JPH02178301A - Production of emulsion polymer - Google Patents
Production of emulsion polymerInfo
- Publication number
- JPH02178301A JPH02178301A JP33435488A JP33435488A JPH02178301A JP H02178301 A JPH02178301 A JP H02178301A JP 33435488 A JP33435488 A JP 33435488A JP 33435488 A JP33435488 A JP 33435488A JP H02178301 A JPH02178301 A JP H02178301A
- Authority
- JP
- Japan
- Prior art keywords
- water
- synthetic resin
- vinyl monomer
- emulsion polymer
- weight
- 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.)
- Granted
Links
- 239000004908 Emulsion polymer Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 46
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 46
- 229920006186 water-soluble synthetic resin Polymers 0.000 claims abstract description 36
- 239000012866 water-soluble synthetic resin Substances 0.000 claims abstract description 36
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000203 mixture Substances 0.000 abstract description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006253 efflorescence Methods 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract description 3
- 206010037844 rash Diseases 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- -1 etc. Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- CKSURTJJJBWBOU-UHFFFAOYSA-N 3-[(3-amino-3-imino-2-methylpropyl)diazenyl]-2-methylpropanimidamide;hydrochloride Chemical compound Cl.NC(=N)C(C)CN=NCC(C)C(N)=N CKSURTJJJBWBOU-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N butyl vinyl ether Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- 102100026788 ATP synthase subunit C lysine N-methyltransferase Human genes 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 241000255925 Diptera Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101000833848 Homo sapiens ATP synthase subunit C lysine N-methyltransferase Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- NDAJNMAAXXIADY-UHFFFAOYSA-N 2-methylpropanimidamide Chemical compound CC(C)C(N)=N NDAJNMAAXXIADY-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 241001507939 Cormus domestica Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- UZDXAQLLVAUBQD-UHFFFAOYSA-N ethyl prop-2-enoate;n-methylmethanamine Chemical compound CNC.CCOC(=O)C=C UZDXAQLLVAUBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 210000003141 lower extremity Anatomy 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
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- JLSGYVNIIASPIZ-UHFFFAOYSA-N n-methylmethanamine;propyl 2-methylprop-2-enoate Chemical group CNC.CCCOC(=O)C(C)=C JLSGYVNIIASPIZ-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は乳化重合体の製造方法に関するものである。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing emulsion polymers.
乳化重合体の製造方法としては従来から界面活性剤の水
溶液中でビニル単量体を乳化重合する方法が提供されて
いる。しかしながら該乳化重合体の製造に乳化剤として
用いる界面活性剤は乳化重合体により形成される塗膜に
も残存し、該塗膜の耐水性、耐薬品性、耐候性、密着性
等を劣化させる0
最近では例えば重合可能な二重結合を有する界面活性剤
が提供されている。このような界面活性剤はビニル単量
体を水中に乳化せしめるとともにビニル単量体と共重合
することによって乳化重合体中に取り込壕れる。また水
溶性アクリル系合成樹脂を分散剤とし通常の界面活性剤
を使用しない、いわゆるソーブレス乳化重合体も提供さ
れている。As a method for producing emulsion polymers, a method has conventionally been provided in which vinyl monomers are emulsion polymerized in an aqueous solution of a surfactant. However, the surfactant used as an emulsifier in the production of the emulsion polymer remains in the coating film formed by the emulsion polymer, deteriorating the water resistance, chemical resistance, weather resistance, adhesion, etc. of the coating film. Recently, for example, surfactants having polymerizable double bonds have been provided. Such a surfactant is incorporated into the emulsion polymer by emulsifying the vinyl monomer in water and copolymerizing it with the vinyl monomer. Also provided is a so-called sorbes emulsion polymer that uses a water-soluble acrylic synthetic resin as a dispersant and does not use an ordinary surfactant.
しかしながら重合可能か界面活性剤を使用する場合には
遊離界面活性剤が塗膜に残存はしないけれども、該界面
活性剤が乳化重合体中に取り込まれるので塗膜の耐水性
、耐薬品性、耐候性、密着性等が充分でなく、また水溶
性アクリル系合成樹脂を使用する場合には該水溶性アク
リル系合成樹脂が塗膜に残存するのでやはり上記塗膜性
能が充分でなく、上波音つの改良方法で得られた乳化重
合体は特にセメント基材、石膏基材、ケイ酸カルシウム
基材等のアルカリ性基材の表面に塗布され死時、耐水性
、耐薬品性、耐候性が問題になり、塗膜剥離や塗膜のエ
フロレッセンス等が起り易い。However, when a polymerizable surfactant is used, although the free surfactant does not remain in the coating film, the surfactant is incorporated into the emulsion polymer, improving the water resistance, chemical resistance, and weather resistance of the coating film. In addition, when a water-soluble acrylic synthetic resin is used, the water-soluble acrylic synthetic resin remains in the coating film, so the coating film performance is not sufficient, and the upper wave sound The emulsion polymer obtained by the improved method is especially applied to the surface of alkaline substrates such as cement substrates, gypsum substrates, calcium silicate substrates, etc., and its water resistance, chemical resistance, and weather resistance are problematic. , paint film peeling and paint film efflorescence are likely to occur.
本発明は上記従来の課題を解決するだめの手段として、
加水分解可能なシリル基を有する水溶性合成樹脂の水溶
液中で、該シリル基と反応可能な官能基を有するビニル
単量体を含む共単量体を乳化重合することを特徴とする
乳化重合体の製造方法を提供するものである。The present invention, as a means to solve the above-mentioned conventional problems,
An emulsion polymer characterized by emulsion polymerization of a comonomer containing a vinyl monomer having a functional group capable of reacting with the silyl group in an aqueous solution of a water-soluble synthetic resin having a hydrolyzable silyl group. The present invention provides a method for manufacturing.
本発明に用いられる加水分解可能なシリル基を有する水
溶性合成樹脂とは、カルボキシル基、水酸基、第4級ア
ンモニウム塩基等の水溶性基を有することによって水溶
性が付与された加水分解可能なシリル基を有する水溶性
合成樹脂である。このような水溶性合成樹脂は例えば加
水分解可能なシリル基を有するビニル単量体Aと、水溶
性基あるいは該水溶性基を生成し得る基を有するビニル
単量体Bと、肢ビニル単量体Aおよび該ビニル単量体B
と共重合可能な他のビニル単量体Cとの共重合体であ・
る。The water-soluble synthetic resin having a hydrolyzable silyl group used in the present invention refers to a hydrolyzable silyl resin that is imparted with water solubility by having a water-soluble group such as a carboxyl group, a hydroxyl group, or a quaternary ammonium base. It is a water-soluble synthetic resin having a group. Such a water-soluble synthetic resin includes, for example, a vinyl monomer A having a hydrolyzable silyl group, a vinyl monomer B having a water-soluble group or a group capable of producing the water-soluble group, and a vinyl monomer B having a hydrolyzable silyl group; body A and the vinyl monomer B
A copolymer with other vinyl monomer C that can be copolymerized with
Ru.
(ビニル単量体A)
本発明に用いられる加水分解可能なシリル基を有するビ
ニル岸量体Aにおいて、加水分解可能なシリル基とは下
記の構造を有するものである。(Vinyl monomer A) In the vinyl monomer A having a hydrolyzable silyl group used in the present invention, the hydrolyzable silyl group has the following structure.
(R)a −n
−8t −Xn
式中Rは炭素数1〜10のアルキル基、アリール基、ア
ラルキル基から選ばれる2価の炭化水素基、Xは例えば
−0CH3゜−0C2H5等のアルコキシル基、−CI
、−Br等のハロゲン等の加水分解可能な基である。(R)a -n -8t -Xn In the formula, R is a divalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, and X is an alkoxyl group such as -0CH3゜-0C2H5. ,-CI
, -Br, and other hydrolyzable groups such as halogens.
上記加水分解可能なシリル基を有するビニル単量体を具
体的に例示すれば、r−メタクリロキシプロピルトリメ
トキシシラン、N−β−(N−ビニルベンジルアミノエ
チル)−r−アミノプロピルトリメトキシシラン・塩酸
塩、ビニルトリアセトキシシラン、ビニルトリメトキシ
シラン等であるO
(ビニル単量体B)
本発明に用いられる水溶性基あるいは該水溶性基を生成
し得る基を有するビニル単量体Bとはアクリル酸、メタ
クリル酸、イタコン酸、クロトン酸、アトロバ酸、シト
ラコン酸、マレイン酸(無水物)等の重合可能な二重結
合を有する脂肪酸、ジメチルアミンエチルアクリレート
、ジメチルアミノエチルメタクリレート、ジメチルアミ
ノプロピルアクリレート、ジメチルアミンプロピルメタ
クリレート等の第3級アミン基を有するアクリレートま
たはメタクリレート、アクリルアミド、メタクリルアミ
ド等の重合可能な二重結合を有する酸アミド、酢酸ビニ
ル、プロピオン酸ビニル等の脂肪酸ビニルエステル等が
例示される。上記重合可能な二重結合を有する脂肪酸は
酸型あるいは塩型のいずれでもビニル単量体Bとして用
いられるが、通常酸型で共重合し、その後中和によって
塩型とする。上記第3級アミン基を有するアクリレート
またはメタクリレートは通常重合後に塩酸、酢酸専の酸
、あるいはモノクロロメタン、モノクロロエタン等のハ
ロゲン化アルキル、無水酢酸等の酸無水物、アセチルク
ロライド等の酸塩化物等によって4級化される。上記脂
肪酸ビニルエステルは重合後アルカリ加水分解によりビ
ニルアルコール部分とされる。Specific examples of the vinyl monomer having a hydrolyzable silyl group include r-methacryloxypropyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-r-aminopropyltrimethoxysilane・O (vinyl monomer B) which is a hydrochloride, vinyltriacetoxysilane, vinyltrimethoxysilane, etc. (vinyl monomer B) and a vinyl monomer B having a water-soluble group used in the present invention or a group capable of producing the water-soluble group is a fatty acid with a polymerizable double bond such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, atrobic acid, citraconic acid, maleic acid (anhydride), dimethylamine ethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl Examples include acrylates or methacrylates with tertiary amine groups such as acrylates and dimethylamine propyl methacrylate, acid amides with polymerizable double bonds such as acrylamide and methacrylamide, and fatty acid vinyl esters such as vinyl acetate and vinyl propionate. be done. The above-mentioned fatty acid having a polymerizable double bond can be used as the vinyl monomer B in either the acid form or the salt form, but it is usually copolymerized in the acid form and then converted into the salt form by neutralization. After polymerization, the acrylate or methacrylate having a tertiary amine group is usually treated with an acid such as hydrochloric acid or acetic acid, or an alkyl halide such as monochloromethane or monochloroethane, an acid anhydride such as acetic anhydride, or an acid chloride such as acetyl chloride. It is classified as quaternary by The fatty acid vinyl ester is converted into a vinyl alcohol moiety by alkaline hydrolysis after polymerization.
(ビニル単量体C)
上記ビニル単量体Aおよびビニル単量体Bと共重合可能
な他のビニル単量体Cとしては、メチルアクリレート、
エチルアクリレート、n−ブチルアクリレート、 1
so−ブチルアクリレート、2−エチルへキシルアクリ
レート、シクロへキシルアクリレート、テトラヒドロフ
ルフリルアクリレート、メチルメタクリレート、エチル
メタクリレート、n−ブチルメタクリレート、1so−
ブチルメタクリレート、2−エチルへキシルメタクリレ
ート、ステアリルメタクリレート、ラウリルメタクリレ
ート、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、1so−ブチルビニルエ
ーテル、n−プチルビニルエーテル、スチレン、α−メ
チルスチレン、アクリロニトリル、メタクリレートリル
、塩化ビニル、塩化ビニリデン、弗化ビニル、弗化ビニ
リデン、エチレン、フロピレン、イソプレン、クロロブ
レン、ブタジェン等のビニル単量体が例示される。(Vinyl Monomer C) Other vinyl monomers C copolymerizable with the vinyl monomer A and vinyl monomer B include methyl acrylate,
Ethyl acrylate, n-butyl acrylate, 1
so-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 1so-
Butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether,
n-propyl vinyl ether, 1so-butyl vinyl ether, n-butyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylaterile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, ethylene, fluoropyrene, isoprene, chlorobrene, butadiene Examples include vinyl monomers such as
(共重合)
上記ビニル単量体Aと上記ビニル単量体Bと上記ビニル
単量体Cとの混合物は通常、メタノール、イソプロパツ
ール、アセトン、テトラヒドロフラン等の水溶性有機溶
剤中において、アゾビスインブチロニトリル、アゾビス
ジメチルバレロニトIJル、ベンゾイルパーオキシド、
ラウロイルパーオキシド、クメンハイドロパーオキシド
等の油溶性重合開始剤を用いて共重合される。この際上
記ビニル単量体Aの上記混合物における割合は通常1〜
50重量%、上記ビニル単量体Bの上記混合物における
割合は通常3〜20重量係である。そしてビニル単量体
Bにおいては該ビニル単量体Bの有する水溶性基あるい
は該水溶性基を生成し得る基の親水性の度合によって上
記範囲内にて添加量が調節される。例えば親水性の度合
は第4級アンモニウム塩基〉カルボキシル基(塩型)〉
カルボキシル基(酸型)〉酸アミド基〉水酸基の順に弱
くなるであろう。(Copolymerization) A mixture of the vinyl monomer A, the vinyl monomer B, and the vinyl monomer C is usually prepared by treating azobis in a water-soluble organic solvent such as methanol, isopropanol, acetone, or tetrahydrofuran. Inbutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide,
It is copolymerized using an oil-soluble polymerization initiator such as lauroyl peroxide or cumene hydroperoxide. At this time, the proportion of the vinyl monomer A in the mixture is usually 1 to 1.
The proportion of the vinyl monomer B in the mixture is usually between 3 and 20% by weight. The amount of vinyl monomer B to be added is adjusted within the above range depending on the degree of hydrophilicity of the water-soluble group that vinyl monomer B has or the group that can generate the water-soluble group. For example, the degree of hydrophilicity is determined by quaternary ammonium base〉carboxyl group (salt type)〉
They will become weaker in the following order: carboxyl group (acid type) > acid amide group > hydroxyl group.
上記組成の水溶性合成樹脂は通常15〜70重を係程度
の固形分で重合される。そしてビニル単量体Bが水溶性
基を生成し得る基を有する場合には加水分解、4級化等
の手段によって該基を水溶性にする。あるいはビニル単
量体Bが酸型のカルボキシル基を含有する場合には重合
後にアンモニア、カセイソーダ、カセイカリ、トリメチ
ルアミン、ジメチルアミン、トリエタノールアミン等に
よって中和してもよい。そして上記水溶性化、4級化、
中和等を行なう場合にはあらかじめ重合後に得られた重
合体溶液を濃縮して有機溶剤含有量を少なくしておいて
もよいし、上記処理を行なった後に有機溶剤を除去して
水と置換してもよい。The water-soluble synthetic resin having the above composition is usually polymerized with a solid content of about 15 to 70 parts by weight. When the vinyl monomer B has a group capable of forming a water-soluble group, the group is made water-soluble by means such as hydrolysis or quaternization. Alternatively, when the vinyl monomer B contains an acid type carboxyl group, it may be neutralized with ammonia, caustic soda, caustic potash, trimethylamine, dimethylamine, triethanolamine, etc. after polymerization. And the above-mentioned water solubility, quaternization,
When performing neutralization, etc., the polymer solution obtained after polymerization may be concentrated in advance to reduce the organic solvent content, or the organic solvent may be removed after the above treatment and replaced with water. You may.
(乳化重合体の製造)
上記水溶性合成樹脂の水溶液中で蚊水溶性合成樹脂に含
まれるシリル基と反応可能な官能基を有するビニル単量
体を含む共単量体を乳化重合する。(Production of emulsion polymer) A comonomer containing a vinyl monomer having a functional group capable of reacting with a silyl group contained in the mosquito water-soluble synthetic resin is emulsion polymerized in an aqueous solution of the water-soluble synthetic resin.
該共単量体とは該シリル基と反応可能な官能基を有する
ビニル単量体りと、該ビニル単量体りと共重合可能なビ
ニル単量体Eとの混合物である。The comonomer is a mixture of a vinyl monomer having a functional group capable of reacting with the silyl group and a vinyl monomer E that can be copolymerized with the vinyl monomer.
(ビニル単量体D)
ビニル単量体りは該シリル基と反応可能な官能基を有す
るものであり、該シリル基と反応可能な官能基とはカル
ボキシル基、水酸基、メチロール基、アミン基、酸アミ
ド基、グリシジル基、加水分解可能なシリル基等である
。このような官能基を有するビニル単量体りのうちカル
ボキシル基を有するものとしてはアクリル酸、メタクリ
ル酸、イタコン酸等、水酸基を有するものとしてはβ−
ハイドロキシエチルアクリレート、β−ハイドロキシエ
チルメタクリレート、β−ハイドロキシプロピルアクリ
レート、β−ハイドロキシプロピルメタアクリレート、
アリルアルコール等、メチロール基を有するものとして
はN−メチロールアク)ルアミド、N−メチロールメタ
クリルアミド等、アミン基を有するものとしてはジメチ
ルアミノエチルアクリレート、ジメチルアミノエチルメ
タクリレート等、酸アミド基を有するものとしてはア。(Vinyl monomer D) The vinyl monomer has a functional group that can react with the silyl group, and the functional groups that can react with the silyl group include a carboxyl group, a hydroxyl group, a methylol group, an amine group, These include acid amide groups, glycidyl groups, and hydrolyzable silyl groups. Among vinyl monomers having such functional groups, those having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, etc., and those having a hydroxyl group include β-
Hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate,
Allyl alcohol, etc., those having a methylol group include N-methylolacrylamide, N-methylol methacrylamide, etc. Those having an amine group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc. Those having an acid amide group Ha.
クリルアミド、メタクリルアミド等、グリシジル基を有
するものとしてはグリシジルアクリレート、グリシジル
メタクリレート、グリシジルアリルエーテル、加水分解
可能なシリル基を有するものとしては前記したr−メタ
クリロキシプロピルトリメトキシシラン、ビニルトリア
セトキシシラン、ビニルトリメトキシシラン等が例示さ
れる。Examples of compounds having a glycidyl group such as acrylamide and methacrylamide include glycidyl acrylate, glycidyl methacrylate, and glycidyl allyl ether; examples of those having a hydrolyzable silyl group include the above-mentioned r-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, Examples include vinyltrimethoxysilane.
(ビニル単量体E)
上記ビニル単量体りと共重合可能ガビニル単量体Eとし
ては、メチルアクリレート、エチルアクリレート、n−
ブチルアクリレート、1llIo−ブチルアクリレート
、2−エチルへキシルアクリレト、シクロヘキシルアク
リレート、テトラヒドロフルフリルアクリレート、メチ
ルメタクリレート、エチルメタクリレート、n−ブチル
メタクリレ−)、 1so−ブチルメタクリレート、
2−エチルへキシルメタクリレート、ステアリルメタク
リレート、ラウリルメタクリレート、メチルビニルエー
チル、エチルビニルエーテル、H−プロピルビニルエー
テル、1so−フチルビニルエーテル、nブチルビニル
エーテル、スチレン、α−メチルスチレン、アクリロニ
トリル、メタクリレートリル、酢酸ビニル、塩化ビニル
、塩化ビニリデン、弗化ビニル、弗化ヒニリテン、エチ
レン、プロピレン、イソプレン、クロロブレン、ブタジ
ェン等のビニル単量体がある。(Vinyl monomer E) Examples of the gavinyl monomer E that can be copolymerized with the above vinyl monomer include methyl acrylate, ethyl acrylate, n-
Butyl acrylate, 11Io-butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate), 1so-butyl methacrylate,
2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ethyl, ethyl vinyl ether, H-propyl vinyl ether, 1so-phthyl vinyl ether, n-butyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylaterile, vinyl acetate , vinyl chloride, vinylidene chloride, vinyl fluoride, hnyritene fluoride, ethylene, propylene, isoprene, chlorobrene, butadiene, and other vinyl monomers.
(乳化重合体の製造)
上記ビニル単量体りと上記ビニル単量体Eとの混合物で
ある共単量体において、上記ビニル単量体りは通常1〜
10重量係程度含有される。上記共単量体は上記したよ
うに上記水溶性合成樹脂の水溶液中に乳化され、過硫酸
アンモン、過硫酸カリウム、過硫酸ソーダ、過硫酸ソー
ダ、アゾビス(2アミジノプロパン)ハイドロクロライ
ド等の水溶性重合開始剤、あるいは上水溶性重合開始剤
とともに該開始剤の分解促進剤として次亜硫酸ソーダ、
重亜硫酸ソーダ、アスコルビン酸等の還元剤を使用して
該乳化された共単量体を重合する。(Production of emulsion polymer) In the comonomer which is a mixture of the above vinyl monomer and the above vinyl monomer E, the vinyl monomer is usually 1 to 1.
Contains about 10% by weight. As mentioned above, the above comonomer is emulsified in an aqueous solution of the above water-soluble synthetic resin, and water-soluble materials such as ammonium persulfate, potassium persulfate, sodium persulfate, sodium persulfate, azobis(2amidinopropane) hydrochloride, etc. Sodium hyposulfite is used as a polymerization initiator or a water-soluble polymerization initiator as well as a decomposition accelerator for the initiator.
The emulsified comonomer is polymerized using a reducing agent such as sodium bisulfite or ascorbic acid.
上記水溶液中に上記水溶性合成樹脂は通常5〜50重量
L重量上4水溶液中に乳化される共単量体は得られる乳
化重合体中の固形分濃度が通常20〜70重量係程度に
なるように添加される。The water-soluble synthetic resin in the aqueous solution is usually 5 to 50 liters (by weight).4 The comonomer emulsified in the aqueous solution has a solid content concentration of usually about 20 to 70 liters in the resulting emulsion polymer. It is added as follows.
上記水溶液には更に乳化補助剤として従来の界面活性剤
、望ましくは上記共単量体と共重合可能力界面活性剤、
ポリビニルアルコール、ポリアクリル酸塩類、アルギン
酸塩類、水溶性アクリル系合成樹脂等の分散安定剤、炭
酸カルシウム、ピロ燐酸ソーダ等の分散剤等が添加され
てもよい。また上記水溶液は必要とあれば酸またはアル
カリによってpHを所定の値に調節してもよい。The above aqueous solution further includes a conventional surfactant as an emulsification aid, preferably a surfactant capable of copolymerizing with the above comonomer,
Dispersion stabilizers such as polyvinyl alcohol, polyacrylates, alginates, water-soluble acrylic synthetic resins, and dispersants such as calcium carbonate and sodium pyrophosphate may be added. Further, the pH of the aqueous solution may be adjusted to a predetermined value with an acid or an alkali, if necessary.
以上のようにして本発明の乳化重合体が製造される。The emulsion polymer of the present invention is produced as described above.
本発明の乳化重合体を基材に塗布し塗膜を生成すると、
乳化剤として用いた加水分解可能なシリル基を有する水
溶性合成樹脂と、乳化重合体中に含まれる該シリル基と
反応可能な官能基とが常温でも反応して架橋を生成する
。このようにして水溶性合成樹脂は乳化重合体と架橋に
よって結合する。When the emulsion polymer of the present invention is applied to a substrate to form a coating film,
The water-soluble synthetic resin having a hydrolyzable silyl group used as an emulsifier and the functional group contained in the emulsion polymer that can react with the silyl group react even at room temperature to form a crosslink. In this way, the water-soluble synthetic resin is bonded to the emulsion polymer through crosslinking.
したがって本発明においては基材がアルカリ性であって
もすぐれた密着性、耐候性、耐水性のある塗膜が得られ
、また高いガラス転移点を有していても低い最低造膜温
度(MFT)を示し、すぐれた耐エフロレッセンス性を
発揮する。したがって従来の加水分解可能なシリル基を
有する乳化重合体では該シリル基濃度を増加させるとシ
リル基の加水分解物であるシラノール基がミセル外側に
配向されるためにミセルがコロイダルシリカ状とガって
ガラス転移点が低くても最低造膜温度が高くなるが、本
発明の乳化重合体では水溶性合成樹脂に含まれるシリル
基が高濃度であっても最低造膜温度の低い乳化重合体が
得られる。このようにしてシリル基!11度を高くすれ
ば架橋密度が大きくカリ、上記塗膜性能が大巾に向上す
るのである。Therefore, in the present invention, a coating film with excellent adhesion, weather resistance, and water resistance can be obtained even if the base material is alkaline, and has a low minimum film forming temperature (MFT) even if the base material has a high glass transition point. and exhibits excellent efflorescence resistance. Therefore, in conventional emulsion polymers having hydrolyzable silyl groups, when the concentration of the silyl groups is increased, the silanol groups, which are hydrolyzed products of the silyl groups, are oriented to the outside of the micelles, causing the micelles to become colloidal silica-like and bulky. However, in the emulsion polymer of the present invention, even if the water-soluble synthetic resin contains a high concentration of silyl groups, the minimum film-forming temperature is low. can get. In this way, the silyl group! If the temperature is increased to 11 degrees, the crosslinking density will be large and the coating performance will be greatly improved.
ψ施例1(水溶性分1y、樹脂原料Aの製造)攪拌機、
温度計、コンデンサーを付した反応器に下記の組成を仕
込む。ψ Example 1 (Water-soluble content 1y, production of resin raw material A) Stirrer,
Charge the following composition into a reactor equipped with a thermometer and condenser.
スチレン 40重量部メチル
メタクリレート 20 In−ブチルアク
リレート 20 #メタクリル酸
10 Iアゾビスイソブチロニトリル
3イソプロパツール 100 l上記
組成は75°Cで10時間加温攪拌することにより重合
され、固形分50重量%、粘度T(ガドナーホルツ)の
溶液重合体を得た。重合後肢溶液重合体を減圧蒸留して
固形分80重量cl)にまで濃縮した。このようにして
水溶性合成樹脂原料Aが製造される。Styrene 40 parts by weight Methyl methacrylate 20 In-butyl acrylate 20 #Methacrylic acid
10 I azobisisobutyronitrile
3 Isopropanol 100 l The above composition was polymerized by heating and stirring at 75°C for 10 hours to obtain a solution polymer having a solid content of 50% by weight and a viscosity of T (Gadner-Holtz). The polymerized hindlimb solution polymer was distilled under reduced pressure to concentrate the solid content to 80 ml by weight. In this way, water-soluble synthetic resin raw material A is produced.
実施例2(水溶性合成樹脂原料Bの製造)実施例1と同
様な反応器に下記の組成を仕込む。Example 2 (Production of water-soluble synthetic resin raw material B) A reactor similar to Example 1 was charged with the following composition.
メチルメタクリレート 40重量部n−ブ
チルアクリレート 25 I。Methyl methacrylate 40 parts by weight n-butyl acrylate 25 I.
イソブチルアクリレート 15重量部レート
ビニルトリアセトキシシラン 10ベンゾイルパー
オキシド 31エタノール
50 Iアセトン 5
0 1上記組成は実施例1と同様にして重合され、固形
分500重量部粘度U(ガードナーホルツフの溶液重合
体を得た。該溶液重合体は実施例1と同様にして固形分
800重量部まで濃縮して水溶性合成樹脂原料Bが製造
される。Isobutyl acrylate 15 parts by weight Vinyltriacetoxysilane 10 Benzoyl peroxide 31 Ethanol
50 I acetone 5
0 1 The above composition was polymerized in the same manner as in Example 1 to obtain a solution polymer with a solid content of 500 parts by weight and a viscosity of U (Gardnerholtz). Water-soluble synthetic resin raw material B is produced by concentrating to 50%.
実施例3(乳化重合体co裂製造
実施例1で得られた水溶性合成樹脂原料A25重量部、
25重量係アンモニア水溶液1.2重量部、イオン交換
水95重量部を実施例1と同様々反応器中に仕込む。核
水溶性合成樹脂原料Aはこのようにして該アンモニア水
溶液により中和されて水溶性合成樹脂Aとなり、紋反応
器中には該水溶性合成樹脂Aの水溶液が形成される。蚊
反応器中には更に下記の組成の共単量体が仕込まれる。Example 3 (emulsion polymer co-crack production 25 parts by weight of the water-soluble synthetic resin raw material A obtained in Example 1,
In the same manner as in Example 1, 1.2 parts by weight of ammonia aqueous solution and 95 parts by weight of ion-exchanged water were charged into a reactor. The core water-soluble synthetic resin raw material A is thus neutralized by the ammonia aqueous solution to become the water-soluble synthetic resin A, and an aqueous solution of the water-soluble synthetic resin A is formed in the reactor. A comonomer having the following composition is also charged into the mosquito reactor.
スチレン 20重量部メチルメ
タクリレート 30 lエチルアクリレー
ト 28 Iビニルトリメトキシシラン
21該共単量体は過硫酸カリウム0.1重量
部を添加して80°Cで6時間重合させる。Styrene 20 parts by weight Methyl methacrylate 30 l Ethyl acrylate 28 I Vinyltrimethoxysilane 21 The comonomer is polymerized at 80°C for 6 hours with the addition of 0.1 part by weight of potassium persulfate.
このようにして固形分50重量%、粘度250cpsの
乳化重合体Cを得た。In this way, an emulsion polymer C having a solid content of 50% by weight and a viscosity of 250 cps was obtained.
実施例4(乳化重合体りの製造)
実施例1で得られた水溶性合成樹脂原料A15重量部、
25重量係トリエチルアミン水溶液0.7重量部、イオ
ン交換水47重量部を実施例1と同様な反応器中に仕込
む。該水溶性合成樹脂原料Aはこのようにして該トリエ
チルアミン水溶液により中和されて水溶性合成樹脂A′
となり、該反応器中には討水溶性合成樹脂A′の水溶液
が形成される。Example 4 (Production of emulsion polymer) 15 parts by weight of the water-soluble synthetic resin raw material A obtained in Example 1,
0.7 parts by weight of an aqueous triethylamine solution and 47 parts by weight of ion-exchanged water were charged into a reactor similar to that in Example 1. The water-soluble synthetic resin raw material A is thus neutralized with the triethylamine aqueous solution to form the water-soluble synthetic resin A'.
Thus, an aqueous solution of the water-soluble synthetic resin A' is formed in the reactor.
診反応器中には更に下記の組成の共単量体が仕込まれる
。A comonomer having the following composition is further charged in the diagnostic reactor.
スチレン
25重量部
メチルメタクリレート33
エチルアクリレート
8 I
トリメトキシシラン
上記共単量体を仕込んだ後頁に下記の組成が添加される
。Styrene 25 parts by weight Methyl methacrylate 33 Ethyl acrylate 8 I Trimethoxysilane After the above comonomers were charged, the following composition was added.
エレミノールJS−2* 0.5重量部イオン
交換水 50 1過硫酸アンモニ
ウム 0651*エレミノールJS−2:
三洋化成■製(重合可能な界面活性剤)
上記混合物は80℃で7時間重合されて固形分50重量
%、粘度100 cpaの乳化重合体を得た。Eleminol JS-2* 0.5 parts by weight Ion exchange water 50 1 Ammonium persulfate 0651*Eleminol JS-2:
Manufactured by Sanyo Kasei (polymerizable surfactant) The above mixture was polymerized at 80° C. for 7 hours to obtain an emulsion polymer having a solid content of 50% by weight and a viscosity of 100 cpa.
実施例5(乳化重合体Eの製造)
実施例2で得られた水溶性合成樹脂原料B25重量部、
氷酢酸0.6重量部、イオン交換水95重量部を実施例
1と同様な反応器中に仕込む。該水溶性合成樹脂原料B
はこのようにして該氷酢酸により4級化されて水溶性合
成樹脂Bとなり、訪反応器中には該水溶性合成樹脂Bの
水溶液が形成される。該反応器中には更に下記の組成の
共単量体が仕込まれる。Example 5 (Production of emulsion polymer E) 25 parts by weight of water-soluble synthetic resin raw material B obtained in Example 2,
0.6 parts by weight of glacial acetic acid and 95 parts by weight of ion-exchanged water are charged into a reactor similar to that in Example 1. The water-soluble synthetic resin raw material B
is thus quaternized by the glacial acetic acid to form water-soluble synthetic resin B, and an aqueous solution of water-soluble synthetic resin B is formed in the reactor. A comonomer having the following composition is further charged into the reactor.
スチレン 20重量部メチルメ
タクリレート 30 lエチルアクリレー
ト 28 Iトリメトキシシラン
該共単量体はアゾビス(2−アミジノプロパン)ハイド
ロクロライド0.5重量部を添加して85°Cで4時間
重合させる。Styrene 20 parts by weight Methyl methacrylate 30 l Ethyl acrylate 28 I trimethoxysilane The comonomer is polymerized at 85°C for 4 hours with the addition of 0.5 part by weight of azobis(2-amidinopropane) hydrochloride.
このようにして固形分50重f%、粘度150cpsの
乳化重合体Eを得た。In this way, an emulsion polymer E having a solid content of 50% by weight and a viscosity of 150 cps was obtained.
実施例6(乳化重合体Fの製造)
実施例2で得られた水溶性合成樹脂原料B15重量部、
アセチルクロライド0.4重量部、イオン交換水45重
量部を実施例1と同様な反応器中に仕込み70’Cで2
時間反応させて該水溶性合成樹脂原料Bに含まれる第3
級アミン基を4級化する。Example 6 (Production of emulsion polymer F) 15 parts by weight of water-soluble synthetic resin raw material B obtained in Example 2,
0.4 parts by weight of acetyl chloride and 45 parts by weight of ion-exchanged water were charged into a reactor similar to that in Example 1 and heated at 70'C for 2 hours.
The third component contained in the water-soluble synthetic resin raw material B is reacted for a time.
Quaternary amine groups are quaternized.
該水溶性合成樹脂原料Bはこのようにしてアセチルクロ
ライドにより4級化さり、て水溶性合成樹脂B′となり
、該反応器中には該水溶性合成樹1指B′の水溶液が形
成される。該反応器中には更に下記の組成の共単量体が
仕込せれる。The water-soluble synthetic resin raw material B is thus quaternized with acetyl chloride to become a water-soluble synthetic resin B', and an aqueous solution of the water-soluble synthetic resin B' is formed in the reactor. . A comonomer having the following composition is further charged into the reactor.
スチレン 25重量部メチルメ
タクリレート33
エチルアクリレ−) 28 #該反
応器中には次いでイオン交換水52重量部、アゾビス(
2アミジノプロパン)ハイドロクロライド05重量部、
カチオゲンしく第1工業製薬■製カチオン界面活性剤)
1重量部の混合液が仕込まれ、85°Cで6時間重合さ
せる。Styrene 25 parts by weight Methyl methacrylate 33 Ethyl acrylate) 28
2 amidinopropane) hydrochloride 05 parts by weight,
Cationic surfactant manufactured by Daiichi Kogyo Seiyaku ■)
1 part by weight of the mixture was charged and polymerized at 85°C for 6 hours.
このようにして固形分50重量%、粘度150epsの
乳化重合体Fを得た。In this way, an emulsion polymer F having a solid content of 50% by weight and a viscosity of 150 eps was obtained.
比較例1(乳化重合体Gの製造)
実施例1と同様な反応器中にエレミノールJS24重量
部、イオン交換水100重を部を仕込み、80°Cに昇
温した後下記の組成の共単量体を仕込む。Comparative Example 1 (Manufacture of Emulsion Polymer G) 24 parts by weight of Eleminol JS and 100 parts by weight of ion-exchanged water were charged into a reactor similar to that in Example 1, and after heating to 80°C, a comonomer with the following composition was added. Prepare the mass.
スチレン 4oM預”部メチル
メタクリレート30
nブチルアクリレート 27次いで過硫酸
カリウム0.3重量部と炭酸水素ナトリウム0.1重口
部とを添加し80°Cに25時間重合して固形分50重
量%、粘度100 cpsの乳化重合体Gを得た。Styrene 4oM deposit Methyl methacrylate 30 n Butyl acrylate 27 Next, 0.3 parts by weight of potassium persulfate and 0.1 parts by weight of sodium hydrogen carbonate were added and polymerized at 80°C for 25 hours to obtain a solid content of 50% by weight. Emulsion polymer G having a viscosity of 100 cps was obtained.
比較例2(乳化重合体Hの製造)
実施例1と同様な反応器中にカチオゲンL4重■部、イ
オン交換水100重量部を仕込み、80’(J昇温した
後比較例1と同一組成の共単量体を仕込む。次いでアゾ
ビス(2アミジノプロパン)ハイドロクロライドO75
重量部を添加し80°Cにて5時間重合して固形分50
ii%、粘度500epHの乳化重合体Hを得た。Comparative Example 2 (Manufacture of Emulsion Polymer H) 4 parts by weight of cation L and 100 parts by weight of ion-exchanged water were charged into a reactor similar to that in Example 1, and after raising the temperature to 80' (J), the same composition as in Comparative Example 1 was prepared. Next, azobis(2amidinopropane) hydrochloride O75 is charged.
Add part by weight and polymerize at 80°C for 5 hours to reach a solid content of 50.
Emulsion polymer H having a viscosity of 500 epH was obtained.
塗膜試験
上記実施例および比較例によって作製した乳化重合体C
,D、E、F、G、Hについて下記の通りの塗膜試験を
行なった。Coating film test Emulsion polymer C prepared according to the above examples and comparative examples
, D, E, F, G, and H were subjected to the following coating film test.
耐水性ニガラス板に各試料を流し塗りして室温で7日間
放置後、室温で水に96時間
浸漬した後の塗膜をL!察する。Each sample was flow-coated on a water-resistant glass plate, left at room temperature for 7 days, and then immersed in water at room temperature for 96 hours. Sympathize.
密着性:燐酸処理を施しだ鉄板に各試料を流し塗りして
室温で7日間放置後、1vRおきでloXIO本のゴバ
ン目を切りセ
ロテープにて剥離テストを行なった。Adhesion: Each sample was flow-coated onto a phosphoric acid-treated iron plate and left at room temperature for 7 days, after which loXIO rows were cut at every 1vR and a peel test was performed using cellophane tape.
l肘アルカリ性:淘・1水性に用いたと同様な塗板を5
重口係カセ・イソーダ水溶液に浸漬した後の′rJS膜
を観察する。l Elbow alkaline: A coating plate similar to that used for 1 aqueous
Observe the 'rJS film after immersing it in a heavy-duty case and isoda aqueous solution.
耐溶剤性:耐水性に用いたと同様々塗板上にアセトンを
含浸した脱脂綿を置き50時
間放置した後の塗膜を観察する。Solvent resistance: As in the case of water resistance, absorbent cotton impregnated with acetone was placed on the coated plate and left to stand for 50 hours, after which the coated film was observed.
上記塗膜試験の結果は下記の第1表に示される。The results of the above coating test are shown in Table 1 below.
第1表にみるように本発明の実施例である乳化重合体C
,D、E、Fは高いガラス転移点(Tg)を示すにもか
\わらず最低造膜温度(MFT)が低く、そして密着性
に非常に優れている。また耐水性、耐アルカリ性、耐溶
剤性にも優れている。As shown in Table 1, emulsion polymer C which is an example of the present invention
, D, E, and F have a low minimum film forming temperature (MFT) despite showing a high glass transition temperature (Tg), and have excellent adhesion. It also has excellent water resistance, alkali resistance, and solvent resistance.
一方比較例G、HはTgが各実施例よりも着干低いにも
か\わらずMFTが極めて高く密着性に劣り、また耐水
性、耐溶剤性にも劣っている。On the other hand, Comparative Examples G and H had extremely high MFT and poor adhesion, even though their Tg was significantly lower than those of the Examples, and they were also poor in water resistance and solvent resistance.
Claims (1)
液中で、該シリル基と反応可能な官能基を有するビニル
単量体を含む共単量体を乳化重合することを特徴とする
乳化重合体の製造方法An emulsion polymer characterized by emulsion polymerization of a comonomer containing a vinyl monomer having a functional group capable of reacting with the silyl group in an aqueous solution of a water-soluble synthetic resin having a hydrolyzable silyl group. manufacturing method
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63334354A JP2734046B2 (en) | 1988-12-28 | 1988-12-28 | Method for producing emulsion polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63334354A JP2734046B2 (en) | 1988-12-28 | 1988-12-28 | Method for producing emulsion polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02178301A true JPH02178301A (en) | 1990-07-11 |
JP2734046B2 JP2734046B2 (en) | 1998-03-30 |
Family
ID=18276432
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP63334354A Expired - Fee Related JP2734046B2 (en) | 1988-12-28 | 1988-12-28 | Method for producing emulsion polymer |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0578229A2 (en) * | 1992-07-07 | 1994-01-12 | Kanegafuchi Chemical Industry Co., Ltd. | Aqueous dispersion composition and production thereof |
JP4652638B2 (en) * | 2001-09-20 | 2011-03-16 | 株式会社カネカ | Water dispersion curing agent composition |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62283114A (en) * | 1986-05-30 | 1987-12-09 | Nippon Paint Co Ltd | Silicon-containing ampholytic polymerizable resin |
-
1988
- 1988-12-28 JP JP63334354A patent/JP2734046B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62283114A (en) * | 1986-05-30 | 1987-12-09 | Nippon Paint Co Ltd | Silicon-containing ampholytic polymerizable resin |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0578229A2 (en) * | 1992-07-07 | 1994-01-12 | Kanegafuchi Chemical Industry Co., Ltd. | Aqueous dispersion composition and production thereof |
EP0578229A3 (en) * | 1992-07-07 | 1994-06-22 | Kanegafuji Chemical Industry C | Aqueous dispersion composition and production thereof |
US5461102A (en) * | 1992-07-07 | 1995-10-24 | Kanegafuchi Chemical Industry Co., Ltd. | Aqueous dispersion composition and production thereof |
JP4652638B2 (en) * | 2001-09-20 | 2011-03-16 | 株式会社カネカ | Water dispersion curing agent composition |
Also Published As
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JP2734046B2 (en) | 1998-03-30 |
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