優れる。しかし、側鎖に導入されたカルボニル基と、ヒドラジン化合物との反応は瞬時に進行するために、ジアセトン基含有ＰＶＡおよびヒドラジン化合物を含む水性組成物が急激に高粘度化し、ゲル化する問題がある。 In addition, a method is known in which a diacetone group-containing PVA in which a carbonyl group is introduced into a side chain is crosslinked with a hydrazine or a hydrazide compound by utilizing the reactivity between a carbonyl group and a hydrazine compound. According to this method, the obtained modified PVA exhibits excellent water resistance without special treatment such as heat treatment or addition of a strong acid. Moreover, the hydrazine compound used for crosslinking is superior in safety compared to other crosslinking agents such as aldehydes and isocyanates. However, since the reaction between the carbonyl group introduced into the side chain and the hydrazine compound proceeds instantaneously, the aqueous composition containing the diacetone group-containing PVA and the hydrazine compound suddenly becomes highly viscous and gels. .
一方、ＰＶＡの酸化により合成される酸化ＰＶＡは、主鎖にカルボニル基を有し、ヒドラジンまたはヒドラジド化合物との反応により、高い耐水性を有する変性ＰＶＡとすることができる。また、酸化ＰＶＡは、カルボニル基を主鎖に有することから、側鎖にカルボニル基を有するＰＶＡに比べて、ヒドラジンまたはヒドラジド化合物との反応がゆっくりと進行し、その結果として水性組成物としたときの粘度上昇が緩やかとなり、取り扱いが容易となる。しかし、酸化ＰＶＡを合成する際に使用する酸化剤の残留物がＰＶＡの物性に悪影響を与えるなどの問題があり、これまで、この方法の実用化には至っていない。 On the other hand, oxidized PVA synthesized by oxidation of PVA can be a modified PVA having a carbonyl group in the main chain and having high water resistance by reaction with hydrazine or a hydrazide compound. In addition, since oxidized PVA has a carbonyl group in the main chain, the reaction with hydrazine or a hydrazide compound proceeds more slowly than PVA having a carbonyl group in the side chain, resulting in an aqueous composition. The increase in viscosity of the resin becomes gradual, and handling becomes easy. However, there is a problem that the residue of the oxidizing agent used when synthesizing the oxidized PVA adversely affects the physical properties of the PVA, so far, this method has not been put into practical use.
これとは別に、カルボニル基を主鎖に有するＰＶＡの製造例として、シクロヘキサン中において酢酸ビニルと一酸化炭素とをラジカル重合し、得られた一酸化炭素−酢酸ビニル共重合体をけん化して、一酸化炭素−ビニルアルコール共重合体を得る方法が、文献１（工業化学雑誌、第６７巻、第６号、９３５−９３９ページ、１９６４年）に報告されている。しかし、この方法では、ラジカル重合の溶媒としてシクロヘキサンを用いているために、ポリマーラジカルなどからの連鎖移動によってシクロヘキシルラジカルが生成する。生成したシクロヘキシルラジカルはポリマーに導入されるため、ポリマー中への疎水基の導入が避けられず、得られた一酸化炭素−ビニルアルコール共重合体の水溶性が低下するという問題がある。 Separately, as an example of producing a PVA having a carbonyl group in the main chain, radical polymerization of vinyl acetate and carbon monoxide in cyclohexane, and saponifying the obtained carbon monoxide-vinyl acetate copolymer, A method for obtaining a carbon monoxide-vinyl alcohol copolymer is reported in Reference 1 (Industrial Chemical Journal, Vol. 67, No. 6, pages 935-939, 1964). However, in this method, since cyclohexane is used as a solvent for radical polymerization, a cyclohexyl radical is generated by chain transfer from a polymer radical or the like. Since the generated cyclohexyl radical is introduced into the polymer, introduction of a hydrophobic group into the polymer is inevitable, and there is a problem that the water solubility of the obtained carbon monoxide-vinyl alcohol copolymer is lowered.
本発明の目的の一つは、主鎖にカルボニル基を有する一酸化炭素−ビニルアルコール系共重合体（ＣＯ変性ＰＶＡ）であって、良好な水溶性を有し、水性組成物としたときの粘度安定性に優れる新規なＣＯ変性ＰＶＡと、その製造方法の提供にある。 One of the objects of the present invention is a carbon monoxide-vinyl alcohol copolymer (CO-modified PVA) having a carbonyl group in the main chain, which has good water solubility and is an aqueous composition. The present invention provides a novel CO-modified PVA excellent in viscosity stability and a method for producing the same.
本発明の目的の別の一つは、水性組成物としての粘度安定性に優れるとともに、形成される皮膜の耐水性に優れる、ＣＯ変性ＰＶＡを含む新規な耐水性組成物の提供にある。 Another object of the present invention is to provide a novel water-resistant composition containing CO-modified PVA, which is excellent in viscosity stability as an aqueous composition and excellent in water resistance of a formed film.
本発明者らは、上記特性を有する新規なＣＯ変性ＰＶＡを開発するべく鋭意研究を重ねた結果、ＣＯとビニルエステル系単量体の共重合を特定の条件下で行うことにより、このようなＣＯ変性ＰＶＡが得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to develop a novel CO-modified PVA having the above characteristics, the present inventors have conducted such copolymerization of CO and vinyl ester monomers under specific conditions. The inventors have found that CO-modified PVA can be obtained, and have completed the present invention.
本発明のＣＯ変性ＰＶＡは、一酸化炭素に基づく単位とビニルアルコール単位とを含む、一酸化炭素−ビニルアルコール系共重合体であって、一酸化炭素に基づく単位の含有量（ＣＯ変性量）が０．０１〜８モル％であり、けん化度が６０〜９９．９９モル％であり、濃度４重量％の水溶液としたときの粘度が２．０〜１５０．０ｍＰａ・ｓである。 The CO-modified PVA of the present invention is a carbon monoxide-vinyl alcohol copolymer containing a unit based on carbon monoxide and a vinyl alcohol unit, and the content of the unit based on carbon monoxide (CO modification amount) Is 0.01 to 8 mol%, the degree of saponification is 60 to 99.99 mol%, and the viscosity when an aqueous solution having a concentration of 4 wt% is 2.0 to 150.0 mPa · s.
本発明の耐水性組成物は、一酸化炭素に基づく単位とビニルアルコール単位とを含む一酸化炭素−ビニルアルコール系共重合体と、分子内にヒドラジド基を２個以上有する多官能ヒドラジド化合物とを含む耐水性組成物であって、前記耐水性組成物における前記多官能ヒドラジド化合物の含有量が、前記共重合体１００重量部に対して１〜１５重量部であり、前記共重合体について、一酸化炭素に基づく単位の含有量（ＣＯ変性量）が０．１〜８モル％であり、けん化度が８５〜９９．９９モル％であり、濃度４重量％の水溶液としたときの粘度が２．０〜１５０．０ｍＰａ・ｓである。 The water-resistant composition of the present invention comprises a carbon monoxide-vinyl alcohol copolymer containing units based on carbon monoxide and vinyl alcohol units, and a polyfunctional hydrazide compound having two or more hydrazide groups in the molecule. A water-resistant composition containing, wherein the content of the polyfunctional hydrazide compound in the water-resistant composition is 1 to 15 parts by weight with respect to 100 parts by weight of the copolymer. The unit content based on carbon oxide (CO modification amount) is 0.1 to 8 mol%, the degree of saponification is 85 to 99.99 mol%, and the viscosity when an aqueous solution having a concentration of 4% by weight is 2 0.0 to 150.0 mPa · s.
本発明の製造方法では、良好な水溶性を有し、水性組成物としたときの粘度安定性に優れるＣＯ変性ＰＶＡを製造できる。また、製造条件によっては、良好な水溶性および優れた粘度安定性に加えて、架橋剤との反応により高い耐水性を示すＣＯ変性ＰＶＡを製造できる。 In the production method of the present invention, it is possible to produce CO-modified PVA having good water solubility and excellent viscosity stability when used as an aqueous composition. Depending on the production conditions, CO-modified PVA that exhibits high water resistance by reaction with a crosslinking agent in addition to good water solubility and excellent viscosity stability can be produced.
本発明のＣＯ変性ＰＶＡは、良好な水溶性を有し、水性組成物としたときの粘度安定性に優れる。また、ＣＯ変性量、けん化度、および濃度４重量％の水溶液としたときの粘度を特定の範囲とすることにより、良好な水溶性および優れた粘度安定性に加えて、架橋剤との反応により高い耐水性を示すＣＯ変性ＰＶＡとすることができる。 The CO-modified PVA of the present invention has good water solubility, and is excellent in viscosity stability when used as an aqueous composition. Further, by setting the CO modification amount, the degree of saponification, and the viscosity when the aqueous solution has a concentration of 4% by weight within a specific range, in addition to good water solubility and excellent viscosity stability, by reaction with a crosslinking agent A CO-modified PVA exhibiting high water resistance can be obtained.
本発明の耐水性組成物によれば、耐水性に優れる皮膜を形成できる。 According to the water-resistant composition of the present invention, a film excellent in water resistance can be formed.
［ＣＯ変性ＰＶＡの製造方法］
本発明のＣＯ変性ＰＶＡの製造方法は、一酸化炭素に基づく単位とビニルアルコール単位とを含む、一酸化炭素−ビニルアルコール系共重合体の製造方法であって、一酸化炭素とビニルエステル系単量体との共重合を、一酸化炭素を含む雰囲気下にて、無溶媒で、またはアルコール系溶媒中において行い、前記共重合により得られた一酸化炭素−ビニルエステル系共重合体をけん化して、一酸化炭素−ビニルアルコール系共重合体を得る方法である。
一酸化炭素（ＣＯ）とビニルエステル系単量体との共重合は、一酸化炭素を含む雰囲気下にて無溶媒で行うか、あるいは、一酸化炭素を含む雰囲気下にてアルコール系溶媒中において行う。
[Method for producing CO-modified PVA]
The method for producing a CO-modified PVA of the present invention is a method for producing a carbon monoxide-vinyl alcohol copolymer containing a unit based on carbon monoxide and a vinyl alcohol unit. Copolymerization with the monomer is carried out in an atmosphere containing carbon monoxide, without solvent, or in an alcohol solvent, and the carbon monoxide-vinyl ester copolymer obtained by the copolymerization is saponified. This is a method for obtaining a carbon monoxide-vinyl alcohol copolymer.
Copolymerization of carbon monoxide (CO) and vinyl ester monomer is performed without solvent in an atmosphere containing carbon monoxide, or in an alcohol solvent in an atmosphere containing carbon monoxide. Do.
共重合は、ＣＯの分圧にして０．０１〜８ＭＰａの圧力下にて行うことが好ましい。ＣＯの分圧が０．０１ＭＰａ未満の場合、得られたＣＯ変性ＰＶＡにおけるＣＯ変性量が過度に小さくなって、望む特性が得られないことがある。またＣＯの分圧が８ＭＰａを超えると、得られたＣＯ変性ＰＶＡにおけるＣＯ変性量が８モル％を超えて、その水溶性が低下することがある。即ち、共重合時のＣＯの分圧を上記範囲とすることにより、水溶性が良好なＣＯ変性ＰＶＡを、より確実に得ることができる。 The copolymerization is preferably performed at a partial pressure of CO and a pressure of 0.01 to 8 MPa. When the partial pressure of CO is less than 0.01 MPa, the amount of CO modification in the obtained CO-modified PVA becomes excessively small, and desired characteristics may not be obtained. On the other hand, if the partial pressure of CO exceeds 8 MPa, the amount of CO modification in the obtained CO-modified PVA may exceed 8 mol%, and the water solubility may decrease. That is, by setting the partial pressure of CO during copolymerization within the above range, CO-modified PVA with good water solubility can be obtained more reliably.
共重合はＣＯ雰囲気下にて行うことが好ましく、この場合、ＣＯの加圧雰囲気下（ＣＯの圧力が０．１ＭＰａ以上。ただし、ＣＯの圧力の上限は８ＭＰａが好ましい）にて行うことがより好ましい。共重合時に、ＣＯに基づく単位（ＣＯ単位）を、より効率的に導入でき、一酸化炭素−ビニルエステル系共重合体をより確実に形成できる。 The copolymerization is preferably performed in a CO atmosphere. In this case, the copolymerization is preferably performed in a pressurized atmosphere of CO (CO pressure is 0.1 MPa or more. However, the upper limit of CO pressure is preferably 8 MPa). preferable. During copolymerization, CO-based units (CO units) can be introduced more efficiently, and a carbon monoxide-vinyl ester copolymer can be more reliably formed.
共重合の方法は、無溶媒で、またはアルコール系溶媒中において実施できる限り特に限定されず、例えば、塊状重合法、溶液重合法、懸濁重合法、乳化重合法など、任意の重合方法を用いることができる。特に、無溶媒の塊状重合法、およびアルコール系溶媒を用いた溶液重合法を好適に採用できる。重合度が高いＣＯ変性ＰＶＡを得たい場合は、乳化重合法を採用すればよい。 The copolymerization method is not particularly limited as long as it can be carried out without a solvent or in an alcohol solvent, and for example, any polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method is used. be able to. In particular, a solvent-free bulk polymerization method and a solution polymerization method using an alcohol solvent can be suitably employed. In order to obtain CO-modified PVA having a high degree of polymerization, an emulsion polymerization method may be employed.
共重合の方式は特に限定されず、例えば、回分重合、半回分重合、連続重合、半連続重合のいずれであってもよい。 The method of copolymerization is not particularly limited, and may be any of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization, for example.
アルコール系溶媒としては特に限定されないが、例えば、メタノール、エタノール、プロピルアルコールなどを単独で、あるいは、２種以上混合して用いることができる。アルコール系溶媒としては、特にメタノールが好ましい。即ち、共重合を、メタノール中において行うことが好ましい。 Although it does not specifically limit as an alcohol solvent, For example, methanol, ethanol, a propyl alcohol, etc. can be used individually or in mixture of 2 or more types. As the alcohol solvent, methanol is particularly preferable. That is, the copolymerization is preferably performed in methanol.
共重合を行う温度は、０〜２００℃が好ましく、３０〜１４０℃がより好ましい。当該温度が０℃より低い場合、十分な重合速度が得られないことがある。一方、当該温度が２００℃より高い場合、溶媒へのＣＯの溶解量が低下して、望むＣＯ変性量を有するＣＯ変性ＰＶＡが得られないことがある。 0-200 degreeC is preferable and the temperature which performs copolymerization has more preferable 30-140 degreeC. When the temperature is lower than 0 ° C., a sufficient polymerization rate may not be obtained. On the other hand, when the temperature is higher than 200 ° C., the amount of CO dissolved in the solvent decreases, and a CO-modified PVA having a desired CO modification amount may not be obtained.
共重合を行う温度の制御方法は特に限定されず、例えば、重合速度を制御することで、重合により生成する熱と、重合反応器の表面からの放熱とのバランスをとる方法や、適当な熱媒を用いた外部ジャケットにより制御する方法などが挙げられる。安全性の面からは、後者の方法が好ましい。 The method for controlling the temperature at which the copolymerization is performed is not particularly limited. For example, by controlling the polymerization rate, a method for balancing the heat generated by the polymerization with the heat radiation from the surface of the polymerization reactor, or an appropriate heat A method of controlling by an external jacket using a medium is exemplified. The latter method is preferable from the viewpoint of safety.
共重合に用いる重合開始剤は、重合方法に応じて、公知の開始剤、例えばアゾ系開始剤、過酸化物系開始剤、レドックス系開始剤など、から適宜選択すればよい。アゾ系開始剤としては、例えば、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）など、が挙げられる。過酸化物系開始剤としては、例えば、ジイソプロピルパーオキシジカーボネート、ジ−２−エチルヘキシルパーオキシジカーボネート、ジエトキシエチルパーオキシジカーボネートなどのパーカーボネート化合物；ｔ−ブチルパーオキシネオデカネート、α−クミルパーオキシネオデカネート、ｔ−ブチルパーオキシデカネートなどのパーエステル化合物；アセチルシクロヘキシルスルホニルパーオキシド；２，４，４−トリメチルペンチル−２−パーオキシフェノキシアセテートなど、が挙げられる。これらの開始剤に、過硫酸カリウム、過硫酸アンモニウム、過酸化水素などを組み合わせて開始剤とすることもできる。レドックス系開始剤としては、例えば、上記過酸化物と、亜硫酸水素ナトリウム、炭酸水素ナトリウム、酒石酸、Ｌ−アスコルビン酸、ロンガリットなどの還元剤とを組み合わせた開始剤が挙げられる。また、ＣＯとビニルエステル系単量体との共重合を高い温度で行った場合に、ビニルエステル系単量体の分解に起因するＰＶＡの着色が見られることがあるが、その場合には、着色の防止を目的として、酒石酸のような酸化防止剤を１〜１００ｐｐｍ（ビニルエステル系単量体に対して）程度、重合系に添加することはなんら差し支えない。 The polymerization initiator used for copolymerization may be appropriately selected from known initiators such as azo initiators, peroxide initiators, redox initiators and the like according to the polymerization method. Examples of the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile) and the like. Examples of the peroxide-based initiator include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, α -Perester compounds such as cumylperoxyneodecanate and t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate and the like. These initiators can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator. Examples of the redox initiator include an initiator in which the peroxide is combined with a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite. In addition, when the copolymerization of CO and vinyl ester monomer is performed at a high temperature, coloring of PVA due to decomposition of the vinyl ester monomer may be seen. In that case, For the purpose of preventing coloring, an antioxidant such as tartaric acid may be added to the polymerization system to the extent of 1 to 100 ppm (based on the vinyl ester monomer).
ＣＯと共重合させるビニルエステル系単量体は特に限定されず、例えば、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル、カプロン酸ビニル、カプリル酸ビニル、ラウリル酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル、オレイン酸ビニル、安息香酸ビニルなど、が挙げられる。なかでも、酢酸ビニルが好ましい。 The vinyl ester monomer to be copolymerized with CO is not particularly limited. For example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, caprylic acid Vinyl, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate and the like. Of these, vinyl acetate is preferred.
ＣＯとビニルエステル系単量体との共重合に際して、本発明の主旨を損なわない範囲で、他の単量体（Ａ）を共重合してもよい。使用しうる単量体（Ａ）として、例えば、エチレン、プロピレン、ｎ−ブテン、イソブチレンなどのα−オレフィン類；アクリル酸およびその塩；アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸ｉ−プロピル、アクリル酸ｎ−ブチル、アクリル酸ｉ−ブチル、アクリル酸ｔ−ブチル、アクリル酸２−エチルヘキシル、アクリル酸ドデシル、アクリル酸オクタデシルなどのアクリル酸エステル類；メタクリル酸およびその塩；メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸ｉ−プロピル、メタクリル酸ｎ−ブチル、メタクリル酸ｉ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸２−エチルヘキシル、メタクリル酸ドデシル、メタクリル酸オクタデシルなどのメタクリル酸エステル類；アクリルアミド；Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、ジアセトンアクリルアミド、アクリルアミドプロパンスルホン酸およびその塩、アクリルアミドプロピルジメチルアミンおよびその塩またはその４級塩、Ｎ−メチロールアクリルアミドおよびその誘導体などのアクリルアミド誘導体；メタクリルアミド；Ｎ−メチルメタクリルアミド、Ｎ−エチルメタクリルアミド、メタクリルアミドプロパンスルホン酸およびその塩、メタクリルアミドプロピルジメチルアミンおよびその塩またはその４級塩、Ｎ−メチロールメタクリルアミドおよびその誘導体などのメタクリルアミド誘導体；メチルビニルエーテル、エチルビニルエーテル、ｎ−プロピルビニルエーテル、ｉ−プロピルビニルエーテル、ｎ−ブチルビニルエーテル、ｉ−ブチルビニルエーテル、ｔ−ブチルビニルエーテル、ドデシルビニルエーテル、ステアリルビニルエーテルなどのビニルエーテル類；アクリロニトリル、メタクリロニトリルなどのニトリル類；塩化ビニル、フッ化ビニルなどのハロゲン化ビニル類；塩化ビニリデン、フッ化ビニリデンなどのハロゲン化ビニリデン類；酢酸アリル、塩化アリルなどのアリル化合物；マレイン酸、イタコン酸、フマル酸などの不飽和ジカルボン酸およびその塩またはそのエステル；ビニルトリメトキシシランなどのビニルシリル化合物；酢酸イソプロペニルなど、が挙げられる。 In the copolymerization of CO and a vinyl ester monomer, another monomer (A) may be copolymerized as long as the gist of the present invention is not impaired. Examples of the monomer (A) that can be used include α-olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and its salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic Acrylic esters such as i-propyl acid, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and salts thereof; methacryl Acid methyl, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Such as methacryl Esters; acrylamide; N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt, acrylamidopropyldimethylamine and its salt or quaternary salt thereof, N-methylol Acrylamide derivatives such as acrylamide and derivatives thereof; methacrylamide; N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid and salts thereof, methacrylamidepropyldimethylamine and salts thereof or quaternary salts thereof, N-methylol Methacrylamide derivatives such as methacrylamide and derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl Vinyl ethers such as propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride Vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and salts or esters thereof; vinyltrimethoxysilane Vinyl silyl compounds such as isopropenyl acetate and the like.
また、ＣＯとビニルエステル系単量体との共重合を、得られる共重合体の重合度を調節することなどを目的として、本発明の主旨を損なわない範囲で、連鎖移動剤の存在下で行ってもよい。連鎖移動剤としては、例えば、アセトアルデヒド、プロピオンアルデヒド、などのアルデヒド類；アセトン、メチルエチルケトンなどのケトン類；２−ヒドロキシエタンチオールなどのメルカプタン類；トリクロロエチレン、パークロロエチレンなどのハロゲン化炭化水素類が挙げられ、なかでもアルデヒド類およびケトン類を好適に用いることができる。連鎖移動剤の添加量は、添加する連鎖移動剤の連鎖移動定数、ならびに目的とするビニルエステル系重合体の重合度に応じて決定すればよいが、一般に、ビニルエステル系単量体に対して０．１〜１０重量％程度が望ましい。 In addition, in the presence of a chain transfer agent, the copolymerization of CO and vinyl ester monomers may be performed in order to adjust the degree of polymerization of the resulting copolymer and the like without departing from the gist of the present invention. You may go. Examples of the chain transfer agent include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; and halogenated hydrocarbons such as trichloroethylene and perchloroethylene. Among them, aldehydes and ketones can be preferably used. The addition amount of the chain transfer agent may be determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target vinyl ester polymer. About 0.1 to 10% by weight is desirable.
ＣＯとビニルエステル系単量体との共重合により得られた一酸化炭素−ビニルエステル系共重合体のけん化方法は特に限定されず、公知の方法を用いればよい。例えば、水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシドなどの塩基性触媒、あるいはｐ−トルエンスルホン酸などの酸性触媒を用いた、加アルコール分解反応または加水分解反応に基づくけん化方法を適用できる。この反応に使用しうる溶媒としては、例えば、メタノール、エタノールなどのアルコール類；酢酸メチル、酢酸エチルなどのエステル類；アセトン、メチルエチルケトンなどのケトン類：ベンゼン、トルエンなどの芳香族炭化水素などが挙げられ、これらを単独で、または２種以上を組み合わせて、用いることができる。なかでも、メタノールまたはメタノール／酢酸メチル混合溶液を溶媒とし、水酸化ナトリウムを触媒に用いて、一酸化炭素−ビニルエステル系共重合体のけん化を行うのが簡便であり好ましい。 The saponification method of the carbon monoxide-vinyl ester copolymer obtained by copolymerization of CO and vinyl ester monomer is not particularly limited, and a known method may be used. For example, a saponification method based on an alcoholysis or hydrolysis reaction using a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide, or an acidic catalyst such as p-toluenesulfonic acid can be applied. Examples of the solvent that can be used in this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone: aromatic hydrocarbons such as benzene and toluene. These can be used alone or in combination of two or more. Among them, it is simple and preferable to saponify the carbon monoxide-vinyl ester copolymer using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.
［ＣＯ変性ＰＶＡ］
本発明のＣＯ変性ＰＶＡは、一酸化炭素に基づく単位（ＣＯ単位）とビニルアルコール単位とを含む、ＣＯ単位由来のカルボニル基を主鎖に有するＰＶＡであり、上述した本発明の製造方法により製造できる。[CO-modified PVA]
The CO-modified PVA of the present invention is a PVA having a carbonyl group derived from a CO unit in the main chain, which includes a unit based on carbon monoxide (CO unit) and a vinyl alcohol unit, and is manufactured by the above-described manufacturing method of the present invention. it can.
本発明のＣＯ変性ＰＶＡでは、そのＣＯ単位の含有量（ＣＯ変性量）が０．０１〜８モル％である。ＣＯ変性量が８モル％を超えると、ＣＯ変性ＰＶＡ一分子あたりに含まれる疎水基の割合が高くなって、該ＰＶＡの水溶性が低下する。一方、ＣＯ変性量が０．０１モル％未満の場合、ＣＯ変性ＰＶＡの水溶性には優れるものの、該ＰＶＡ中に含まれるカルボニル基の数が少ないために、ＣＯ変性に基づく特性が発現しない。 In the CO-modified PVA of the present invention, the CO unit content (CO-modified amount) is 0.01 to 8 mol%. When the CO modification amount exceeds 8 mol%, the proportion of hydrophobic groups contained in one molecule of CO-modified PVA increases, and the water solubility of the PVA decreases. On the other hand, when the CO modification amount is less than 0.01 mol%, the water-solubility of the CO-modified PVA is excellent, but since the number of carbonyl groups contained in the PVA is small, the characteristics based on CO modification are not exhibited.
本発明のＣＯ変性ＰＶＡが、本発明の耐水性組成物の成分として用いられる場合、そのＣＯ変性量は、０．１モル％以上であることが必要であり、０．５モル％以上が好ましく、０．９モル％以上および１．０モル％以上の順に、より好ましい。 When the CO-modified PVA of the present invention is used as a component of the water-resistant composition of the present invention, the CO modification amount needs to be 0.1 mol% or more, preferably 0.5 mol% or more. , 0.9 mol% or more and 1.0 mol% or more are more preferable in this order.
本発明のＣＯ変性ＰＶＡでは、ＣＯ変性量の上限に関する以下の式（Ｉ）が満たされることが好ましい。この場合、より水溶性が良好なＣＯ変性ＰＶＡとなる。式（Ｉ）において、Ｘは、ＪＩＳ−Ｋ６７２６に準じて測定したＣＯ変性ＰＶＡの粘度平均重合度（以下、単に「重合度」ともいう）であり、Ｙは、ＣＯ変性ＰＶＡにおけるＣＯ変性量（モル％）である。換言すれば、本発明のＣＯ変性ＰＶＡでは、重合度ＸとＣＯ変性量Ｙとが、以下の式（Ｉ）を満たすことが好ましい、ともいえる。
Ｙ＜（−１．２１×１０-3）Ｘ＋８．２４ ・・・（Ｉ）In the CO-modified PVA of the present invention, the following formula (I) relating to the upper limit of the CO modification amount is preferably satisfied. In this case, CO-modified PVA with better water solubility is obtained. In the formula (I), X is the viscosity average polymerization degree of CO-modified PVA (hereinafter, also simply referred to as “polymerization degree”) measured according to JIS-K6726, and Y is the amount of CO modification in the CO-modified PVA ( Mol%). In other words, in the CO-modified PVA of the present invention, it can be said that the polymerization degree X and the CO modification amount Y preferably satisfy the following formula (I).
Y <(− 1.21 × 10 −3 ) X + 8.24 (I)
ＣＯ変性ＰＶＡにおけるＣＯ変性量Ｙは、該ＰＶＡの前駆体である一酸化炭素−ビニルエステル系共重合体に対するプロトンＮＭＲ測定により求めることができる。具体的には、以下のように求めればよい：ｎ−ヘキサン／アセトン混合液により、一酸化炭素−ビニルエステル系共重合体の再沈精製を３回以上十分に行った後、５０℃の減圧下で２日間乾燥し、分析用の共重合体を作製する。次に、該共重合体をＣＤＣｌ3に溶解させ、室温におけるプロトンＮＭＲのプロファイルを求める（実施例ではＪＥＯＬ製ＧＸ−５００を用いた）。得られたプロファイルから、ビニルエステルの主鎖のメチン（−ＣＨ−）に由来するピークα（化学シフトが４．７〜５．２ｐｐｍ）と、カルボニル基に隣接するメチレン（−ＣＨ2−）に由来するピークβ（化学シフトが２．２〜３．０ｐｐｍ）とを判別し、以下の式（II）によりＣＯ変性量を評価できる。
ＣＯ変性量(モル％)＝{（βのプロトン数／２）／(αのプロトン数＋βのプロトン数／２)}×１００(％) ・・・（II）The CO modification amount Y in the CO-modified PVA can be determined by proton NMR measurement on the carbon monoxide-vinyl ester copolymer that is a precursor of the PVA. Specifically, it may be obtained as follows: After reprecipitation and purification of the carbon monoxide-vinyl ester copolymer sufficiently with an n-hexane / acetone mixed solution three times or more, a reduced pressure at 50 ° C. Dry for 2 days to produce a copolymer for analysis. Next, the copolymer is dissolved in CDCl 3 to obtain a proton NMR profile at room temperature (in the examples, GX-500 manufactured by JEOL was used). From the obtained profile, the peak α (chemical shift is 4.7 to 5.2 ppm) derived from methine (—CH—) of the main chain of the vinyl ester and the methylene (—CH 2 —) adjacent to the carbonyl group are observed. The derived peak β (chemical shift is 2.2 to 3.0 ppm) is discriminated, and the CO modification amount can be evaluated by the following formula (II).
CO modification amount (mol%) = {(number of protons of β / 2) / (number of protons of α + number of protons of β / 2)} × 100 (%) (II)
ＣＯ変性ＰＶＡの粘度平均重合度Ｐは、ＪＩＳ−Ｋ６７２６に準じて測定される。即ち、ＣＯ変性ＰＶＡを再けん化し、精製した後、３０℃の水中で測定した極限粘度［η］から、以下の式（III）により評価できる。
Ｐ＝(［η］×１０3／８．２９)(1/0.62) ・・・（III）The viscosity average polymerization degree P of the CO-modified PVA is measured according to JIS-K6726. That is, after re-saponifying and purifying CO-modified PVA, it can be evaluated by the following formula (III) from the intrinsic viscosity [η] measured in water at 30 ° C.
P = ([η] × 10 3 /8.29) (1 / 0.62) (III)
ＣＯ変性ＰＶＡの重合度は２００〜３５００が好ましい。重合度が３５００を超えると、該ＰＶＡの水溶性が低下し、水性組成物としての粘度安定性が低下することがある。なお、本明細書において、ＣＯ変性ＰＶＡの水性組成物には、ＣＯ変性ＰＶＡの水溶液を含む。 The degree of polymerization of the CO-modified PVA is preferably 200-3500. When the degree of polymerization exceeds 3500, the water solubility of the PVA may decrease, and the viscosity stability as an aqueous composition may decrease. In the present specification, the aqueous composition of CO-modified PVA includes an aqueous solution of CO-modified PVA.
本発明のＣＯ変性ＰＶＡが、本発明の耐水性組成物の成分として用いられる場合、その重合度は、５００〜３５００が好ましく、８００〜３５００がより好ましい。重合度が５００未満では、耐水性組成物の耐水性が発現しないことがある。 When the CO-modified PVA of the present invention is used as a component of the water-resistant composition of the present invention, the degree of polymerization is preferably 500-3500, more preferably 800-3500. If the degree of polymerization is less than 500, the water resistance of the water resistant composition may not be exhibited.
本発明のＣＯ変性ＰＶＡの粘度（濃度４重量％の水溶液としたときの粘度：以下、単に「４％粘度」ともいう）は、２．０〜１５０．０ｍＰａ・ｓである。４％粘度が２．０ｍＰａ・ｓ未満では、該ＰＶＡの生産が困難になるので実用的ではない。４％粘度が１５０ｍＰａ・ｓを超えると、水性組成物としての粘度安定性が低下する。なお、ここでいう水溶液の粘度とは、ＪＩＳ−Ｋ６７２６により測定した粘度をいう。 The viscosity of the CO-modified PVA of the present invention (viscosity when an aqueous solution having a concentration of 4% by weight: hereinafter, also simply referred to as “4% viscosity”) is 2.0 to 150.0 mPa · s. If the 4% viscosity is less than 2.0 mPa · s, production of the PVA becomes difficult, which is not practical. When the 4% viscosity exceeds 150 mPa · s, the viscosity stability as an aqueous composition is lowered. In addition, the viscosity of aqueous solution here means the viscosity measured by JIS-K6726.
本発明のＣＯ変性ＰＶＡが、本発明の耐水性組成物の成分として用いられる場合、その４％粘度は、５．０〜１５０．０ｍＰａ・ｓが好ましく、この場合、該組成物の耐水性を向上できる。 When the CO-modified PVA of the present invention is used as a component of the water-resistant composition of the present invention, its 4% viscosity is preferably 5.0 to 150.0 mPa · s. In this case, the water resistance of the composition is reduced. It can be improved.
本発明のＣＯ変性ＰＶＡが上記式（Ｉ）を満たす場合、その４％粘度は、１４０ｍＰａ・ｓ以下が好ましく、この場合、該ＰＶＡの水溶性を向上できる。また、その４％粘度を１１０ｍＰａ・ｓ以下とすることにより、該ＰＶＡの水性組成物としての粘度安定性を向上できる。 When the CO-modified PVA of the present invention satisfies the above formula (I), the 4% viscosity is preferably 140 mPa · s or less, and in this case, the water solubility of the PVA can be improved. Moreover, the viscosity stability as an aqueous composition of this PVA can be improved by making the 4% viscosity into 110 mPa * s or less.
本発明のＣＯ変性ＰＶＡのけん化度は、６０〜９９．９９モル％である。けん化度が６０モル％未満の場合、ＣＯ変性ＰＶＡの水溶性が低下して、ＰＶＡの水性組成物を得ることが困難となる。一方、けん化度が９９．９９モル％を超えると、該ＰＶＡの生産が困難になるので実用的ではない。 The saponification degree of the CO-modified PVA of the present invention is 60 to 99.99 mol%. When the saponification degree is less than 60 mol%, the water solubility of the CO-modified PVA is lowered, and it becomes difficult to obtain an aqueous composition of PVA. On the other hand, if the degree of saponification exceeds 99.99 mol%, production of the PVA becomes difficult, which is not practical.
本発明のＣＯ変性ＰＶＡが、本発明の耐水性組成物の成分として用いられる場合、そのけん化度は、８５〜９９．９９モル％である必要があり、９５モル％以上が好ましく、９５〜９９．９モル％、および９８〜９９．９モル％の順により好ましい。けん化度が８５モル％未満の場合、該組成物の耐水性が低下する傾向にある。 When the CO-modified PVA of the present invention is used as a component of the water-resistant composition of the present invention, the saponification degree needs to be 85 to 99.99 mol%, preferably 95 mol% or more, and 95 to 99. It is more preferable in order of 0.9 mol% and 98-99.9 mol%. When the saponification degree is less than 85 mol%, the water resistance of the composition tends to decrease.
本発明のＣＯ変性ＰＶＡにおいて、ＣＯ単位に隣接するビニルアルコール単位の一部がエノン構造（−ＣＯ−ＣＨ＝ＣＨ−）に変化することがある。この構造は、一酸化炭素−ビニルエステル系共重合体をけん化する際に、水酸化ナトリウムなどを触媒とする脱酢酸反応または脱水反応が進行することにより生じる。この構造は、さらに、けん化後の乾燥工程において、該構造に隣接するビニルアルコール単位が脱水されることにより、ジエンあるいはトリエン構造などになることがある。即ち、本発明のＣＯ変性ＰＶＡでは、ＣＯ単位に隣接するビニルアルコール単位の一部が、エノン構造（−ＣＯ−ＣＨ＝ＣＨ−）に変化していてもよく、ジエンあるいはトリエン構造に変化していてもよい。 In the CO-modified PVA of the present invention, a part of the vinyl alcohol unit adjacent to the CO unit may change to an enone structure (—CO—CH═CH—). This structure is generated by the progress of a deacetic acid reaction or a dehydration reaction using sodium hydroxide or the like as a catalyst when saponifying a carbon monoxide-vinyl ester copolymer. Furthermore, this structure may be a diene or triene structure by dehydrating vinyl alcohol units adjacent to the structure in the drying step after saponification. That is, in the CO-modified PVA of the present invention, a part of the vinyl alcohol unit adjacent to the CO unit may be changed to an enone structure (—CO—CH═CH—), or changed to a diene or triene structure. May be.
［耐水性組成物］
本発明の耐水性組成物は、ＣＯ変性ＰＶＡと、分子内にヒドラジド基を２個以上有する多官能ヒドラジド化合物とを含む。このＣＯ変性ＰＶＡは、ＣＯ変性量、４％粘度およびけん化度について、上述した数値範囲を満たす。[Water resistant composition]
The water-resistant composition of the present invention contains CO-modified PVA and a polyfunctional hydrazide compound having two or more hydrazide groups in the molecule. This CO-modified PVA satisfies the numerical range described above with respect to the amount of CO modification, 4% viscosity and degree of saponification.
本発明の耐水性組成物に含まれるＣＯ変性ＰＶＡは、その重合度ＸとＣＯ変性量Ｙとが、上記式（Ｉ）を満たすことが好ましい。この場合、該組成物の耐水性を向上できる。 The CO-modified PVA contained in the water-resistant composition of the present invention preferably has a polymerization degree X and a CO modification amount Y satisfying the above formula (I). In this case, the water resistance of the composition can be improved.
また、本発明の耐水性組成物に含まれるＣＯ変性ＰＶＡは、重合度に関し、上述した数値範囲を満たすことが好ましい。 Further, the CO-modified PVA contained in the water-resistant composition of the present invention preferably satisfies the numerical range described above with respect to the degree of polymerization.
多官能ヒドラジド化合物は、分子内にヒドラジド基を２個以上有する化合物である限り特に限定されず、例として、アジピン酸ジヒドラジド、ポリアクリル酸ヒドラジド、イタコン酸ジヒドラジド、フマル酸ジヒドラジド、マレイン酸ジヒドラジド、セバシン酸ジヒドラジド、グルタル酸ジヒドラジド、コハク酸ジヒドラジド、マロン酸ジヒドラジド、シュウ酸ジヒドラジド、テレフタル酸ジヒドラジド、イソフタル酸ジヒドラジド、フタル酸ジヒドラジド、ピメリン酸ジヒドラジド、スベリン酸ジヒドラジド、アゼライン酸ジヒドラジド、ヘキサデカンジヒドラジド、リンゴ酸ジヒドラジド、イミノジ酢酸ジヒドラジド、エチレンジアミン四酢酸テトラヒドラジド、クエン酸トリヒドラジド、ブタントリカルボヒドラジド、ニトリロ酢酸トリヒドラジド、シクロヘキサントリカルボン酸トリヒドラジド、ピロメリット酸テトラヒドラジド、などが挙げられる。耐水性組成物として得られる耐水性、水溶性および安全性などを考慮すると、多官能性ヒドラジド化合物として、アジピン酸ジヒドラジドおよびポリアクリル酸ヒドラジドを用いることが好ましい。 The polyfunctional hydrazide compound is not particularly limited as long as it is a compound having two or more hydrazide groups in the molecule. Acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, malonic acid dihydrazide, oxalic acid dihydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, phthalic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide Iminodiacetic acid dihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, citric acid trihydrazide, butanetricarbohydrazide, nitriloacetic acid Hydrazide, cyclohexane tricarboxylic acid trihydrazide, pyromellitic acid tetrahydrazide, and the like. In view of water resistance, water solubility and safety obtained as the water resistant composition, it is preferable to use adipic acid dihydrazide and polyacrylic acid hydrazide as the polyfunctional hydrazide compound.
本発明の耐水性組成物における多官能ヒドラジド化合物の含有量は特に限定されないが、ＣＯ変性ＰＶＡ１００重量部に対して１〜１５重量部が好ましく、２〜８重量部がより好ましい。多官能ヒドラジド化合物の含有量が上記数値範囲未満の場合、架橋が十分に進行せずに、該組成物の耐水性が低下する傾向がある。一方、含有量が上記数値範囲を超えると、未反応の多官能ヒドラジド化合物が溶出して、該組成物の耐水性が却って低下する傾向となる。 Although content of the polyfunctional hydrazide compound in the water-resistant composition of this invention is not specifically limited, 1-15 weight part is preferable with respect to 100 weight part of CO modified PVA, and 2-8 weight part is more preferable. When the content of the polyfunctional hydrazide compound is less than the above numerical range, crosslinking does not proceed sufficiently, and the water resistance of the composition tends to decrease. On the other hand, when the content exceeds the above numerical range, the unreacted polyfunctional hydrazide compound is eluted, and the water resistance of the composition tends to decrease.
本発明の耐水性組成物の用途は特に限定されず、例えば、クリアコーティング剤、顔料コーティング剤、内添サイズ剤、感熱紙に用いるオーバーコートのバインダー、などの紙用コート剤の他、各種のバインダー、接着剤、繊維糊剤、表面処理剤、フィルムなどの各種の用途、特に耐水性が求められる用途、への適用が可能である。 The use of the water-resistant composition of the present invention is not particularly limited, and for example, various paper coating agents such as a clear coating agent, a pigment coating agent, an internal sizing agent, an overcoat binder used for thermal paper, and the like. The present invention can be applied to various uses such as binders, adhesives, fiber pastes, surface treatment agents, and films, particularly those requiring water resistance.
以下、実施例および比較例により、本発明をより詳細に説明する。本発明は、以下の実施例に限定されない。なお、これ以降、「部」および「％」は、特に断りのない限り、重量基準である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples. Hereinafter, “parts” and “%” are based on weight unless otherwise specified.
本実施例では、以下の製造例により得たＣＯ変性ＰＶＡについて、その水への溶解性（水溶性）、ならびに水溶液としたときの粘度安定性を評価した。また、該ＣＯ変性ＰＶＡを用いて調整したＰＶＡ水溶液と、架橋剤（多官能ヒドラジド化合物）とを混合して得た水性組成物を流延して形成した皮膜の耐水性を評価した。 In this example, the CO-modified PVA obtained in the following production examples was evaluated for its water solubility (water solubility) and viscosity stability when used as an aqueous solution. Moreover, the water resistance of the film formed by casting an aqueous composition obtained by mixing a PVA aqueous solution prepared using the CO-modified PVA and a crosslinking agent (polyfunctional hydrazide compound) was evaluated.
最初に、上記溶解性、粘度安定性および耐水性の評価方法を示す。 Initially, the evaluation method of the said solubility, viscosity stability, and water resistance is shown.
［ＣＯ変性ＰＶＡの溶解性試験］
最初に、蒸留水９６ｇとＣＯ変性ＰＶＡ４ｇとを室温で混合し、３０分間攪拌した。次に、得られたＣＯ変性ＰＶＡの水溶液を９０℃に昇温して１時間攪拌した後、室温まで冷却し、該水溶液を金網（１０５ｍｍφ、２５０メッシュ相当、目開き６３μｍ）を用いて濾過した。次に、濾過後の金網を１０５℃で３時間乾燥し、デシケータに収容した状態で室温まで冷却した後、その重量を測定して、水溶液を濾過する前に予め測定しておいた金網の重量からの増加分ａ（ｇ）を求めた。求めた増加分ａ（ｇ）と、最初に蒸留水に混合したＰＶＡの純分ｂ（％）とから、該ＰＶＡの不溶解分（％）を以下の式（IV）により算出した。
不溶解分（％）＝ａ(ｇ)／{４(ｇ)×１００／ｂ}×１００(％) ・・・（IV）
なお、純分ｂ（％）は、以下の式（Ｖ）から求めた値である。
純分ｂ（％）＝１０５℃で３時間乾燥させた後のＣＯ変性ＰＶＡの重量（ｇ）／乾燥前のＣＯ変性ＰＶＡの重量（ｇ） ・・・（Ｖ）[Solubility test of CO-modified PVA]
First, 96 g of distilled water and 4 g of CO-modified PVA were mixed at room temperature and stirred for 30 minutes. Next, the obtained aqueous solution of CO-modified PVA was heated to 90 ° C. and stirred for 1 hour, and then cooled to room temperature, and the aqueous solution was filtered using a wire mesh (corresponding to 105 mmφ, 250 mesh, opening 63 μm). . Next, the filtered wire mesh is dried at 105 ° C. for 3 hours, cooled to room temperature in a desiccator, the weight is measured, and the weight of the wire mesh measured before filtering the aqueous solution is measured. The increase a (g) from was obtained. From the obtained increase a (g) and the pure content b (%) of PVA first mixed in distilled water, the insoluble content (%) of the PVA was calculated by the following formula (IV).
Insoluble matter (%) = a (g) / {4 (g) × 100 / b} × 100 (%) (IV)
The pure content b (%) is a value obtained from the following equation (V).
Pure content b (%) = weight of CO-modified PVA after drying at 105 ° C. for 3 hours (g) / weight of CO-modified PVA before drying (g) (V)
ＣＯ変性ＰＶＡの水への溶解性は、算出した不溶解分の値により、以下の基準に従って判定した。Ｄ、Ｃ、Ｂ、Ａの順に、該ＰＶＡの水への溶解性が良好となる。
Ａ：０．０１％未満
Ｂ：０．０１〜０．５％
Ｃ：０．５〜２．０％
Ｄ：２．０％以上The solubility of CO-modified PVA in water was determined according to the following criteria based on the calculated insoluble content. In order of D, C, B, and A, the solubility of the PVA in water becomes better.
A: Less than 0.01% B: 0.01 to 0.5%
C: 0.5 to 2.0%
D: 2.0% or more
［水溶液の粘度安定性試験］
濃度１０％のＣＯ変性ＰＶＡ水溶液を調製し、調製した水溶液を恒温水槽により１０℃に保持して、調製後、該水溶液の温度が１０℃になった時点における該水溶液の粘度（初期粘度）η１と、１０℃で７日間保持した後の該水溶液の粘度η２とを測定した。なお、水溶液の粘度は、上述した方法により測定した。[Viscosity stability test of aqueous solution]
A CO-modified PVA aqueous solution having a concentration of 10% was prepared, and the prepared aqueous solution was kept at 10 ° C. by a constant temperature water bath. After the preparation, the viscosity of the aqueous solution at the time when the temperature of the aqueous solution reached 10 ° C. (initial viscosity) η1 And the viscosity η2 of the aqueous solution after being held at 10 ° C. for 7 days. The viscosity of the aqueous solution was measured by the method described above.
水溶液としたときのＣＯ変性ＰＶＡの粘度安定性は、測定したη１およびη２から、η２／η１（即ち、７日間保存後の粘度／初期粘度）を求め、求めた値により、以下の基準に従って判定した。Ｄ、Ｃ、Ｂ、Ａの順に、該ＰＶＡの水溶液としたときの粘度安定性が良好となる。
Ａ：２．０倍未満
Ｂ：２．０倍以上４．０倍未満
Ｃ：４．０倍以上、またはＰＶＡ水溶液のゲル化The viscosity stability of the CO-modified PVA when it is used as an aqueous solution is determined from the measured η1 and η2 by obtaining η2 / η1 (that is, the viscosity after storage for 7 days / initial viscosity) and determining the value according to the following criteria: did. In the order of D, C, B, and A, the viscosity stability when the aqueous solution of the PVA is obtained becomes good.
A: Less than 2.0 times B: 2.0 times or more and less than 4.0 times C: 4.0 times or more, or gelation of PVA aqueous solution
［皮膜の耐水性試験］
濃度４％のＣＯ変性ＰＶＡ水溶液を調製し、これに、多官能ヒドラジド化合物としてアジピン酸ジヒドラジドを、ＣＯ変性ＰＶＡに対して５部加えた後、得られた水性組成物を２０℃で流延して、厚さ４０μｍの皮膜を形成した。次に、得られた皮膜を、縦５ｃｍ×横５ｃｍの大きさに切り出して試験片を作製した。次に、作製した試験片を、９０℃の蒸留水に３０分間浸漬した後、回収し、試験片の表面に付着した水分をガーゼで拭き取った後に、その重量Ａを測定した。次に、重量測定後の試験片を、さらに１０５℃で１６時間乾燥した後、その重量Ｂを測定した。[Water resistance test of film]
A CO-modified PVA aqueous solution having a concentration of 4% was prepared, and 5 parts of adipic acid dihydrazide as a polyfunctional hydrazide compound was added to the CO-modified PVA, and the resulting aqueous composition was cast at 20 ° C. A film having a thickness of 40 μm was formed. Next, the obtained film was cut into a size of 5 cm long × 5 cm wide to prepare a test piece. Next, after the prepared test piece was immersed in distilled water at 90 ° C. for 30 minutes, and then collected, the moisture adhering to the surface of the test piece was wiped off with gauze, and the weight A was measured. Next, after the weight-measured test piece was further dried at 105 ° C. for 16 hours, its weight B was measured.
皮膜の耐水性は、測定した重量Ａおよび重量Ｂから、重量Ａ／重量Ｂの値を求めてこれを膨潤度とし、求めた膨潤度の値により、以下の基準に従って判定した。Ｄ、Ｃ、Ｂ、Ａの順に、皮膜の耐水性が良好となる。
Ａ：３．０倍未満
Ｂ：３．０倍以上４．５倍未満
Ｃ：４．５倍以上６．０倍未満
Ｄ：６．０倍以上、または試験片が溶解して回収できなかったThe water resistance of the film was determined from the measured weight A and weight B by determining the value of weight A / weight B as the degree of swelling, and using the obtained value of swelling degree, the determination was made according to the following criteria. The water resistance of the film becomes better in the order of D, C, B, and A.
A: Less than 3.0 times B: 3.0 times or more and less than 4.5 times C: 4.5 times or more and less than 6.0 times D: 6.0 times or more or the test piece was dissolved and could not be recovered
［ＣＯ変性ＰＶＡの製造］
（製造例１：ＰＶＡ１の製造）
撹拌機、窒素導入口、ＣＯ導入口および重合開始剤の添加口を備えた内容積１Ｌの加圧反応槽に、酢酸ビニル単量体２７５ｇ、メタノール２２５ｇおよび酒石酸１０ｍｇを仕込み、内容物を６０℃に昇温した後、３０分間の窒素バブリングにより反応系内を窒素置換した。次に、３０分間のＣＯバブリングにより反応系内をＣＯ置換した後、反応槽内の圧力が１．０ＭＰａとなるようにＣＯを導入し、次いで、重合開始剤として２，２’−アゾビスイソブチロニトリル（ＡＩＢＮ）０．２５ｇを槽内に圧入して、酢酸ビニル単量体とＣＯとの共重合を開始させた。重合中は、ＣＯの加圧により反応槽内の圧力を１．０ＭＰａに保つとともに、重合温度を６０℃に維持した。重合開始から２時間が経過し、重合率が３５％となったところで反応系にソルビン酸３０ｍｇを添加し、冷却して重合を停止させた。反応槽に設けられた排ガスラインから槽内のＣＯを排出した後、窒素ガスのバブリングにより、反応系内のＣＯを完全に脱気した。次に、反応槽を減圧して、反応系内に残留した未反応の酢酸ビニル単量体を除去し、ＣＯ変性ポリ酢酸ビニル（ＣＯ変性ＰＶＡｃ）のメタノール溶液を得た。[Production of CO-modified PVA]
(Production Example 1: Production of PVA1)
A pressurized reaction tank having an internal volume of 1 L equipped with a stirrer, a nitrogen inlet, a CO inlet and a polymerization initiator addition port was charged with 275 g of vinyl acetate monomer, 225 g of methanol and 10 mg of tartaric acid, and the contents were kept at 60 ° C. The temperature in the reaction system was replaced with nitrogen by bubbling for 30 minutes. Next, after the inside of the reaction system was CO-substituted by CO bubbling for 30 minutes, CO was introduced so that the pressure in the reaction tank was 1.0 MPa, and then 2,2′-azobisiso is used as a polymerization initiator. 0.25 g of butyronitrile (AIBN) was injected into the tank to initiate copolymerization of vinyl acetate monomer and CO. During the polymerization, the pressure in the reaction vessel was maintained at 1.0 MPa by pressurizing CO, and the polymerization temperature was maintained at 60 ° C. When 2 hours passed from the start of polymerization and the polymerization rate reached 35%, 30 mg of sorbic acid was added to the reaction system and cooled to stop the polymerization. After exhausting the CO in the tank from the exhaust gas line provided in the reaction tank, the CO in the reaction system was completely degassed by bubbling nitrogen gas. Next, the reaction tank was decompressed to remove unreacted vinyl acetate monomer remaining in the reaction system, and a methanol solution of CO-modified polyvinyl acetate (CO-modified PVAc) was obtained.
次に、得られた溶液にメタノールを加えて濃度を調整し、調整後の溶液１８８．８４ｇ（ＣＯ変性ＰＶＡｃが４０ｇ含まれる）に１１．１６ｇのアルカリ溶液（水酸化ナトリウムのメタノール溶液：濃度５％）を加えて、ＣＯ変性ＰＶＡｃのけん化を行った。なお、けん化溶液におけるＣＯ変性ＰＶＡｃの濃度は２０％、ＣＯ変性ＰＶＡｃ中の酢酸ビニル単位に対する水酸化ナトリウムのモル比は０．０３とした。 Next, methanol was added to the resulting solution to adjust the concentration, and 11.16 g of an alkali solution (sodium hydroxide in methanol: concentration 5) was added to 188.84 g of the adjusted solution (40 g of CO-modified PVAc was contained). %) Was added to saponify the CO-modified PVAc. The concentration of CO-modified PVAc in the saponified solution was 20%, and the molar ratio of sodium hydroxide to vinyl acetate units in the CO-modified PVAc was 0.03.
アルカリ溶液の添加後、約２分でゲル状物が生成したため、形成したゲルを反応槽から取り出して粉砕機により粉砕し、４０℃で１時間放置してけん化をさらに進行させた後、酢酸メチル２００ｇを加えて、ゲル中に残存するアルカリを中和した。フェノールフタレイン指示薬により中和の完了を確認した後、濾別して得た白色固体をメタノール１０００ｇに投入し、室温で３時間放置して洗浄した。次に、濾別および当該濾別により得た白色固体をメタノールに投入する洗浄操作を３回繰り返した後、遠心分離により得られた白色固体を、６５℃に保持した乾燥機中に２日間放置して乾燥させ、ＣＯ変性ＰＶＡ（ＰＶＡ１）を得た。得られたＰＶＡ１の重合度、けん化度、ＣＯ変性量および４％粘度を、上述の方法により評価したところ、重合度が８６０、けん化度が９８．４モル％、ＣＯ変性量が０．９モル％、４％粘度が８．５ｍＰａ・ｓであった。 Since a gel was formed in about 2 minutes after the addition of the alkaline solution, the formed gel was taken out of the reaction vessel, pulverized by a pulverizer, allowed to stand at 40 ° C. for 1 hour, and further saponified, and then methyl acetate. 200 g was added to neutralize the alkali remaining in the gel. After confirming the completion of neutralization with a phenolphthalein indicator, a white solid obtained by filtration was poured into 1000 g of methanol and washed by leaving it at room temperature for 3 hours. Next, the filtration and the washing operation of adding the white solid obtained by the filtration into methanol were repeated three times, and then the white solid obtained by centrifugation was left in a dryer maintained at 65 ° C. for 2 days. And dried to obtain CO-modified PVA (PVA1). When the polymerization degree, saponification degree, CO modification amount and 4% viscosity of the obtained PVA1 were evaluated by the above-mentioned methods, the polymerization degree was 860, the saponification degree was 98.4 mol%, and the CO modification amount was 0.9 mol. %, 4% viscosity was 8.5 mPa · s.
（製造例２〜３０：ＰＶＡ２〜３０の製造）
酢酸ビニル単量体およびメタノールの仕込み量、重合時におけるＣＯの圧力（表１における「重合ＣＯ圧」）などの重合条件、ならびに、けん化時におけるＣＯ変性ＰＶＡｃの濃度、酢酸ビニル単位に対する水酸化ナトリウムのモル比（表１における「ＮａＯＨモル比」）などのけん化条件を、以下の表１に示すように変更した以外は製造例１と同様にして、各種のＣＯ変性ＰＶＡ（ＰＶＡ２〜３０）を製造した。(Production Examples 2 to 30: Production of PVA 2 to 30)
Polymerization conditions such as the amount of vinyl acetate monomer and methanol charged, the pressure of CO during polymerization ("polymerization CO pressure" in Table 1), the concentration of CO-modified PVAc during saponification, sodium hydroxide relative to vinyl acetate units In the same manner as in Production Example 1 except that the saponification conditions such as the molar ratio (“NaOH molar ratio” in Table 1) were changed as shown in Table 1 below, various CO-modified PVA (PVA 2 to 30) were prepared. Manufactured.
（製造例３１：ＰＶＡ３１の製造）
重合溶媒としてメタノールの代わりにシクロヘキサンを用い、さらに、酢酸ビニル単量体およびシクロヘキサンの仕込み量、重合時におけるＣＯの圧力などの重合条件を、以下の表１に示すように変更した以外は製造例１と同様にして、ＣＯ変性ＰＶＡ（ＰＶＡ３１）を製造した。(Production Example 31: Production of PVA31)
Production Example except that cyclohexane was used in place of methanol as the polymerization solvent, and the polymerization conditions such as the charged amount of vinyl acetate monomer and cyclohexane and the pressure of CO during polymerization were changed as shown in Table 1 below. In the same manner as in Example 1, CO-modified PVA (PVA31) was produced.
（実施例１〜２５、参照例１および比較例１〜５）
上記のように製造したＰＶＡ１〜３１について、溶解性試験および水溶液の粘度安定性試験を実施した結果を表２に示す。また、表２には、各ＣＯ変性ＰＶＡの重合度、ＣＯ変性量（モル％）、けん化度（モル％）および４％粘度（ｍＰａ・ｓ）を示す。(Examples 1 to 25, Reference Example 1 and Comparative Examples 1 to 5)
Table 2 shows the results of carrying out the solubility test and the aqueous solution viscosity stability test for the PVA 1 to 31 produced as described above. Table 2 shows the polymerization degree, CO modification amount (mol%), saponification degree (mol%), and 4% viscosity (mPa · s) of each CO-modified PVA.
表２に示すように、ＣＯ変性量、けん化度、および４％粘度が上述した範囲にある実施例１〜２５の各ＣＯ変性ＰＶＡは、その溶解性および水溶液の粘度安定性に優れていた。特に、重合度ＸとＣＯ変性量Ｙとが上述した式（Ｉ）を満たすＣＯ変性ＰＶＡの溶解性が良好となり、式（Ｉ）を満たすとともに、４％水溶液の粘度が１４０ｍＰａ・ｓ以下のＣＯ変性ＰＶＡでは、その溶解性が全て「Ａ」となった。 As shown in Table 2, each CO-modified PVA of Examples 1 to 25 in which the CO modification amount, the degree of saponification, and the 4% viscosity are in the above-described ranges were excellent in the solubility and the viscosity stability of the aqueous solution. In particular, the solubility of the CO-modified PVA satisfying the above-described formula (I) with the degree of polymerization X and the CO modification amount Y becomes good, satisfies the formula (I), and the viscosity of the 4% aqueous solution is 140 mPa · s or less. In the modified PVA, the solubility was all “A”.
重合時に溶媒としてシクロヘキサンを用いた比較例５（ＰＶＡ３１）は、４％水溶液の粘度が１．５ｍＰａ・ｓと低く、水へ溶解させた際の不溶解分が多く、その溶解性に劣った。 In Comparative Example 5 (PVA31) using cyclohexane as a solvent at the time of polymerization, the viscosity of a 4% aqueous solution was as low as 1.5 mPa · s, and there were many insolubles when dissolved in water, and the solubility was poor.
なお、参照例１として挙げているＰＶＡ２９は、溶解性および水溶液の粘度安定性の双方が「Ａ」となったが、重合度が１００と低いために生産性に劣り、実用的ではないことから、参照例とした。 In addition, although PVA29 quoted as the reference example 1 became both "A" in the solubility and the viscosity stability of aqueous solution, since the polymerization degree is as low as 100, it is inferior in productivity and is not practical. Reference example.
（実施例２６〜３３および比較例６〜９）
ＰＶＡ１、２、４、９〜１１、１４〜１８、２９について、皮膜の耐水性試験を実施した結果を、以下の表３〜５に示す。(Examples 26 to 33 and Comparative Examples 6 to 9)
The following Tables 3 to 5 show the results of conducting the water resistance test of the coating on PVA1, 2, 4, 9-11, 14-18, and 29.
表３〜５に示すように、４％水溶液の粘度が２．０ｍＰａ・ｓ以上、ＣＯ変性量が０．１モル％以上、かつけん化度が８５モル％以上のＣＯ変性ＰＶＡにおいて、形成された皮膜の耐水性が向上した。 As shown in Tables 3 to 5, it was formed in a CO-modified PVA having a viscosity of 4% aqueous solution of 2.0 mPa · s or more, a CO modification amount of 0.1 mol% or more, and a caking degree of 85 mol% or more. The water resistance of the film was improved.
本発明は、その意図および本質的な特徴から逸脱しない限り、他の実施形態に適用しうる。この明細書に開示されている実施形態は、あらゆる点で説明的なものであってこれに限定されない。本発明の範囲は、上記説明ではなく添付したクレームによって示されており、クレームと均等な意味および範囲にあるすべての変更はそれに含まれる。 The present invention can be applied to other embodiments without departing from the spirit and essential characteristics thereof. The embodiments disclosed in this specification are illustrative in all respects and are not limited thereto. The scope of the present invention is shown not by the above description but by the appended claims, and all modifications that fall within the meaning and scope equivalent to the claims are embraced therein.
本発明の一酸化炭素−ビニルアルコール系共重合体は、良好な水溶性を有し、水性組成物としたときの粘度安定性に優れている。さらに、分子内にヒドラジド基を２個以上有する多官能ヒドラジド化合物と組合せることにより、優れた耐水性を発現させることも可能である。このため、本発明の一酸化炭素−ビニルアルコール系共重合体は、クリアコーティング剤、顔料コーティング剤、内添サイズ剤、感熱紙に用いるオーバーコートのバインダー、などの紙用コート剤の他、各種のバインダー、接着剤、繊維糊剤、表面処理剤、フィルムなどの各種の用途、特に耐水性が求められる用途、に、好適に用いることができる。 The carbon monoxide-vinyl alcohol copolymer of the present invention has good water solubility, and is excellent in viscosity stability when used as an aqueous composition. Furthermore, by combining with a polyfunctional hydrazide compound having two or more hydrazide groups in the molecule, it is possible to develop excellent water resistance. Therefore, the carbon monoxide-vinyl alcohol copolymer of the present invention includes various paper coating agents such as clear coating agents, pigment coating agents, internal sizing agents, and overcoat binders used for thermal paper. It can be suitably used for various uses such as binders, adhesives, fiber pastes, surface treatment agents, and films, particularly those requiring water resistance.
Claims (7)
一酸化炭素に基づく単位の含有量が０．０１〜８モル％であり、
けん化度が６０〜９９．９９モル％であり、
濃度４重量％の水溶液としたときの粘度が、２．０〜１５０．０ｍＰａ・ｓである、一酸化炭素−ビニルアルコール系共重合体。A carbon monoxide-vinyl alcohol copolymer comprising a unit based on carbon monoxide and a vinyl alcohol unit,
The content of units based on carbon monoxide is 0.01 to 8 mol%,
The degree of saponification is 60-99.99 mol%,
A carbon monoxide-vinyl alcohol copolymer having a viscosity of 2.0 to 150.0 mPa · s when an aqueous solution having a concentration of 4% by weight is used.
Ｙ＜（−１．２１×１０-3）Ｘ＋８．２４ （Ｉ）And JIS-K6726 viscosity average polymerization degree was measured according to X, the amount and Y is carbon monoxide according to claim 1 which satisfies the following Formulas (I) - vinyl alcohol copolymer.
Y <(− 1.21 × 10 −3 ) X + 8.24 (I)
前記耐水性組成物における前記多官能ヒドラジド化合物の含有量が、前記共重合体１００重量部に対して１〜１５重量部であり、
前記共重合体について、
一酸化炭素に基づく単位の含有量が０．１〜８モル％であり、けん化度が８５〜９９．９９モル％であり、濃度４重量％の水溶液としたときの粘度が、２．０〜１５０．０ｍＰａ・ｓである、耐水性組成物。A water-resistant composition comprising a carbon monoxide-vinyl alcohol copolymer containing carbon monoxide-based units and vinyl alcohol units, and a polyfunctional hydrazide compound having two or more hydrazide groups in the molecule. ,
The content of the polyfunctional hydrazide compound in the water resistant composition is 1 to 15 parts by weight with respect to 100 parts by weight of the copolymer,
About the copolymer,
The unit content based on carbon monoxide is 0.1 to 8 mol%, the degree of saponification is 85 to 99.99 mol%, and the viscosity when an aqueous solution having a concentration of 4% by weight is 2.0 to A water-resistant composition, which is 150.0 mPa · s.
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| JP2008544120A JP5009302B2 (en) | 2006-11-15 | 2007-11-09 | Process for producing carbon monoxide-vinyl alcohol copolymer, carbon monoxide-vinyl alcohol copolymer and water-resistant composition using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS633025A (en) * | 1986-06-20 | 1988-01-08 | シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ | Novel polymer |
| JPS63154737A (en) * | 1986-11-27 | 1988-06-28 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Novel polymer of carbon monoxide and alpha-olefinic unsaturated compound |
| JPH08151412A (en) * | 1994-11-28 | 1996-06-11 | Unitika Chem Kk | Method for water-proofing polyvinyl alcohol resin |
| JPH1135771A (en) * | 1997-07-18 | 1999-02-09 | Unitika Chem Co Ltd | Polyvinyl alcohol resin composition, paper coating agent based thereon and aqueous emulsion composition |
| WO2008096727A1 (en) * | 2007-02-07 | 2008-08-14 | Kuraray Co., Ltd. | Dispersion stabilizer for suspension polymerization of vinyl compound, and method for production of vinyl compound polymer |
-
2007
- 2007-11-09 WO PCT/JP2007/071794 patent/WO2008059763A1/en active Application Filing
- 2007-11-09 JP JP2008544120A patent/JP5009302B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS633025A (en) * | 1986-06-20 | 1988-01-08 | シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ | Novel polymer |
| JPS63154737A (en) * | 1986-11-27 | 1988-06-28 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Novel polymer of carbon monoxide and alpha-olefinic unsaturated compound |
| JPH08151412A (en) * | 1994-11-28 | 1996-06-11 | Unitika Chem Kk | Method for water-proofing polyvinyl alcohol resin |
| JPH1135771A (en) * | 1997-07-18 | 1999-02-09 | Unitika Chem Co Ltd | Polyvinyl alcohol resin composition, paper coating agent based thereon and aqueous emulsion composition |
| WO2008096727A1 (en) * | 2007-02-07 | 2008-08-14 | Kuraray Co., Ltd. | Dispersion stabilizer for suspension polymerization of vinyl compound, and method for production of vinyl compound polymer |
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| JPWO2008059763A1 (en) | 2010-03-04 |
| WO2008059763A1 (en) | 2008-05-22 |
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