JPH0269507A - Dispersing unit composition for ambient temperature curing type coating - Google Patents
Dispersing unit composition for ambient temperature curing type coatingInfo
- Publication number
- JPH0269507A JPH0269507A JP22152388A JP22152388A JPH0269507A JP H0269507 A JPH0269507 A JP H0269507A JP 22152388 A JP22152388 A JP 22152388A JP 22152388 A JP22152388 A JP 22152388A JP H0269507 A JPH0269507 A JP H0269507A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated monomer
- group
- fluorine
- ethylenically unsaturated
- ethylene based
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 title claims description 20
- 239000011248 coating agent Substances 0.000 title claims description 18
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 239000006185 dispersion Substances 0.000 claims abstract description 31
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 25
- 239000011737 fluorine Substances 0.000 claims abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 10
- 230000007774 longterm Effects 0.000 abstract description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003381 stabilizer Substances 0.000 abstract description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000003973 paint Substances 0.000 description 17
- 125000000524 functional group Chemical group 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- -1 vinyl ether p-tert-butylbenzoic acid vinyl ester Chemical compound 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 229920001567 vinyl ester resin Polymers 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000012948 isocyanate Chemical group 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-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
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-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
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000006364 carbonyl oxy methylene group Chemical group [H]C([H])([*:2])OC([*:1])=O 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking 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
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 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
- 238000004134 energy conservation Methods 0.000 description 1
- JZRGFKQYQJKGAK-UHFFFAOYSA-N ethenyl cyclohexanecarboxylate Chemical compound C=COC(=O)C1CCCCC1 JZRGFKQYQJKGAK-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-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
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-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
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-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
- 210000003739 neck Anatomy 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 239000004645 polyester resin Substances 0.000 description 1
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- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-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
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 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、鉄骨構造物、船舶、橋梁、建築部−般、車輌
等に使用され、長期耐候性、高耐久性、耐食性、耐溶剤
性、耐薬品性の濠れた、低公害の、塗料用分散体組成物
、すなわち、非水分散型樹脂組成物に関するものである
。Detailed Description of the Invention (Field of Industrial Application) The present invention is used for steel structures, ships, bridges, general construction, vehicles, etc., and has long-term weather resistance, high durability, corrosion resistance, and solvent resistance. The present invention relates to a chemically resistant, low-pollution dispersion composition for coatings, that is, a non-aqueous dispersion type resin composition.
（従来の技術及びその解決すべき課題）従来から非水分
散型塗料は通常の有機溶剤溶解型塗料に比較し、高固形
分にすることが可能であり、かつ低公害である等の特徴
を有しているため、各種被塗物への塗装に広く採用され
るようになってきている。(Prior art and problems to be solved) Non-aqueous dispersion type paints have traditionally had characteristics such as being able to have a high solids content and being less polluting than ordinary organic solvent-soluble paints. Because of this, it has become widely used for coating various objects.
このような従来の非水分散型塗料は分散安定剤としてア
クリル樹脂、アルキド樹脂、ポリエステル樹脂等が利用
されてきていたが、近年、省資源、省エネルギーの観点
から塗膜寿命の長い、すなわち長期耐候性のよい非水分
散型塗料の開発が強く要望されており、前記分散安定剤
樹脂ではこれらの要望に対し充分こたえるものでなかっ
た。Such conventional non-aqueous dispersion paints have used acrylic resins, alkyd resins, polyester resins, etc. as dispersion stabilizers, but in recent years, from the viewpoint of resource and energy conservation, the use of long-life coatings, that is, long-term weather resistance. There has been a strong demand for the development of non-aqueous dispersible paints with good properties, and the above-mentioned dispersion stabilizer resins have not satisfactorily met these demands.
一方、長期耐候性のよい塗料として特開昭５７−３４１
０７号公報に記載された樹脂に代表される有機溶剤溶解
型フッ素樹脂系塗料が注目され、さらに最近では、この
ようなフッ素樹脂を分散安定剤として用いて長期耐候性
を改良した非水分散体が開発された。On the other hand, as a paint with good long-term weather resistance, JP-A-57-341
Organic solvent-soluble fluororesin paints, typified by the resin described in Publication No. 07, have attracted attention, and more recently, non-aqueous dispersions with improved long-term weather resistance using such fluororesins as dispersion stabilizers have been developed. was developed.
しかしながら、このような含フッ素樹脂非水分散体を使
用した塗料は、常温で硬化させると得られる塗膜の耐溶
剤性が劣り、その欠点を解消するためにはポリインシア
ネート化合物等の硬化剤を塗装置前に混合する、いわゆ
る二液型塗料にする必要があった。However, paints using such non-aqueous fluororesin dispersions have poor solvent resistance when cured at room temperature, and in order to overcome this drawback, it is necessary to use a curing agent such as a polyincyanate compound. It was necessary to use a so-called two-component paint that was mixed before painting.
しかも、二液型塗料は、塗装置前に主剤と硬化剤を混合
したり、ポットライフ等の点で塗装作業性が一液型塗料
に比較して悪い。In addition, two-component paints have poor painting workability compared to one-component paints in terms of mixing the base agent and curing agent before coating, pot life, and the like.
本発明者等はこのような現状に鑑み、塗装作業性のよい
一液型で、かつフッ素樹脂のもつ長期耐候性等の良さを
生かしつつ、さらに耐溶剤性を改良した、常温硬化型塗
料用非水分散体を開発すべく鋭意検討した結果、本発明
に到ったものである。In view of the current situation, the present inventors have developed a one-component type paint with good painting workability, which takes advantage of the long-term weather resistance of fluororesin, and has further improved solvent resistance. As a result of intensive studies aimed at developing a non-aqueous dispersion, the present invention was arrived at.
（課題を解決するための手段）
すなわち、本発明は、
有機溶媒（Ａ）中で、分子中にフッ素原子及びα、β−
エチレン性不飽和基を存しかつ前記有機溶媒（Ａ）に溶
解した含フッ素共重合体（Ｂ）の存在下に、単量体は前
記有機溶媒（Ａ）に溶解するが該単量体の重合によって
形成される重合体は溶解しないような、エチレン佐倉硅
素不飽和単量体（Ｃ′）を含有するエチレン性不飽和単
量体（Ｃ）を重合することによって得られる常温硬化型
塗料用分散体組成物に関するものである。(Means for Solving the Problems) That is, the present invention provides the following methods: In an organic solvent (A), fluorine atoms and α, β-
In the presence of the fluorine-containing copolymer (B) having an ethylenically unsaturated group and dissolved in the organic solvent (A), the monomer is dissolved in the organic solvent (A), but the monomer is dissolved in the organic solvent (A). For cold-curing paints obtained by polymerizing an ethylenically unsaturated monomer (C) containing an ethylene Sakura silicon unsaturated monomer (C'), the polymer formed by polymerization does not dissolve. The present invention relates to a dispersion composition.
本発明において使用する有機溶媒（Ａ）としては、ヘキ
サン、ヘプタン、オクタン等の脂肪族炭化水素類；ベン
ゼン、トルエン、キシレン等の芳香族炭化水素類；酢酸
エチル、酢酸ブチル等のエステル頚；メチルエチルケト
ン、メチルイソブチルケトン、シクロヘキサノン、イソ
ホロン等ノケトン類等が代表的なものとして挙げられる
が、これらに限定される訳ではなく、基本的には、含フ
ッ素共重合体（Ｂ）との反応性を有さず、かつエチレン
性不飽和単量体（Ｃ）、例えばエチレン佐倉硅素不飽和
単量体（Ｃ′）中の加水分解性シリル基等との反応性を
有さないものであれば特に制限なく各種有機溶媒を使用
することが可能である。The organic solvent (A) used in the present invention includes aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; ester necks such as ethyl acetate and butyl acetate; methyl ethyl ketone Typical examples include, but are not limited to, ketones such as , methyl isobutyl ketone, cyclohexanone, and isophorone. There are no particular restrictions if it does not have any reactivity with the ethylenically unsaturated monomer (C), such as the hydrolyzable silyl group in the ethylene Sakura silicon unsaturated monomer (C'). It is possible to use various organic solvents.
しかしながら、特に公害規制の観点から極性の低い脂肪
族炭化水素類を主体とするものが望ましい。However, especially from the viewpoint of pollution control, it is desirable to use a material mainly composed of aliphatic hydrocarbons with low polarity.
本発明において使用する、（Ｂ）成分である「分子中に
フッ素原子及びα、β−エチレン性不飽和基を有する含
フッ素共重合体」としては、通常、水酸基、カル°ボキ
シル基、グリシジル基あるいはアミノ基等の官能基を有
する含フッ素共重合体（Ｘ）に、その官能基と反応性を
有し、かつ分子中にα、β−エチレン性不飽和結合を有
するものを公知の方法で反応させることにより得られた
ものが挙げられる。The "fluorine-containing copolymer having a fluorine atom and an α,β-ethylenically unsaturated group in the molecule" used in the present invention, which is the component (B), is usually a hydroxyl group, a carboxyl group, or a glycidyl group. Alternatively, a fluorine-containing copolymer (X) having a functional group such as an amino group, which is reactive with the functional group and has an α,β-ethylenically unsaturated bond in the molecule, is prepared using a known method. Examples include those obtained by reaction.
上記官能基含有含フッ素共重合体（Ｘ）としては、特開
昭５７−３４１０７号、特開昭５９−１０２９６１号、
特開昭５９−１０２９６２号、特開昭５９−１８９１０
８号、特開昭６０＝６７５１８号、特開昭６１−５７６
０９号、特開昭６２−７７６７号、特姶昭６１−４９３
２３号公報などに記載されている共重合体が挙げられる
。Examples of the functional group-containing fluorine-containing copolymer (X) include JP-A-57-34107, JP-A-59-102961,
JP-A-59-102962, JP-A-59-18910
No. 8, JP-A-60=67518, JP-A-61-576
No. 09, JP-A-62-7767, JP-A-61-493
Examples include copolymers described in Publication No. 23 and the like.
すなわち、該共重合体は、フルオロオレフィン、官能基
を有するビニルエーテルと、官能基を含まないビニルエ
ーテル（含フッ素ビニルエーテルであってもよい）及び
／又はカルボン酸ビニルエステルを構成成分とし、夫々
４０〜６０モル％、０、５〜２５モル％、５〜６０モル
％及ヒ／又は５〜６０モル％の割合で含有するものが好
適である。That is, the copolymer contains a fluoroolefin, a vinyl ether having a functional group, a vinyl ether not containing a functional group (which may be a fluorine-containing vinyl ether), and/or a carboxylic acid vinyl ester, each having a molecular weight of 40 to 60%. Preferably, the content is 0, 5-25 mol%, 5-60 mol%, and/or 5-60 mol%.
なお、フルオロオレフィン含量の低すぎるものは普通、
耐候性が低下し、逆に高すぎるものは、製造面で難があ
る。In addition, those with too low fluoroolefin content are usually
If the weather resistance is too high and the weather resistance is too high, it will be difficult to manufacture.
また、共重合体（Ｘ）中に含まれる官能基は、これと反
応性の誘導体によりエチレン性不飽和二重結合を導入す
るために不可欠のものであり、通常は官能基を有するビ
ニルエーテルを共重合することによって、水酸基、グリ
シジル基、アミノ基等の官能基を供給するか、あるいは
特公昭６１−４９３２３号公報に記載されている如く、
水酸基を有するビニルエーテルを共重合させたものに二
塩基酸無水物を反応させてカルボキシル基を供給する。Furthermore, the functional group contained in the copolymer (X) is essential for introducing an ethylenically unsaturated double bond using a derivative reactive with the functional group, and usually a vinyl ether having a functional group is used as a copolymer. By polymerizing, functional groups such as hydroxyl groups, glycidyl groups, and amino groups are supplied, or as described in Japanese Patent Publication No. 61-49323,
A copolymerized vinyl ether having a hydroxyl group is reacted with a dibasic acid anhydride to supply a carboxyl group.
ただし、本発明においては、これらに限定される訳では
なく、前記共重合体の前記構成成分以外の他の共重合体
として２５モル％をこえない範囲で、水酸基、カルボキ
シル基、グリシジル基、アミノ基、スルホン酸基等を含
む、アクリル酸、メタクリル酸系の単量体を共重合する
ことによって供給することなども可能である。However, in the present invention, the present invention is not limited to these, and other copolymers other than the above-mentioned constituent components of the copolymer may contain hydroxyl groups, carboxyl groups, glycidyl groups, amino It is also possible to supply it by copolymerizing an acrylic acid or methacrylic acid monomer containing a group, a sulfonic acid group, or the like.
本発明において、前記共重合体（Ｘ）の原料のフルオロ
オレフィンとしては、パーハロオレフィン、特にクロロ
トリフルオロエチレンあるいはテトラフルオロエチレン
を使用することが好ましい。In the present invention, it is preferable to use perhaloolefins, particularly chlorotrifluoroethylene or tetrafluoroethylene, as the fluoroolefins as raw materials for the copolymer (X).
また、官能基を含まないビニルエーテルとしてはシクロ
ヘキシルビニルエーテルと炭素数２〜８の直鎖状あるい
は分岐上のアルキル基を有するビニルエーテルが好マシ
く、カルボン酸ビニルエステルとしては、シクロヘキサ
ンカルボン酸ビニルエステル、安息香酸ビニルエーテル
ペｐ−ｔｅｒｔ−ブチル安息香酸ビニルエステルまたは
Ｃ１〜ＣＩＯの脂肪族カルボン酸のエステルが好ましい
。Furthermore, as vinyl ethers that do not contain functional groups, cyclohexyl vinyl ether and vinyl ethers that have a linear or branched alkyl group having 2 to 8 carbon atoms are preferable, and as carboxylic acid vinyl esters, cyclohexane carboxylic acid vinyl ester, benzoyl vinyl ether, Acid vinyl ether p-tert-butylbenzoic acid vinyl ester or esters of C1-CIO aliphatic carboxylic acids are preferred.
前記共重合体（Ｘ）として例えば、旭硝子製ルミフロン
ＬＦ１００、ルミフロンＬＦ２００、ルミフロンＬＦ２
１０、ルミフロンＬＦ３００、ルミフロンＬＦ４００お
よび大日本インキ化学工業製フッ素樹脂に−７００、Ｋ
−７０１等が挙げられ、これらは１種または２種以上を
併用することも可能である。Examples of the copolymer (X) include Lumiflon LF100, Lumiflon LF200, and Lumiflon LF2 manufactured by Asahi Glass.
10. Lumiflon LF300, Lumiflon LF400 and Dainippon Ink Chemical Industry Co., Ltd. fluororesin -700, K
-701, etc., and these can be used alone or in combination of two or more.
前記α、β−エチレン性不飽和基を導入させ含フッ素共
重合体（Ｂ）を製造する方法としては、以下の方法が代
表的なものとして挙げられる。As a method for producing the fluorine-containing copolymer (B) by introducing the α,β-ethylenically unsaturated group, the following method is exemplified as a typical method.
前記官能基含有含フッ素共重合体（Ｘ）中の官能基が水
酸基の場合、水酸基と無水マレイン酸、アクリル酸、メ
タクリル酸、無水アクリル酸、無水メタクリル酸及びこ
れらの酸クロライド等のα。When the functional group in the functional group-containing fluorine-containing copolymer (X) is a hydroxyl group, α of the hydroxyl group and maleic anhydride, acrylic acid, methacrylic acid, acrylic anhydride, methacrylic anhydride, and their acid chlorides.
β−不飽和カルボン酸との反応を利用する方法、水酸基
とトリメチルアミン−メタクリルイミド、Ｎ−メチロー
ルアクリルアミド、Ｎ−ｎ−ブトキンメチルアクリルア
ミド等のアミン−メタクリルイミド類あるいはアクリル
アミド順との反応を利用する方法、
水酸基とイソ／アネートエチルメタクリレート、インシ
アネートエチルアクリレート等のイソシアネート基末端
不飽和化合物との反応を利用する方法、
水酸基とグリシジルメタクリレート、グリシジルアクリ
レート等のグリシジル基との反応を利用する方法、
等が挙げられ、アルコール性水酸基と反応性を有しかつ
分子中にα、β−エチレン性不飽和結合を持っている物
質であれば前記いずれのものを使用してもよい。A method utilizing a reaction with a β-unsaturated carboxylic acid, a reaction between a hydroxyl group and an amine-methacrylimide such as trimethylamine-methacrylimide, N-methylolacrylamide, N-n-butquine methylacrylamide, or acrylamide. A method utilizing a reaction between a hydroxyl group and an isocyanate group-terminated unsaturated compound such as iso/anetoethyl methacrylate or incyanatoethyl acrylate; A method utilizing a reaction between a hydroxyl group and a glycidyl group such as glycidyl methacrylate or glycidyl acrylate; Any of the above-mentioned substances may be used as long as they are reactive with alcoholic hydroxyl groups and have an α,β-ethylenically unsaturated bond in the molecule.
また、官能基がカルボキシル基である場合、カルボキシ
ル基とグリシジルメタクリレート、グリシジルアクリレ
ート等のグリシジル基との反応を利用する方法、カルボ
キシル基とメタクリル酸−ｔｅｒｔ−ブチルアミノエチ
ル等のアミノ基との反応を利用する方法、及びカルボキ
シル基とトリメチルアミン−メタクリルイミド、Ｎ−メ
チロールアクリルアミド、Ｎ−ｎ−ブトキシメチルアク
リルアミド頚との反応を利用する方法等が好ましく採用
されるが、カルボキシル基と反応性を有しかつ分子中に
α、β−エチレン性不飽和結合を持っている物質であれ
ばいずれを使用してもよい。In addition, when the functional group is a carboxyl group, a method using a reaction between a carboxyl group and a glycidyl group such as glycidyl methacrylate or glycidyl acrylate, or a method using a reaction between a carboxyl group and an amino group such as tert-butylaminoethyl methacrylate is used. Preferred methods include methods utilizing reactions between carboxyl groups and trimethylamine-methacrylimide, N-methylolacrylamide, and N-n-butoxymethylacrylamide. Any substance having an α,β-ethylenically unsaturated bond in its molecule may be used.
さらに、官能基がグリシジル基である場合、グリシジル
基とアクリル酸、メタクリル酸あるいはこれらの無水物
等のα、β−不飽和カルボン酸類との反応を利用する方
法、グリシジル基とアクリル酸−２−ヒドロキシエチル
、メタクリル酸−２−ヒドロキシエチル等の水酸基末端
不飽和単量体、グリシジル基とメタクリル酸−ｔｅｒｔ
−ブチルアミノエチル等のアミン基との反応を利用する
方法、及びアミノ基とトリメチルアミン−メタクリルイ
ミド、Ｎ−メチロールアクリルアミド、Ｎｎ−ブトキシ
メチルアクリルアミド類との反応を利用する方法が採用
されるが、グリシジル基と反応性を有しかつ分子中にα
、β−エチレン性不飽和結合を持っている物質であれば
いずれを使用してもよい。Furthermore, when the functional group is a glycidyl group, a method utilizing a reaction between the glycidyl group and α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, or anhydride thereof, and a method using a reaction between the glycidyl group and acrylic acid-2- Hydroxyl group-terminated unsaturated monomers such as hydroxyethyl and 2-hydroxyethyl methacrylate, glycidyl groups and methacrylic acid-tert
-A method that utilizes a reaction with an amine group such as butylaminoethyl, and a method that utilizes a reaction between an amino group and trimethylamine-methacrylimide, N-methylolacrylamide, Nn-butoxymethylacrylamide, etc. Reactive with groups and α in the molecule
, any substance having a β-ethylenically unsaturated bond may be used.
また、官能基がアミン基である場合、アミン基とイソシ
アネートエチルメタクリレート、イソシアネートエチル
アクリレート等イソシアネート基末端不飽和化合物との
反応を利用する方法、無水マレイン酸、アクリル酸、メ
タクリル酸、無水アクリル酸、無水メタクリル酸及びこ
れらの酸等のα、β−エチレン性不飽和カルボン酸との
反応を利用する方法、アミノ基とグリシジルメタクリレ
ート、グリシジルアクリレート等のグリシジル基との反
応を利用する方法が採用されるが、アミ７基と反応性を
有しかつ分子中にα、β−エチレン性不飽和結合を持っ
ている物質であればいずれを使用してもよい。なお、反
応生成物は１種で使用または２種以上で併用することも
可能である。In addition, when the functional group is an amine group, a method utilizing a reaction between an amine group and an isocyanate group-terminated unsaturated compound such as isocyanate ethyl methacrylate, isocyanate ethyl acrylate, maleic anhydride, acrylic acid, methacrylic acid, acrylic anhydride, A method that utilizes a reaction with α,β-ethylenically unsaturated carboxylic acid such as methacrylic anhydride and these acids, and a method that utilizes a reaction between an amino group and a glycidyl group such as glycidyl methacrylate or glycidyl acrylate are adopted. However, any substance may be used as long as it is reactive with the amide 7 group and has an α,β-ethylenically unsaturated bond in its molecule. Note that the reaction products can be used alone or in combination of two or more.
本発明において、また、α、β−エチレン性不飽和結合
の導入は、通常は後に行うエチレン性不飽和単量体＜Ｃ
）の重合の前に完結させておくのが好ましいが、場合に
よっては、エチレン性不飽和単量体（Ｃ）の重合と同時
にすすめてもよい。In the present invention, the introduction of the α,β-ethylenically unsaturated bond is usually carried out later when the ethylenically unsaturated monomer <C
Although it is preferable to complete the polymerization before the polymerization of (C), in some cases, it may be completed simultaneously with the polymerization of the ethylenically unsaturated monomer (C).
α、β−エチレン性不飽和二重結合は、含フッ素共重合
体（Ｂ）１００ｇ中にＯ，ＯＯＯｌ〜０．２モルの範囲
で使用できるが、特に０．０００４〜０．０４モル含有
することが好ましい。前記範囲において、０．０００１
モル未満では、後に重合するエチレン性不飽和単量体（
Ｃ）がグラフト重合しにくく、一方０．２モルより多く
なると単量体重合時に系が不安定になりゲル化を起こし
易い傾向がある。The α,β-ethylenically unsaturated double bond can be used in the range of O,OOOOl to 0.2 mol in 100 g of the fluorine-containing copolymer (B), but it is particularly contained in the range of 0.0004 to 0.04 mol. It is preferable. In the above range, 0.0001
In less than a molar amount, the ethylenically unsaturated monomer (
C) is difficult to graft polymerize, and on the other hand, if the amount exceeds 0.2 mol, the system tends to become unstable during monomer polymerization and gelation tends to occur.
分散安定剤である含フッ素共重合体（Ｂ）の存在下で重
合するエチレン性不飽和単量体（Ｃ）は、得られる塗膜
の耐溶剤を改良するために、その−部としてエチレン佐
倉硅素不飽和単量体（Ｃ′）を含むものである。The ethylenically unsaturated monomer (C) polymerized in the presence of the fluorine-containing copolymer (B), which is a dispersion stabilizer, contains ethylene Sakura as its -part in order to improve the solvent resistance of the resulting coating film. It contains a silicon unsaturated monomer (C').
エチレン佐倉硅素不飽和単量体（Ｃ′）としては、例え
ば、ビニルトリス（β−メトキシエトキシ）シラン、ビ
ニルトリエトキシシラン、ビニルトリメトキシシラン、
Ｔ−メタクリロキシプロピルトリメトキシシラン等が挙
げられる。たｓ’ Ｌこれらに限定されるものではなく
、分子中に加水分解可能な基をもつものであればいずれ
でもよい。Examples of the ethylene Sakura silicon unsaturated monomer (C') include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane,
Examples include T-methacryloxypropyltrimethoxysilane. s' L is not limited to these, but any compound having a hydrolyzable group in the molecule may be used.
エチレン佐倉硅素不飽和単量体（Ｃ′）は塗膜形成時、
重合体粒子内及び粒子間での架橋を誘発させ、その結果
塗膜の耐溶剤性を向上させるものと考えられる。Ethylene Sakura silicon unsaturated monomer (C') is used during coating film formation.
It is thought that this induces crosslinking within and between polymer particles, thereby improving the solvent resistance of the coating film.
このような効果を発揮させるためにはエチレン佐倉硅素
不飽和単量体（Ｃ′）を分散体固形分中央なくとも０．
１重量％以上、好ましくは１〜２０重量％の割合になる
ように使用するのが適当である。In order to exhibit such an effect, the ethylene Sakura silicon unsaturated monomer (C') must be added to the center of the solid content of the dispersion at least 0.
It is appropriate to use it in a proportion of 1% by weight or more, preferably 1 to 20% by weight.
なお、使用量が過剰になると重合時、系が不安定になる
傾向にある。エチ、レン佐倉硅素不飽和単量体（Ｃ′）
以外のエチレン性不飽和単量体（Ｃ）としては例えばア
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、アクリル酸イソプロピル、アクリル酸ｎ−ブチ
ル、アクリル酸イソブチル、アクリル酸ｔｅｒｔ−プチ
ノペアクリル酸２−エチルヘキシル、アクリル酸ラウリ
ル、アクリル酸トリデシノペアグリル酸ステアリノペア
グリル酸シクロヘキシル、アクリル酸ジメチルアミノエ
チル、アクリル酸グリシジル、アクリル酸２−ヒドロキ
シエチル、アクリル酸２−ヒドロキシプロピル等のアク
リル酸エステル類；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−ブロビル、メタクリル酸イソ
プロピル、メタクリル酸ｎ−ブチル、メタクリル酸イン
ブチノペメタクリル酸ｔｅｒｔ−ブチル、メタクリル酸
−２エチルヘキシル、メタクリル酸ラウリル、メタクリ
ル酸トリデシル、メタクリル酸ステアリノペメククリル
酸ステアリル、メタクリル酸シクロヘキシル、メタクリ
ル酸ジメチルアミノエチノペメタクリル酸ジエチルアミ
ノエチル、メタクリル酸ｔｅｒｔ−ブチルアミノエチル
、メタクリル酸グリシジル、メタクリル酸２−ヒドロキ
シエチル、メタクリル酸２−ヒドロキシプロピル等のメ
タクリル酸エステル類；スチレン若しくはビニルトルエ
ン、α−メチルスチレン、クロロスチレン等の置換スチ
レン；アクリロニトリル、メタクリレートリル、塩化ビ
ニル、ギ酸ビニル、プロピオン酸ビニル、ステアリン酸
ビニル、マレイン酸ジアルキルエステノペジビニルベン
セ゛ン、グリセリン、トリメチロールプロパン等の多価
アルコールのモノアクリレートまたはモノメタクリレー
ト、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメ
タクリルアミド、アクリルアミド、メタクリルアミド、
アクリル酸、メタクリル酸、マレイン酸、フマル酸、ク
ロトン酸、イクコン酸等が挙げられる。Note that if the amount used is excessive, the system tends to become unstable during polymerization. Ethyl, Ren Sakura silicon unsaturated monomer (C')
Other ethylenically unsaturated monomers (C) include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butinope acrylate. Acrylics such as 2-ethylhexyl acrylate, lauryl acrylate, tridecynopear acrylate stearinopear acrylate, cyclohexyl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate. Acid esters; methyl methacrylate, ethyl methacrylate, n-brobyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, inbutinope methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, Tridecyl methacrylate, stearinopeme methacrylate, stearyl methacrylate, cyclohexyl methacrylate, dimethylaminoethinope methacrylate, diethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid Methacrylic acid esters such as 2-hydroxypropyl; substituted styrenes such as styrene or vinyltoluene, α-methylstyrene, and chlorostyrene; acrylonitrile, methacrylaterile, vinyl chloride, vinyl formate, vinyl propionate, vinyl stearate, dialkyl maleate Estenopedivinylbenzene, glycerin, monoacrylate or monomethacrylate of polyhydric alcohol such as trimethylolpropane, N-methylolacrylamide, N-methylolmethacrylamide, acrylamide, methacrylamide,
Examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, and ichconic acid.
さちにエチレン性不飽和単量体（Ｃ）の一部として、耐
候性を低下させないため、またエチレン性不飽和単量体
（Ｃ）の重合体である粒子成分と分散安定剤である含フ
ッ禦共重合体（Ｂ）との相溶性をよくするため、アルキ
ル基の水素の全部または一部がフッ素によって置換され
、かつ１分子中のアルキル基の炭素数の合計が１〜２０
であるアルコールのアクリル酸エステルまたはメタクリ
ル酸エステルを使用するのが望ましい。First, as part of the ethylenically unsaturated monomer (C), in order not to reduce weather resistance, a particle component that is a polymer of the ethylenically unsaturated monomer (C) and a fluorine-containing dispersion stabilizer are added. In order to improve compatibility with the copolymer (B), all or part of the hydrogen atoms in the alkyl group are replaced with fluorine, and the total number of carbon atoms in the alkyl group in one molecule is 1 to 20.
Preferably, acrylic or methacrylic esters of alcohols are used.
該単量体は一般式ＣＨ２＝Ｃ−Ｃ００Ｘで表わされる化
合物、例えば
ＣＨ２＝ＣＨＣ００ＣＨ２ＣＦ。The monomer is a compound represented by the general formula CH2=C-C00X, for example, CH2=CHC00CH2CF.
ＣＨ２＝ＣＨＣ００ＣＨ２ＣＦ２ＣＦ２ＨＣＨ２＝ＣＨ
ＣＯＯＣＨ２（ＣＦ２ＣＦ２）２ＨＣＨ２＝ＣＨＣＯＯ
ＣＨ，（ＣＦ、ＣＦ、）、ＨＣ，Ｈ。CH2=CHC00CH2CF2CF2HCH2=CH
COOCH2(CF2CF2)2HCH2=CHCOO
CH, (CF, CF,), HC, H.
ＣＨ２＝ ＣＨＣＯＯＣＨ２ＣＨ２Ｎ Ｓ−Ｃ８Ｆ １
□Ｃト１３ Ｃ，
Ｈ。CH2= CHCOOCH2CH2N S-C8F 1
□C 13 C,
H.
ＣＨ２＝ＣＣ００ＣＨ２ＣＨ２ＮＳ２Ｃ８Ｆ１７ＣＦ（
２＝ＣＨＣ○○ＣＨ２Ｃ，Ｆ、５、ＣＨ２＝ＣＨＣ００
ＣＨ２ＣＨ２Ｃ，Ｆ、７、ＣＨ２＝ＣＨＣ○ＯＣＨ２Ｃ
Ｈ３Ｐ Ｆ（ＲＦ ： Ｃｓ Ｆ １３〜Ｃｌ２Ｆ２５
の混合物）等が代表的なものとして挙げられる。CH2=CC00CH2CH2NS2C8F17CF(
2=CHC○○CH2C,F,5,CH2=CHC00
CH2CH2C, F, 7, CH2=CHC○OCH2C
H3P F (RF: Cs F 13 ~ Cl2F25
A typical example is a mixture of
エチレン性不飽和単量体（Ｃ）は分散体固形分中１０〜
９０重量％、好ましくは２０〜６０重量％の割合になる
よう使用するのが適当であり、この範囲において、耐候
性に優れ、かつ安定性のよい分散体が得られる。Ethylenically unsaturated monomer (C) is contained in the solid content of the dispersion from 10 to
It is appropriate to use it in a proportion of 90% by weight, preferably 20 to 60% by weight, and within this range a dispersion with excellent weather resistance and good stability can be obtained.
本発明において共重合体分散体の合成の際、重合触媒と
しては過酸化ベンソイル、ジクーシャリブチルパーオキ
サイド等の過酸化物系ラジカル開始剤、アゾビスイソブ
チロニ） ＩＪル、アソビスバレロニ） ＩＪル等のア
ゾ系ラジカル開始剤、その池のラジカル開始剤が使用さ
れ得る。また、該重合反応は通常のラジカル重合条件で
行うことができる。好ましくは約８０〜１４０℃で３〜
１０時間行われる。In the present invention, during the synthesis of the copolymer dispersion, as a polymerization catalyst, a peroxide-based radical initiator such as benzoyl peroxide, dikushabutyl peroxide, azobisisobutyroni) IJ, azobisvaleroni) IJ, etc. Azo-based radical initiators and other radical initiators may be used. Further, the polymerization reaction can be carried out under normal radical polymerization conditions. Preferably at about 80-140°C
It will be held for 10 hours.
本発明の塗料用分散体組成物は、固形分濃度が２０〜６
５％の範囲で単独にクリヤー塗料として用いることが出
来る。必要に応じて、チタン白、カドミウムイエロー、
カーボンブラック等の無機系着色顔料、フタロンアニン
系、アゾ系等の有機系着色顔料、炭酸カルシウム、タル
ク等の体質顔料、及び成膜助剤、紫外線吸収剤、光安定
剤等の添加剤を含有せしめることができる。尚、無機顔
料および有機顔料は、それらの必要量を適宜決定して使
用できる。The coating dispersion composition of the present invention has a solid content concentration of 20 to 6.
It can be used alone as a clear paint in a range of 5%. Titanium white, cadmium yellow, as required
Contains inorganic coloring pigments such as carbon black, organic coloring pigments such as phthalonanine and azo, extender pigments such as calcium carbonate and talc, and additives such as film-forming aids, ultraviolet absorbers, and light stabilizers. be able to. Incidentally, the inorganic pigment and the organic pigment can be used by appropriately determining the necessary amounts thereof.
また本発明の塗料用分散体組成物は常温硬化型で、かつ
−波型であるが必要に応じポリイソシアネート化合物等
の硬化剤を使用してもよい。Further, the coating dispersion composition of the present invention is a room-temperature curing type and has a corrugated type, but a curing agent such as a polyisocyanate compound may be used if necessary.
（発明の効果）
以上説明した通り、本発明の常温硬化型金フン素塗料用
分散体組成吻は、長期耐候性、耐食性等に優れ、かつ従
来公知の含フッ素塗料用分散体の欠点である耐溶剤性の
悪さを解消しつつ、分散体特有の高固形、低公害性を充
分満足する画期的なものである。(Effects of the Invention) As explained above, the room-temperature curing dispersion composition for metal fluorine-containing paints of the present invention has excellent long-term weather resistance, corrosion resistance, etc., and has the drawbacks of conventionally known dispersions for fluorine-containing paints. This is an epoch-making product that fully satisfies the high solidity and low pollution properties characteristic of dispersions while eliminating the problem of poor solvent resistance.
以下、本発明を実施例によりさらに詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
なお、実施例中「部」、「％２は重量基準である。In the examples, "part" and "%2" are based on weight.
〈官能基含有含フッ素共重合体Ａ、Ｂの調製〉常法に従
い、第１表記載の単量体組成比の重合体へ及びＢを製造
した。該重合体の極限粘度（テトラヒドロフラン中で３
０℃で測定される粘度）、水酸基価ならびにキシレン、
ミネラルスピリットに対する溶解性を第１表下欄に示す
。<Preparation of functional group-containing fluorine-containing copolymers A and B> Polymers having the monomer composition ratios listed in Table 1 and B were prepared according to a conventional method. The intrinsic viscosity of the polymer (3 in tetrahydrofuran)
viscosity measured at 0°C), hydroxyl value and xylene,
The solubility in mineral spirits is shown in the lower column of Table 1.
くα、β−エチレン件不飽和基含有含フッ素共重合体溶
液（ア）、（イ）の調製〉
前記官能基含有含フッ素共重合体、該官能基と反応性を
有するエチレン性不飽和単量体、反応触媒、及び有限溶
媒を第２表に示すように混合した後、表中の反応条件で
反応を行い、不飽和基含有含フッ素共重合体溶液（ア）
、（イ）を調製した。Preparation of α, β-ethylenically unsaturated group-containing fluorine-containing copolymer solutions (a) and (b) After mixing the polymer, reaction catalyst, and finite solvent as shown in Table 2, the reaction was carried out under the reaction conditions shown in the table to obtain an unsaturated group-containing fluorine-containing copolymer solution (A).
, (a) was prepared.
合成例１〜４及び参考例１〜３
第３表記載の有機溶媒及び不飽和基含有含フッ素共重合
体溶液をフラスコに仕込み、９２℃に昇温した後、第３
表記載の単量体と重合開始剤の混合物を３時間にかけて
滴下し、さらに第３表記載の重合開始剤及び有機溶媒を
加え１１０℃にて４時間熟成した。得られた共重合体分
散体の安定性、用いた含珪素単量体及びエチレン性不飽
和基含有含フッ素共重合体の分散体固形分中の割合を第
３表下欄に示した。Synthesis Examples 1 to 4 and Reference Examples 1 to 3 The organic solvent and unsaturated group-containing fluorine-containing copolymer solution listed in Table 3 were charged into a flask, heated to 92°C, and then
A mixture of monomers and polymerization initiators listed in the table was added dropwise over 3 hours, and the polymerization initiators and organic solvents listed in Table 3 were further added and aged at 110°C for 4 hours. The stability of the obtained copolymer dispersion and the proportions of the silicon-containing monomer and the ethylenically unsaturated group-containing fluorine-containing copolymer used in the solid content of the dispersion are shown in the lower column of Table 3.
実施例１〜４および比較例１〜５
合成例１〜４ならびに参考例１〜３で得られた非水分散
体組成物、及び水酸基含有含フッ素共重合体Ａ、Ｂを使
用して、第４表の配合にて塗料を調製した。得られた塗
料組成物をミネラルスピリット（ただし、実施例４、及
び比較例３〜５については、キシレン／酢酸ブチル＝５
０１５０混合溶剤）にて粘度２２秒（フォードカップＮ
α４．２０℃）に調整し、これをみがき軟鋼板に、乾燥
膜厚３０μｍになるようエアスプレー塗装し、温度２０
℃、相対湿度７５％の条件下で１週間乾燥させた。Examples 1 to 4 and Comparative Examples 1 to 5 Using the nonaqueous dispersion compositions obtained in Synthesis Examples 1 to 4 and Reference Examples 1 to 3, and the hydroxyl group-containing fluorine-containing copolymers A and B, Paints were prepared according to the formulations shown in Table 4. The obtained coating composition was mixed with mineral spirit (however, for Example 4 and Comparative Examples 3 to 5, xylene/butyl acetate = 5
0150 mixed solvent) with a viscosity of 22 seconds (Ford Cup N
α4.Adjusted to 20℃), air sprayed this onto a polished mild steel plate to a dry film thickness of 30μm, and
It was dried for one week at 75% relative humidity.
得ちれた塗膜につき、各種塗膜試験をしたところ、試験
結果は第４表の下段の通りであった。The obtained coating film was subjected to various coating film tests, and the test results were as shown in the lower row of Table 4.
これらの試験結果からも明らかな通り本発明の分散体組
成物を使用した塗料は優れた塗膜性能を有していた。As is clear from these test results, the paint using the dispersion composition of the present invention had excellent coating performance.
すなわち、加水分解性のアルコキシルシリル基を有する
エチレン佐倉硅素不飽和単量体を用いて作製した分散体
組成物を使用した塗料実施例１〜４は、これを用いなか
った比較例１〜３に比べ、塗膜の耐溶剤性に著しく優れ
、また塗膜の初期光沢、鉛筆硬度、密着性、耐薬品性な
らびに促進耐候性試験においても同等あるいはそれより
以上の性能を有していた。That is, coating Examples 1 to 4 using a dispersion composition prepared using an ethylene Sakura silicon unsaturated monomer having a hydrolyzable alkoxysilyl group are different from Comparative Examples 1 to 3 in which this was not used. In comparison, the solvent resistance of the coating film was significantly superior, and the coating film had the same or better performance in initial gloss, pencil hardness, adhesion, chemical resistance, and accelerated weathering tests.
一方、実施例１〜４の塗膜を、これらのもととなる水酸
基含有含フッ素共重合体を塗料化した比較例４．５の塗
膜と比較すると、初期光沢、基材との密着性、耐溶剤性
の点に著しく優れていた。On the other hand, when comparing the coating films of Examples 1 to 4 with the coating film of Comparative Example 4.5, which was made from a hydroxyl group-containing fluorine-containing copolymer, the initial gloss and adhesion to the substrate were , it was extremely excellent in solvent resistance.
Claims (2)
，β−エチレン性不飽和基を有しかつ前記有機溶媒（Ａ
）に溶解した含フッ素共重合体（Ｂ）の存在下に、単量
体は前記有機溶媒（Ａ）に溶解するが該単量体の重合に
よって形成される重合体は溶解しないような、エチレン
性含硅素不飽和単量体（Ｃ′）を含有するエチレン性不
飽和単量体（Ｃ）を重合することによって得られる常温
硬化型塗料用分散体組成物。(1) In the organic solvent (A), fluorine atoms and α
, β-ethylenically unsaturated group and the organic solvent (A
) in the presence of the fluorine-containing copolymer (B), the monomer is dissolved in the organic solvent (A), but the polymer formed by polymerization of the monomer is not dissolved. A dispersion composition for a room temperature-curable coating material obtained by polymerizing an ethylenically unsaturated monomer (C) containing a silicon-containing unsaturated monomer (C').
体（Ｃ）が１０〜９０重量％、前記エチレン性含硅素不
飽和単量体（Ｃ′）が１〜２０重量％の割合になるよう
使用することからなる請求項（１）記載の常温硬化型塗
料用分散体組成物。(2) The proportion of the ethylenically unsaturated monomer (C) in the solid content of the dispersion is 10 to 90% by weight, and the proportion of the ethylenically silicon-containing unsaturated monomer (C') is 1 to 20% by weight. The dispersion composition for a room-temperature curable coating according to claim (1), which is used so as to have the following properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22152388A JPH0269507A (en) | 1988-09-05 | 1988-09-05 | Dispersing unit composition for ambient temperature curing type coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22152388A JPH0269507A (en) | 1988-09-05 | 1988-09-05 | Dispersing unit composition for ambient temperature curing type coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0269507A true JPH0269507A (en) | 1990-03-08 |
Family
ID=16768048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22152388A Pending JPH0269507A (en) | 1988-09-05 | 1988-09-05 | Dispersing unit composition for ambient temperature curing type coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0269507A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02206641A (en) * | 1989-02-03 | 1990-08-16 | Asahi Glass Co Ltd | Non-aqueous dispersion of fluorine-containing polymer and production thereof |
| US5777052A (en) * | 1996-06-28 | 1998-07-07 | Dow Corning Toray Slicone Co., Ltd. | Silicone modified vinyl polymers and method for the preparation thereof |
| WO2006073058A1 (en) * | 2005-01-07 | 2006-07-13 | Daikin Industries, Ltd. | Curable fluorine-containing coating composition |
| WO2012036183A1 (en) * | 2010-09-16 | 2012-03-22 | 関西ペイント株式会社 | Contamination resistant coating composition having excellent durability |
| JP2012077167A (en) * | 2010-09-30 | 2012-04-19 | Toagosei Co Ltd | Curable composition |
| JP2017061632A (en) * | 2015-09-25 | 2017-03-30 | Dic株式会社 | Nonaqueous dispersion type resin composition, method for producing the same, and coating material |
| US11008418B2 (en) | 2004-09-01 | 2021-05-18 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6466273A (en) * | 1987-09-07 | 1989-03-13 | Dainippon Toryo Kk | Dispersion composition for coating |
-
1988
- 1988-09-05 JP JP22152388A patent/JPH0269507A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6466273A (en) * | 1987-09-07 | 1989-03-13 | Dainippon Toryo Kk | Dispersion composition for coating |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02206641A (en) * | 1989-02-03 | 1990-08-16 | Asahi Glass Co Ltd | Non-aqueous dispersion of fluorine-containing polymer and production thereof |
| US5777052A (en) * | 1996-06-28 | 1998-07-07 | Dow Corning Toray Slicone Co., Ltd. | Silicone modified vinyl polymers and method for the preparation thereof |
| US11008418B2 (en) | 2004-09-01 | 2021-05-18 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
| WO2006073058A1 (en) * | 2005-01-07 | 2006-07-13 | Daikin Industries, Ltd. | Curable fluorine-containing coating composition |
| JP2006188639A (en) * | 2005-01-07 | 2006-07-20 | Daikin Ind Ltd | Composition for curable fluorine-containing coating |
| WO2012036183A1 (en) * | 2010-09-16 | 2012-03-22 | 関西ペイント株式会社 | Contamination resistant coating composition having excellent durability |
| JP5840132B2 (en) * | 2010-09-16 | 2016-01-06 | 関西ペイント株式会社 | Anti-stain coating composition with excellent durability |
| JP2012077167A (en) * | 2010-09-30 | 2012-04-19 | Toagosei Co Ltd | Curable composition |
| JP2017061632A (en) * | 2015-09-25 | 2017-03-30 | Dic株式会社 | Nonaqueous dispersion type resin composition, method for producing the same, and coating material |
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