JPH0586434B2 - - Google Patents
Info
- Publication number
- JPH0586434B2 JPH0586434B2 JP23787584A JP23787584A JPH0586434B2 JP H0586434 B2 JPH0586434 B2 JP H0586434B2 JP 23787584 A JP23787584 A JP 23787584A JP 23787584 A JP23787584 A JP 23787584A JP H0586434 B2 JPH0586434 B2 JP H0586434B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- fluorine
- paint
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003973 paint Substances 0.000 claims description 46
- 229920001577 copolymer Polymers 0.000 claims description 38
- 229910052731 fluorine Inorganic materials 0.000 claims description 38
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 36
- 239000011737 fluorine Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 238000000576 coating method Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 30
- 229920005862 polyol Polymers 0.000 claims description 28
- 150000003077 polyols Chemical class 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 25
- -1 isocyanate compound Chemical class 0.000 claims description 21
- 239000012948 isocyanate Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000011342 resin composition Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 229920003180 amino resin Polymers 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 230000007423 decrease Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 150000003926 acrylamides Chemical class 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 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 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000004640 Melamine resin Substances 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
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000010941 cobalt Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- OCDFTWVGTADYMH-UHFFFAOYSA-N cobalt dodecanoic acid Chemical group [Co].CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O OCDFTWVGTADYMH-UHFFFAOYSA-N 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 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
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 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
- 239000002562 thickening agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 239000013638 trimer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Description
〔産業上の利用分野〕
本発明は長期耐候性、耐久性、耐食性を有し、
かつ高光沢等の塗膜外観に優れた塗料用樹脂組成
物に関するものである。
〔従来技術〕
近年、タンク、橋梁等の鋼構造物やカーテンウ
オール、プレコートメタル等の金属塗装分野に於
いて、塗膜の高寿命化が要求されるようになり、
そこでフツ素樹脂塗料が注目されてきている。
従来のフツ素樹脂塗料としては、ポリフツ化ビ
ニリデン樹脂粉末を溶媒中もしくは溶媒及び液状
樹脂からなる溶液中に分散した分散型フツ素樹脂
塗料が主流を占めている。該塗料は耐候性、耐久
性、耐食性が優れているものの、ポリフツ化ビニ
リデン樹脂粉末は、融点が高く、または分散用液
状樹脂に溶融均一相とするため高温焼付を必要と
し、また得られた塗膜は、密着性、補修時の再塗
装性が劣り、また光沢も劣るという致命的な問題
を有していた。
そこでこのような問題点を解消した塗料用フツ
素樹脂が開発された特許出願（特開昭57−34107
号）されている。
該フツ素樹脂は、フルオロオレフイン、シクロ
ヘキシルビニルエーテル等を構成成分とする、水
酸基含有含フツ素共重合体であつて、常温で通常
の有機溶媒に溶解し、かつ水酸基を有しているた
め常温もしくは低温焼付でも塗膜を形成すること
が出来、また得られた塗膜は耐候性、耐久性はも
とより耐食性、耐薬品性、密着性、補修時の再塗
装性等が優れ、画期的な樹脂といえる。
〔発明が解決しようとする問題点〕
しかしながら、上記水酸基含有含フツ素共重合
体を使用した塗料は、顔料の分散性に選択性があ
り、それ故顔料によつては色分れや、浮きなどの
欠陥が生じることがあり、また得られる塗膜は、
伸び率が小さく、さらにアクリル樹脂系塗料や、
アミノアルキツド樹脂系塗料等に比較し、塗膜の
光沢や鮮映性が多少劣るという欠点があつた。
このような欠点があるため、上記塗料は初期の
塗膜外観や美観を重視する当該塗料分野に於いて
は商品価値が未だ充分とは云えず、それ故優れた
耐候性、耐久性は認めつつも早期改良が要望され
ていた。
〔問題点を解決するための手段〕
本発明者等は、以上の如き現状に鑑み、前記欠
点を解消すべく鋭意検討の結果、本発明に到つた
ものである。
すなわち、本発明は、
(i) (a)フルオロオレフインを必須成分として得ら
れる主鎖にフツ素原子が結合した、水酸基を有
する含フツ素共重合体100重量部とアミン−メ
タクリルイミド類及び／又はアクリルアミド類
３〜60重量部との反応生成物……10〜97重量％
と、
(b) アクリル酸及び／又はメタクリル酸のアルキ
ル及び／又はシクロアルキルエステルからなる
群から選択されるα，β−エチレン性不飽和単
量体……３〜90重量％
との反応生成物である水酸基価５〜150のポリ
オール樹脂及び
(ii) 硬化剤
とからなる塗料用樹脂組成物に関するものであ
る。
すなわち、本発明においては水酸基を有する含
フツ素共重合体と該含フツ素共重合体の水酸基と
反応する反応結合基及びα，β−不飽和エチレン
基を有するアミン−メタクリルイミド類及び／又
はアクリルアミド類とを反応させ、次いで得られ
た反応生成物中のα，β−不飽和エチレン基に対
しα，β−エチレン性不飽和単量体を付加反応さ
せた、含フツ素共重合体主鎖と結合したアクリル
共重合体側鎖を持つ、ポリオール樹脂を使用して
いるため、前記水酸基含有含フツ素共重合体を使
用した塗料の諸欠点が解消されるのである。
それ故、本発明の塗料用樹脂組成物は顔料の分
散性がよく、また得られた塗膜は耐候性、耐久
性、耐食性、耐薬品性、密着性、補修時の再塗装
性等に優れ、加えてエナメル塗膜の光沢が格段に
向上するという特徴を有している。
以下、本発明を詳細に説明する。
本発明において使用する水酸基を有する含フツ
素共重合体としては、好適には前記特開昭57−
34107号公報に記載される含フツ素共重合体が挙
げられる。即ち含フツ素共重合体はフルオロオレ
フイン、シクロヘキシルビニルエーテル、アルキ
ルビニルエーテル及びヒドロキシアルキルビニル
エーテルを必須成分とし、夫々30〜70重量％、５
〜60重量％、３〜50重量％及び３〜20重量％の割
合で含有するものである。重量平均分子量約２万
〜約10万の含フツ素共重合体が好適である。
なおフルオロオレフイン含量の低すぎるものは
耐候性が低下し、逆に高すぎるものは製造面で難
がある。またシクロヘキシルビニルエーテル含量
の低すぎるものは塗膜としたときの硬度が低下
し、またアルキルビニルエーテル含量の低すぎる
ものは可撓性が低下する。
またヒドロキシアルキルビニルエーテルを前記
範囲の割合で含有することが塗料ベースとしての
種々の有用な特性を損なうことなく硬化性を改善
するという面から特に重要である。すなわちヒド
ロキシアルキルビニルエーテル含量の高すぎるも
のは、共重合体の有機溶媒に対する溶解性が低下
し、逆に低すぎるものは反応基である水酸基が少
なくなり、それ故側鎖を形成するアクリル共重合
体の数が少なくなり、塗膜の光沢向上等の前記効
果が低下する。
含フツ素共重合体において、フルオロオレフイ
ンとしては、パーハロオレフイン、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
レンが好ましい。
またアルキビニルエーテルとしては、炭素数２
〜８の直鎖状または分岐状のアルキル基を含有す
るもの、特にアルキル基の炭素数が２〜４である
ものが好適である。
また前記含フツ素共重合体は40重量％を越えな
い範囲で前記４種の必須構成成分以外の他の共単
量体を含有することが出来る。かかる共単量体と
してはエチレン、プロピレン、イソブチレン、塩
化ビニル、塩化ビニリデン、メタクリル酸メチ
ル、酢酸ブチル等が代表的なものとして挙げられ
る。前記含フツ素共重合体は所定割合の単量体混
合物に重合媒体共存下に重合開始剤を作用せしめ
て共重合反応を行なわしめることによつて製造可
能である。
本発明においては、水酸基を有する含フツ素共
重合体とα，β−エチレン性不飽和単量体とを反
応させる橋かけ剤としてアミン−メタクリルイミ
ド類、アクリルアミド類の一種もしくは二種以上
の混合物を使用する。
アミン−メタクリルイミド類としては、トリメ
チルアミン−メタクリルイミド、１，１−ジメチ
ル−１−（２−ヒドロキシプロピル）アミン−メ
タクリルイミド、１，１−ジメチル−１−（２，
３−ジヒドロキシプロピル）アミン−メタクリル
イミド、またアクリルアミド類としては、Ｎ−メ
チロールアクリルアミド、Ｎ−ｎ−ブトキシメチ
ルアクリルアミド等が代表的なものとして挙げら
れる。
水酸基を有する含フツ素共重合体とアミン−メ
タクリルイミド類もしくはアクリルアミド類との
反応生成物は、有機溶媒中にて反応促進触媒の存
在下で約30〜160℃で、約１〜３時間溶液重合す
ることにより得られる。
なお、水酸基を有する含フツ素共重合体とアミ
ン−メタクリルイミド類及び／又はアクリルアミ
ド類との反応混合割合（重量基準）は（100：３
〜60）、特に好ましくは（100：５〜50）が適当で
ある。アミン−メタクリルイミド類及び／又はア
クリルアミド類の割合が前記範囲より少ないと、
α，β−エチレン性不飽和単量体と反応するα，
β−不飽和エチレン基が少なくなり前記本発明の
効果が得られ難くなり、逆に多過ぎると得られる
塗膜の耐候性、耐薬品性等が低下するとともに含
フツ素共重合体と反応しない、すなわちα，β−
エチレン性不飽和単量体同志が共重合体を形成
し、それがワニスの白濁の原因となり、塗膜の光
沢低下等を生じる。
また、前記反応促進触媒としては、アミン−メ
タクリルイミド類の反応の場合には第４級アミン
類、ラウリル酸コバルト、オクチル酸コバルト、
ジブチル錫ジラウレート等が使用出来、アクリル
アミド類の反応の場合には塩酸、硝酸、酢酸、パ
ラトルエンスルホン酸等の無機もしくは有機酸が
使用出来る。
本発明で使用するポリオール樹脂は、以上の通
りにして得られた水酸基を有する含フツ素共重合
体とアミン−メタクリルイミド類及び／又はアク
リルアミド類との反応生成物に、α，β−エチレ
ン性不飽和単量体を付加反応させることにより得
られる。すなわち、有機溶媒中に溶解させた前記
反応生成物中に重合開始剤の存在下でα，β−エ
チレン性不飽和単量体を加え、約80〜140℃で３
〜10時間程度溶液重合させることにより得られ
る。
前記α，β−エチレン性不飽和単量体は、アク
リル酸及び／又はメタクリル酸のアルキル及び又
はシクロアルキルエステルからなる群から選択さ
れる。このようなエステルとしては、アクリル酸
メチル、メタクリル酸メチル、アクリル酸エチ
ル、メタクリル酸エチル、アクリル酸プロピル、
メタクリル酸プロピル、アクリル酸ｎ−ブチル、
メタクリル酸ｎ−ブチル、アクリル酸イソブチ
ル、メタクリル酸イソブチル、アクリル酸ターシ
ヤリイブチル、メタクリル酸ターシヤリイブチ
ル、アクリル酸２エチルヘキシル、メタクリル酸
シクロヘキシル等のアクリル酸又はメタクリル酸
のアルキル又はシクロアルキルエステル類等が代
表的なものとして挙げられる。上記α，β−エチ
レン性不飽和単量体は、その他の共単量体を含ん
でもよく、このような共単量体としては、例え
ば、アクリル酸ヒドロキシエチル、メタクリル酸
ヒドロキシエチル、アクリル酸ヒドロキシプロピ
ル、メタクリル酸ヒドロキシプロピル等の水酸基
含有単量体類；アクリル酸、メタクリル酸、イタ
コン酸、フマル酸等の酸単量体類；その他スチレ
ン、ビニルピリジン等の一種もしくは二種以上の
混合物が挙げられる。特に本発明においては、
α，β−エチレン性不飽和単量体として該単量体
中アクリル酸及び／又はメタクリル酸の炭素数２
〜４のアルキルエステルを40重量％以上含むもの
が透明性に優れたポリオール樹脂が得られるため
好適である。また、前記水酸基含有単量体は得ら
れるポリオール樹脂の水酸基価が５〜150の範囲
内になるよう適宜使用される。
なお、前記含フツ素共重合体とアミン−メタク
リルイミド類及び／又はアクリルアミド類との反
応生成物とα，β−エチレン性不飽和単量体との
反応混合割合（重量基準）は、（10：90）〜
（97：３）、特に好ましくは（30：70）〜（80：
20）が適当である。α，β−エチレン性不飽和単
量体が前記範囲より少ないと本発明の高光沢等の
前記効果が得られず、逆に多過ぎると長期耐候性
等が低下するためいずれも好ましくない。
本発明において使用する前記ポリオール樹脂の
水酸基価は５〜150、特に好ましくは10〜120であ
る。水酸基価が前記範囲より低いと塗膜の硬化性
が悪くなり、また硬度、耐汚染性等も低下するの
で好ましくなく、一方逆に高過ぎると塗膜の可撓
性が低下し、後加工性等が損なわれるので好まし
くない。
次に、本発明において前記ポリオール樹脂の硬
化剤として多価イソシアネート化合物及び（また
は）アミノプラスト化合物を使用する。
多価イソシアネート化合物としてはヘキサメチ
レンジイソシアネート、テトラメチレンジイソシ
アネート、イソホロンジイソシアネート、水添ジ
フエニルジイソシアネート、水添キシリレンジイ
ソシアネート等の脂肪族もしくは脂環族ジイソシ
アネート、あるいはこれらのビユーレツト体、二
量体、三量体、あるいはこれらイソシアネート化
合物の過剰量とエチレングリコール、グリセリ
ン、トリメチロールプロパン、ペンタエリスリト
ール等の低分子ポリオールとの反応生成物が代表
的なものとして挙げられる。これらの多価イソシ
アネート化合物はポリオール樹脂に所定割合で混
合することにより常温でも硬化させることが可能
な二液型塗料となる。
また前記多価イソシアネート化合物をフエノー
ル類、アルコール類、オキシム類、ラクタタム
類、アミン類、アミド類等のマスク剤でマスクし
たブロツクイソシアネート化合物も使用出来、こ
の場合は前記ポリオール樹脂に所定割合で混合す
ることにより焼付硬化可能な一液型塗料となる。
前記ポリオール樹脂と多価イソシアネート化合
物硬化剤成分の混合割合は、イソシアネート化合
物のイソシアネート基対ポリオール樹脂の水酸基
の当量比（NCO／OH）が（0.15〜1.5／１）、特
に好ましくは（0.2〜1.2／１）となるような範囲
であり、この範囲で本来の樹脂特性を発揮するこ
とが可能となる。
イソシアネート基が前記範囲より多過ぎると遊
離イソシアネート基が空気中の水分等と反応し、
耐候性等が低下し、逆に少なすぎると、満足な硬
化性が得られず、架橋密度が低いため耐溶剤性、
耐汚染性、耐薬品性、耐候性等が低下するのでい
ずれも好ましくない。
また、前記の如く硬化剤としてアミノプラスト
化合物も使用できる。アミノプラスト化合物は、
メラミン、尿素、ベンゾグアナミン、アセトグア
ナミン等のアミノ化合物とアルデヒド化合物との
縮合生成物あるいは該縮合生成物をさらにブタノ
ールの如きアルコールでエーテル化した化合物で
ある。アミノプラスト化合物を使用した場合は、
前記ポリオール樹脂に所定割合で混合することに
より焼付硬化可能な一液型塗料となる。
ポリオール樹脂とアミノプラスト化合物の混合
比（重量基準）は（95：５〜60：40）の範囲で本
来の樹脂特性を発揮することが可能となる。
アミノプラスト化合物が前記範囲より多過ぎる
とアミノプラスト化合物同志の反応が起こり易く
なり、塗膜の可撓性、耐薬品性が低下し、逆に少
な過ぎると満足な硬化性が得られず架橋密度が低
いため耐溶解性、耐汚染性等が低下するのでいず
れも好ましくない。
本発明の塗料用樹脂組成物は、前記ポリオール
樹脂と硬化剤とからなり、必要に応じ各種顔料、
有機溶剤あるいは添加剤等を配合し塗料として使
用可能となる。
顔料としては、通常塗料用として利用されてい
る顔料がそのまま使用可能である。具体的には酸
化チタン、亜鉛華、酸化鉄、黄鉛等の着色無機顔
料、フタロシアニンブルー、ベンジジンイエロー
等の着色有機顔料、石英粉、酸化アルミナ、沈降
性硫酸バリウム等の体質顔料、ステンレス粉、亜
鉛粉、アルミニウム粉、ブロンズ粉、雲母粉等の
金属粉等が代表的なものとして挙げられる。また
有機溶剤としては、トルエン、キシレン等の炭化
水素系溶剤；酢酸エチル、酢酸ブチル等のエステ
ル系溶剤；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、イソホロン等のケ
トン系溶剤；メタノール、エタノール、ブタノー
ル、等のアルコール系溶剤が代表的なものとして
挙げられる。
また添加剤としては表面調整列、分散剤、紫外
線吸収剤、増粘剤、反応調整触媒等の通常塗料用
添加剤として知られている添加剤が挙げられる。
このようにして得られる塗料は、鋼板、ステン
レス板、アルミ板等の多種金属材料は勿論のこと
モルタル、コンクリート、ガラス等の無機材料、
プラスチツク、木材等の塗装にも適用可能であ
る。
塗装方法としてはエアースプレー、エアレスス
プレー、静電スプレー、シヤワーコート、デイツ
プ塗装、ハケ刷、ロール塗装等の従来から一般に
行われている方法がそのまま採用出来る。
また硬化条件も前記硬化剤等を選択することに
より常温乾燥から、130〜150℃、20〜30分間の低
温焼付、200〜230℃、30〜200秒間の高温短時間
焼付まで各種条件が採用できる。
〔発明の効果〕
以上説明した通り、本発明の塗料用樹脂組成物
は長期耐候性、耐久性、耐食性、耐薬品性、可撓
性はもとより、光沢、鮮映性等の塗膜外観の優れ
た塗膜を得ることが出来る。
以下、本発明を実施例によりさらに詳細に説明
する。なお、実施例中「部」、「％」は重量基準で
ある。
また実施例及び比較例に使用した含フツ素共重
合体は以下のものを使用した。
＜含フツ素共重合体＞
(1) 含フツ素共重合体溶液(A)
クロロトリフルオロエチレン55.2％、シクロヘ
キシルビニルエーテル20.0％、エチルビニルエー
テル15.0％及びヒドロキシブチルビニルエーテル
9.8％からなる単量体を特開昭57−34107号公報に
記載の方法に従つて、含フツ素共重合体（水酸基
価28.3Tg45℃）の60％キシロール溶液を調整し
た。（これを含フツ素共重合体(A)という）
(2) 含フツ素共重合体溶液(B)
テトロフルオロエチレン47％、シクロヘキシル
ビニルエーテル30％、エチルビニルエーテル８％
及びヒドロキシブチルビニルエーテル15％からな
る単量体を同様にして重合し、含フツ素共重合体
（水酸基価43.4、Tg35℃）の60％キシロール溶液
を調整した。（これを含フツ素共重合体溶液(B)と
いう）
実施例 １
含フツ素共重合体溶液(A)100部にトリメチルア
ミン−メタクリルイミド６部、ジブチル錫ジラウ
レート0.5部を加え、140℃、１時間反応させ、し
かる後、キシロール24部、酢酸ブチル24部を加え
た。
この溶液に80℃に保持した状態でメタクリル酸
メチル９％、メタクリル酸ターシヤリイブチル50
％、メタクリル酸１％、メタクリル酸ヒドロキシ
エチル40％からなる単量体混合物66部及びアゾビ
スイソブチロニトリル１部の混合物を２時間かけ
て滴下し反応させた。さらにアゾビスイソブチロ
ニトリルを0.5部加え、85℃に昇温し、４時間撹
拌反応させ、不揮発分60％のポリオール樹脂（ガ
ラス転移温度60℃、水酸基価85）の透明な溶液を
得た。
このポリオール樹脂溶液100部に鱗片状アルミ
ニウムペースト（固形分65％）10部、キシロール
10部、ブロツクイソシアネート溶液（「コロネー
トDC2725」〔日本ポリウレタン社製商品名〕、固
形分80％、ワニスイソシアネート当量362）33部、
ジブチル錫ジラウレート0.5部及び表面調整剤0.3
部を混合分散し、メタリツク塗料を調整した。
また、前記メタリツク塗料において、鱗片状ア
ルミニウムペースト及びキシロールを除く以外は
同様にしてクリヤー塗料を調整した。
軟鋼板にカチオン電着塗膜、ポリエステル／メ
ラミン樹脂系中塗塗膜を施した被塗物上に前記メ
タリツク塗料をキシロールにて粘度17秒（フオー
ドカツプ＃４，20℃）に調整後、エアスプレーに
て乾燥膜厚20μになるよう塗布した。
次いで３分間放置後前記クリヤー塗料をトルオ
ール／キシロール＝50／50の混合溶剤にて粘度22
秒に調整後、エアスプレーにて乾燥膜厚25μにな
るよう塗り重ねた。次いで13分間フラツシユオフ
後、150℃、25分間焼付けた。
得られた塗膜は優れたメタリツク外観を有して
おり、またクリヤー塗膜は透明であり、光沢（60
度鏡面反射率）85であつた。
比較例 １
含フツ素共重合体溶液(A)100部に、実施例１と
同様にして鱗片状アルミニウムペースト10部、キ
シロール10部、ブロツクイソシアネート溶液17.4
部、ジブチル錫ジラウレート0.5部及び表面調整
剤0.3部を混合分散し、メタリツク塗料を調製し
た。
また、前記メタリツク塗料において鱗片状アル
ミニウムペースト及びキシロールを除く以外は同
様にしてクリヤー塗料を調製した。
このようにして得られたメタリツク塗料とクリ
ヤー塗料を実施例１と同様にして塗り重ね焼付け
た。得られた塗膜は実施例１と同様のメタリツク
外観を有していたが、光沢70と低かつた。
実施例 ２
含フツ素共重合体溶液(B)100部に、Ｎ−ｎ−ブ
トキシメチルアクリルアミド30部、パラトルエン
スルホン酸0.1部を加え、120℃、２時間反応さ
せ、しかる後、キシロール18.5部、酢酸ブチル
18.6部を加えた。
この溶液に、80℃に保持した状態で、メタクリ
ル酸メチル26.4％：メタクリル酸シクロヘキシル
59.1％、アクリル酸2.5％、メタクリル酸ヒドロ
キシエチル12％からなる単量体混合物25.7部及び
アゾビスイソブチロニトリル0.5部の混合物を２
時間かけて滴下し、反応させた。さらにアゾビス
イソブチロニトリル0.5部を加え85℃に昇温し、
４時間撹拌反応させ不揮発分60％のポリオール樹
脂（ガラス転移温度45℃、水酸基価12）の極くわ
ずか乳濁した溶液を得た。
このポリオール樹脂溶液100部にイソブチルエ
ーテル化メラミン溶液（「ユーバン20SE−60」
〔三井東圧化学社製商品名〕、固形分60％）６部、
チタン白40部、キシロール30部、酢酸ブチル30部
及び表面調整剤0.3部を練合分散し、白色塗料を
調整した。
クロム酸系化成処理を施した0.5mm厚のアルミ
ニウム板に前記白色塗料をナイフコーターにて乾
燥膜厚25μになるよう塗布し、230℃、１分間焼
付けた。
得られた塗膜の光沢、耐候性、耐ラビング性、
折曲性、耐衝撃性、耐溶剤性の塗膜性能は第１表
の通りであつた。
実施例 ３
実施例２において、メタクリル酸メチル26.4
％、メタクリル酸シクロヘキシル59.1％の代わり
にメタクリル酸イソブチル85.5％を使用する以外
は、同様にしてポリオール樹脂（ガラス転移温度
39℃、水酸基価12）の無色透明な溶液を得た。
以下、実施例２と同様にして白色塗料を調製し
同様にして塗装し、得られた塗膜性能は第１表の
通りであつた。
実施例 ４
含フツ素共重合体(B)100部にＮ−ｎ−ブトキシ
メチルアクリルアミド30部、パラトルエンスルホ
ン酸0.1部を加え、120℃、２時間反応させ、しか
る後キシロール74.5部、酢酸ブチル74.5部を加え
た。この溶液に実施例２において単量体混合物
25.7部を195部に変更する以外は、同様にして滴
下反応させポリオール樹脂（ガラス転移温度63
℃、水酸基価35）の極くわずか乳濁した溶液を得
た。
このポリオール樹脂溶液100部にイソブチルエ
ーテル化メラミン溶液（ユーバン20SE−60）43
部、チタン白40部、キシロール30部、酢酸ブチル
30部及び表面調整剤0.3部を練合分散し、白色塗
料を調製した。
以下、実施例２と同様にして塗装し、得られた
塗膜性能は第１表の通りであつた。
比較例 ２
含フツ素共重合体溶液(B)100部にＮ−ｎ−ブト
キシメチルアクリルアミド1.2部、パラトルエン
スルホン酸0.1部を加え、120℃、２時間反応さ
せ、しかる後キシロール8.4部、酢酸ブチル8.4部
を加えた。
次いで実施例２と同様にして、この溶液に単量
体混合物を滴下反応させ、ポリオール樹脂（ガラ
ス転移温度45℃、水酸基価37）の白濁した溶液を
得た。
以下、実施例２と同様にして白色塗料を調製
し、同様にして塗装し、得られた塗膜性能は第１
表の通りであつた。
比較例 ３
含フツ素共重合体溶液(B)100部に、Ｎ−ｎ−ブ
トキシメチルアクリルアミド30部、パラトルエン
スルホン酸0.1部を加え、120℃、２時間反応さ
せ、しかる後キシロール10.3部、酢酸ブチル10.3
部を加えた。
この溶液に実施例２に記載の単量体混合物25.7
部を2.6部に変更する以外は、実施例２と同様に
して滴下反応させ、ポリオール樹脂（ガラス転移
温度36℃、水酸基価２）の極くわずか乳濁した溶
液を得た。
以下、実施例２と同様にして白色塗料を調製し
同様にして塗装し、得られた塗膜性能は第１表の
通りであつた。
比較例 ４
含フツ素共重合体(B)100部にイソブチルエーテ
ル化メラミン溶液（ユーバン20SE−60）６部、
チタン白40部、キシロール30部酢酸ブチル30部及
び表面調整剤0.3部を練合分散し、白色塗料を調
製した。
以下、実施例２と同様にして塗装し、得られた
塗膜性能は第１表の通りであつた。
[Industrial Application Field] The present invention has long-term weather resistance, durability, and corrosion resistance,
The present invention also relates to a resin composition for paint that has excellent coating film appearance such as high gloss. [Prior art] In recent years, in the field of metal coating for steel structures such as tanks and bridges, curtain walls, pre-coated metal, etc., there has been a demand for longer lifespan of coating films.
Therefore, fluorocarbon resin paints are attracting attention. The mainstream of conventional fluororesin paints is a dispersion type fluororesin paint in which polyvinylidene fluoride resin powder is dispersed in a solvent or in a solution consisting of a solvent and a liquid resin. Although the paint has excellent weather resistance, durability, and corrosion resistance, polyvinylidene fluoride resin powder has a high melting point or requires high temperature baking to melt into a uniform phase in the liquid resin for dispersion, and the resulting paint The film had fatal problems of poor adhesion, poor repaintability during repair, and poor gloss. Therefore, a patent application (Japanese Unexamined Patent Publication No. 57-34107
No.) has been done. The fluororesin is a hydroxyl group-containing fluorine-containing copolymer containing fluoroolefin, cyclohexyl vinyl ether, etc. as constituent components, and is soluble in ordinary organic solvents at room temperature. It is an innovative resin that can form a paint film even when baked at low temperatures, and the resulting paint film has excellent weather resistance and durability, as well as corrosion resistance, chemical resistance, adhesion, and repaintability during repairs. It can be said. [Problems to be solved by the invention] However, paints using the above-mentioned hydroxyl group-containing fluorine-containing copolymer have selectivity in pigment dispersibility, and therefore, depending on the pigment, color separation or floating may occur. Defects such as
The elongation rate is small, and acrylic resin paints,
Compared to aminoalkyd resin-based paints, etc., it had the disadvantage that the gloss and sharpness of the coating film were somewhat inferior. Due to these drawbacks, the above paints still do not have sufficient commercial value in the field of paints where initial coating appearance and aesthetics are important, and therefore, although they have excellent weather resistance and durability, they cannot be said to have sufficient commercial value. There were also requests for early improvements. [Means for Solving the Problems] In view of the current situation as described above, the present inventors have arrived at the present invention as a result of intensive studies to eliminate the above-mentioned drawbacks. That is, the present invention provides (i) (a) 100 parts by weight of a fluorine-containing copolymer having a hydroxyl group in which a fluorine atom is bonded to the main chain obtained by using fluoroolefin as an essential component, an amine-methacrylimide, and/or Or reaction product with 3-60 parts by weight of acrylamide...10-97% by weight
and (b) a reaction product with 3 to 90% by weight of an α,β-ethylenically unsaturated monomer selected from the group consisting of alkyl and/or cycloalkyl esters of acrylic acid and/or methacrylic acid. The present invention relates to a coating resin composition comprising a polyol resin having a hydroxyl value of 5 to 150 and (ii) a curing agent. That is, in the present invention, a fluorine-containing copolymer having a hydroxyl group, a reactive bonding group that reacts with the hydroxyl group of the fluorine-containing copolymer, and an amine-methacrylimide having an α,β-unsaturated ethylene group and/or A fluorine-containing copolymer mainly produced by reacting with acrylamide and then adding an α,β-ethylenically unsaturated monomer to the α,β-unsaturated ethylene groups in the resulting reaction product. Since a polyol resin having an acrylic copolymer side chain bonded to the chain is used, various drawbacks of paints using the hydroxyl group-containing fluorine-containing copolymer described above are eliminated. Therefore, the paint resin composition of the present invention has good pigment dispersibility, and the resulting paint film has excellent weather resistance, durability, corrosion resistance, chemical resistance, adhesion, and repaintability during repair. In addition, it has the characteristic that the gloss of the enamel coating is significantly improved. The present invention will be explained in detail below. The fluorine-containing copolymer having a hydroxyl group used in the present invention is preferably
Examples include fluorine-containing copolymers described in Publication No. 34107. That is, the fluorine-containing copolymer contains fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether, and hydroxyalkyl vinyl ether as essential components, each containing 30 to 70% by weight and 5% by weight.
It is contained in proportions of ~60% by weight, 3~50% by weight, and 3~20% by weight. A fluorine-containing copolymer having a weight average molecular weight of about 20,000 to about 100,000 is preferred. Note that if the fluoroolefin content is too low, the weather resistance will decrease, and if the fluoroolefin content is too high, it will be difficult to manufacture. Furthermore, if the cyclohexyl vinyl ether content is too low, the hardness of the coating film will decrease, and if the alkyl vinyl ether content is too low, the flexibility will decrease. Furthermore, it is particularly important to contain hydroxyalkyl vinyl ether in a proportion within the above range from the viewpoint of improving curability without impairing various useful properties as a paint base. In other words, if the hydroxyalkyl vinyl ether content is too high, the copolymer's solubility in organic solvents will decrease, and if it is too low, there will be fewer hydroxyl groups, which are reactive groups, and therefore the acrylic copolymer will form side chains. As a result, the above-mentioned effects such as improving the gloss of the coating film are reduced. In the fluorine-containing copolymer, the fluoroolefin is preferably perhaloolefin, particularly chlorotrifluoroethylene or tetrafluoroethylene. In addition, as alkivinyl ether, carbon number 2
Those containing up to 8 linear or branched alkyl groups, particularly those in which the alkyl group has 2 to 4 carbon atoms, are preferred. Further, the fluorine-containing copolymer may contain comonomers other than the four essential components in an amount not exceeding 40% by weight. Typical examples of such comonomers include ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, methyl methacrylate, and butyl acetate. The fluorine-containing copolymer can be produced by causing a copolymerization reaction by allowing a polymerization initiator to act on a monomer mixture in a predetermined proportion in the presence of a polymerization medium. In the present invention, one or a mixture of two or more of amine-methacrylimides and acrylamides is used as a crosslinking agent for reacting a fluorine-containing copolymer having a hydroxyl group with an α,β-ethylenically unsaturated monomer. use. Examples of amine-methacrylimides include trimethylamine-methacrylimide, 1,1-dimethyl-1-(2-hydroxypropyl)amine-methacrylimide, 1,1-dimethyl-1-(2,
Representative examples of 3-dihydroxypropyl)amine-methacrylimide and acrylamides include N-methylolacrylamide and Nn-butoxymethylacrylamide. The reaction product of a fluorine-containing copolymer having a hydroxyl group and an amine-methacrylimide or acrylamide is dissolved in an organic solvent at about 30 to 160°C in the presence of a reaction promoting catalyst for about 1 to 3 hours. Obtained by polymerization. The reaction mixture ratio (by weight) of the fluorine-containing copolymer having a hydroxyl group and the amine-methacrylimide and/or acrylamide is (100:3
~60), particularly preferably (100:5~50). When the proportion of amine-methacrylimides and/or acrylamides is less than the above range,
α,β-reacts with ethylenically unsaturated monomer,
If the amount of β-unsaturated ethylene groups decreases, it becomes difficult to obtain the effects of the present invention, and conversely, if the amount is too high, the weather resistance, chemical resistance, etc. of the resulting coating film decreases, and it does not react with the fluorine-containing copolymer. , i.e. α, β−
The ethylenically unsaturated monomers form a copolymer, which causes the varnish to become cloudy and cause a decrease in the gloss of the coating film. In addition, as the reaction promoting catalyst, in the case of the amine-methacrylimide reaction, quaternary amines, cobalt laurate, cobalt octylate,
Dibutyltin dilaurate and the like can be used, and in the case of acrylamide reactions, inorganic or organic acids such as hydrochloric acid, nitric acid, acetic acid, and paratoluenesulfonic acid can be used. The polyol resin used in the present invention has α,β-ethylenic properties in the reaction product of the fluorine-containing copolymer having hydroxyl groups obtained as described above and amine-methacrylimides and/or acrylamides. Obtained by addition reaction of unsaturated monomers. That is, an α,β-ethylenically unsaturated monomer is added to the reaction product dissolved in an organic solvent in the presence of a polymerization initiator, and the mixture is heated at about 80 to 140°C for 30 minutes.
Obtained by solution polymerization for about 10 hours. The α,β-ethylenically unsaturated monomer is selected from the group consisting of alkyl and/or cycloalkyl esters of acrylic acid and/or methacrylic acid. Such esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate,
Propyl methacrylate, n-butyl acrylate,
Alkyl or cycloalkyl esters of acrylic acid or methacrylic acid such as n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, etc. It is mentioned as a typical example. The α,β-ethylenically unsaturated monomer may also contain other comonomers, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, etc. Hydroxyl group-containing monomers such as propyl and hydroxypropyl methacrylate; acid monomers such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid; and one or a mixture of two or more of styrene, vinylpyridine, etc. It will be done. In particular, in the present invention,
As the α,β-ethylenically unsaturated monomer, acrylic acid and/or methacrylic acid has 2 carbon atoms in the monomer.
A polyol resin containing 40% by weight or more of the alkyl esters of 4 to 4 is preferable because a polyol resin with excellent transparency can be obtained. Further, the hydroxyl group-containing monomer is used appropriately so that the hydroxyl value of the resulting polyol resin falls within the range of 5 to 150. The reaction mixture ratio (by weight) of the reaction product of the fluorine-containing copolymer with the amine-methacrylimide and/or acrylamide and the α,β-ethylenically unsaturated monomer is (10 :90)～
(97:3), particularly preferably (30:70) to (80:
20) is appropriate. If the amount of the α,β-ethylenically unsaturated monomer is less than the above range, the above-mentioned effects such as the high gloss of the present invention cannot be obtained, whereas if it is too much, long-term weather resistance etc. will be deteriorated, which is not preferable. The polyol resin used in the present invention has a hydroxyl value of 5 to 150, particularly preferably 10 to 120. If the hydroxyl value is lower than the above range, the curing properties of the coating film will deteriorate, and the hardness, stain resistance, etc. will also decrease, which is undesirable.On the other hand, if it is too high, the flexibility of the coating film will decrease, making post-processing difficult. This is not preferable because it damages the Next, in the present invention, a polyvalent isocyanate compound and/or an aminoplast compound are used as a curing agent for the polyol resin. Examples of polyvalent isocyanate compounds include aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenyl diisocyanate, and hydrogenated xylylene diisocyanate, or biuret forms, dimers, and trimers thereof. Typical examples include reaction products of isocyanate compounds or excess amounts of these isocyanate compounds and low-molecular polyols such as ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. By mixing these polyvalent isocyanate compounds with a polyol resin in a predetermined ratio, a two-component paint can be obtained that can be cured even at room temperature. Blocked isocyanate compounds obtained by masking the polyvalent isocyanate compounds with masking agents such as phenols, alcohols, oximes, lactams, amines, and amides can also be used, and in this case, they are mixed with the polyol resin in a predetermined ratio. This results in a one-component paint that can be cured by baking. The mixing ratio of the polyol resin and the polyvalent isocyanate compound curing agent component is such that the equivalent ratio of isocyanate groups of the isocyanate compound to hydroxyl groups of the polyol resin (NCO/OH) is (0.15 to 1.5/1), particularly preferably (0.2 to 1.2). /1), and within this range it is possible to exhibit the original resin properties. If the amount of isocyanate groups is too large than the above range, the free isocyanate groups will react with moisture in the air, etc.
Weather resistance etc. will decrease, and if it is too low, satisfactory curability will not be obtained, and the crosslinking density will be low, resulting in poor solvent resistance,
All of these are unfavorable because they reduce stain resistance, chemical resistance, weather resistance, and the like. Furthermore, as described above, an aminoplast compound can also be used as a curing agent. Aminoplast compounds are
It is a condensation product of an amino compound such as melamine, urea, benzoguanamine, or acetoguanamine and an aldehyde compound, or a compound obtained by further etherifying the condensation product with an alcohol such as butanol. When using aminoplast compounds,
By mixing it with the polyol resin in a predetermined ratio, it becomes a one-component paint that can be cured by baking. The original resin properties can be exhibited when the mixing ratio (by weight) of the polyol resin and the aminoplast compound is in the range of (95:5 to 60:40). If the amount of the aminoplast compound is too much than the above range, reactions between the aminoplast compounds will easily occur, resulting in a decrease in the flexibility and chemical resistance of the coating film, while if it is too little, satisfactory curability will not be obtained and the crosslinking density will decrease. Both are unfavorable because the dissolution resistance, stain resistance, etc. are lowered due to the low . The resin composition for paint of the present invention comprises the polyol resin and a curing agent, and optionally various pigments,
It can be used as a paint by adding organic solvents or additives. As the pigment, pigments commonly used for paints can be used as they are. Specifically, colored inorganic pigments such as titanium oxide, zinc white, iron oxide, and yellow lead, colored organic pigments such as phthalocyanine blue and benzidine yellow, extender pigments such as quartz powder, alumina oxide, and precipitated barium sulfate, stainless steel powder, Typical examples include metal powders such as zinc powder, aluminum powder, bronze powder, and mica powder. Examples of organic solvents include hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; methanol, ethanol, butanol, etc. Alcohol solvents are typical examples. Examples of additives include additives commonly known as additives for paints, such as surface conditioning agents, dispersants, ultraviolet absorbers, thickeners, and reaction regulating catalysts. The paint obtained in this way can be applied to various metal materials such as steel plates, stainless steel plates, and aluminum plates, as well as inorganic materials such as mortar, concrete, and glass.
It can also be applied to coating plastics, wood, etc. As a coating method, conventionally commonly used methods such as air spray, airless spray, electrostatic spray, shower coating, dip coating, brush printing, roll coating, etc. can be used as they are. Furthermore, by selecting the curing agent mentioned above, various curing conditions can be adopted, from drying at room temperature to low-temperature baking at 130-150℃ for 20-30 minutes, and high-temperature short-time baking at 200-230℃ for 30-200 seconds. . [Effects of the Invention] As explained above, the resin composition for paint of the present invention not only has long-term weather resistance, durability, corrosion resistance, chemical resistance, and flexibility, but also has excellent coating film appearance such as gloss and sharpness. A coating film can be obtained. Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, "parts" and "%" are based on weight. Further, the following fluorine-containing copolymers were used in Examples and Comparative Examples. <Fluorine-containing copolymer> (1) Fluorine-containing copolymer solution (A) 55.2% chlorotrifluoroethylene, 20.0% cyclohexyl vinyl ether, 15.0% ethyl vinyl ether, and hydroxybutyl vinyl ether
A 60% xylene solution of a fluorine-containing copolymer (hydroxyl value: 28.3 Tg, 45 DEG C.) was prepared using 9.8% monomer according to the method described in JP-A-57-34107. (This is called fluorine-containing copolymer (A)) (2) Fluorine-containing copolymer solution (B) 47% tetrafluoroethylene, 30% cyclohexyl vinyl ether, 8% ethyl vinyl ether
and 15% hydroxybutyl vinyl ether were polymerized in the same manner to prepare a 60% xylene solution of a fluorine-containing copolymer (hydroxyl value 43.4, Tg 35°C). (This is referred to as fluorine-containing copolymer solution (B)) Example 1 6 parts of trimethylamine-methacrylimide and 0.5 parts of dibutyltin dilaurate were added to 100 parts of fluorine-containing copolymer solution (A), and the mixture was heated at 140°C for 1 hour. The mixture was allowed to react for an hour, and then 24 parts of xylol and 24 parts of butyl acetate were added. In this solution, 9% methyl methacrylate and 50 tert-butyl methacrylate were added while maintaining the temperature at 80°C.
A mixture of 66 parts of a monomer mixture consisting of 1% methacrylic acid, 40% hydroxyethyl methacrylate, and 1 part of azobisisobutyronitrile was added dropwise over 2 hours to cause a reaction. Furthermore, 0.5 part of azobisisobutyronitrile was added, the temperature was raised to 85°C, and the reaction was stirred for 4 hours to obtain a transparent solution of polyol resin (glass transition temperature 60°C, hydroxyl value 85) with a nonvolatile content of 60%. . To 100 parts of this polyol resin solution, 10 parts of scaly aluminum paste (solid content 65%), xylol
10 parts, 33 parts of blocked isocyanate solution ("Coronate DC2725" [trade name manufactured by Nippon Polyurethane Co., Ltd.], solid content 80%, varnish isocyanate equivalent weight 362),
Dibutyltin dilaurate 0.5 part and surface conditioner 0.3
A metallic paint was prepared by mixing and dispersing the following parts. A clear paint was prepared in the same manner as the metallic paint except that the flaky aluminum paste and xylene were removed. After adjusting the metallic paint to a viscosity of 17 seconds (Food cup #4, 20℃) with xylene on a coated object with a cationic electrodeposition coating and a polyester/melamine resin intermediate coating on a mild steel plate, air spray it. The coating was applied to a dry film thickness of 20μ. After standing for 3 minutes, the clear paint was diluted to a viscosity of 22 with a mixed solvent of toluol/xylol = 50/50.
After adjusting to 25 seconds, it was coated with air spray to a dry film thickness of 25 μm. After flashing off for 13 minutes, it was baked at 150°C for 25 minutes. The resulting coating has an excellent metallic appearance, and the clear coating is transparent and has a gloss (60
degree specular reflectance) was 85. Comparative Example 1 To 100 parts of fluorine-containing copolymer solution (A), 10 parts of scaly aluminum paste, 10 parts of xylene, and 17.4 parts of blocked isocyanate solution were added in the same manner as in Example 1.
1 part, 0.5 part of dibutyltin dilaurate, and 0.3 part of a surface conditioner were mixed and dispersed to prepare a metallic paint. In addition, a clear paint was prepared in the same manner as the metallic paint except that the flaky aluminum paste and xylene were removed. The metallic paint and clear paint thus obtained were coated and baked in the same manner as in Example 1. The resulting coating had a metallic appearance similar to that of Example 1, but had a low gloss of 70. Example 2 30 parts of N-n-butoxymethylacrylamide and 0.1 part of para-toluenesulfonic acid were added to 100 parts of the fluorine-containing copolymer solution (B), and the mixture was reacted at 120°C for 2 hours, followed by 18.5 parts of xylol. , butyl acetate
Added 18.6 parts. In this solution, 26.4% methyl methacrylate: cyclohexyl methacrylate was added while keeping it at 80℃.
25.7 parts of a monomer mixture consisting of 59.1% acrylic acid, 2.5% acrylic acid, 12% hydroxyethyl methacrylate, and 0.5 part of azobisisobutyronitrile.
It was added dropwise over a period of time and allowed to react. Furthermore, 0.5 part of azobisisobutyronitrile was added and the temperature was raised to 85℃.
The reaction was carried out with stirring for 4 hours to obtain a slightly emulsified solution of a polyol resin (glass transition temperature: 45° C., hydroxyl value: 12) with a non-volatile content of 60%. Add 100 parts of this polyol resin solution to an isobutyl etherified melamine solution ("Yuban 20SE-60").
[Product name manufactured by Mitsui Toatsu Chemical Co., Ltd.], solid content 60%) 6 parts,
A white paint was prepared by kneading and dispersing 40 parts of titanium white, 30 parts of xylene, 30 parts of butyl acetate, and 0.3 parts of a surface conditioner. The white paint was applied to a 0.5 mm thick aluminum plate that had been subjected to a chromic acid chemical conversion treatment using a knife coater to a dry film thickness of 25 μm, and baked at 230° C. for 1 minute. The gloss, weather resistance, and rubbing resistance of the resulting coating film,
The coating film performance in terms of bendability, impact resistance, and solvent resistance was as shown in Table 1. Example 3 In Example 2, methyl methacrylate 26.4
%, polyol resin (glass transition temperature
A colorless and transparent solution with a hydroxyl value of 12) was obtained at 39°C. Thereafter, a white paint was prepared in the same manner as in Example 2 and coated in the same manner, and the resulting coating film performance was as shown in Table 1. Example 4 30 parts of N-n-butoxymethylacrylamide and 0.1 part of para-toluenesulfonic acid were added to 100 parts of the fluorine-containing copolymer (B), and the mixture was reacted at 120°C for 2 hours, followed by 74.5 parts of xylol and butyl acetate. Added 74.5 parts. To this solution was added the monomer mixture in Example 2.
Polyol resin (glass transition temperature 63
A slightly emulsified solution with a temperature of 35° C. and a hydroxyl value of 35) was obtained. Add 43 parts of isobutyl etherified melamine solution (Yuban 20SE-60) to 100 parts of this polyol resin solution.
parts, titanium white 40 parts, xylol 30 parts, butyl acetate
A white paint was prepared by kneading and dispersing 30 parts and 0.3 parts of a surface conditioner. Thereafter, coating was carried out in the same manner as in Example 2, and the coating film performance obtained was as shown in Table 1. Comparative Example 2 1.2 parts of N-n-butoxymethylacrylamide and 0.1 part of para-toluenesulfonic acid were added to 100 parts of the fluorine-containing copolymer solution (B), and the mixture was reacted at 120°C for 2 hours, followed by 8.4 parts of xylol and acetic acid. 8.4 parts of butyl was added. Next, in the same manner as in Example 2, a monomer mixture was added dropwise to this solution to obtain a cloudy solution of a polyol resin (glass transition temperature: 45° C., hydroxyl value: 37). Hereinafter, a white paint was prepared in the same manner as in Example 2, and applied in the same manner.
It was as shown in the table. Comparative Example 3 30 parts of N-n-butoxymethylacrylamide and 0.1 part of para-toluenesulfonic acid were added to 100 parts of the fluorine-containing copolymer solution (B), and the mixture was reacted at 120°C for 2 hours. After that, 10.3 parts of xylol, Butyl acetate 10.3
Added a section. To this solution was added 25.7% of the monomer mixture described in Example 2.
A dropwise reaction was carried out in the same manner as in Example 2, except that the part was changed to 2.6 parts, to obtain a slightly emulsified solution of a polyol resin (glass transition temperature: 36° C., hydroxyl value: 2). Thereafter, a white paint was prepared in the same manner as in Example 2 and coated in the same manner, and the resulting coating film performance was as shown in Table 1. Comparative Example 4 6 parts of isobutyl etherified melamine solution (Yuban 20SE-60) to 100 parts of fluorine-containing copolymer (B),
A white paint was prepared by kneading and dispersing 40 parts of titanium white, 30 parts of xylene, 30 parts of butyl acetate, and 0.3 parts of a surface conditioner. Thereafter, coating was carried out in the same manner as in Example 2, and the coating film performance obtained was as shown in Table 1.
【表】【table】
Claims (1)
得られる主鎖にフツ素原子が結合した、水酸
基を有する含フツ素共重合体100重量部とア
ミン−メタクリルイミド類及び／又はアクリ
ルアミド類３〜60重量部との反応生成物……
10〜97重量％と、 (b) アクリル酸及び／又はメタクリル酸のアル
キル及び／又はシクロアルキルエステルから
なる群から選択されるα，β−エチレン性不
飽和単量体……３〜90重量％ との反応生成物である水酸基価５〜150のポリオ
ール樹脂及び (ii) 硬化剤 とからなる塗料用樹脂組成物。 ２ 前記硬化剤が多価イソシアネート化合物であ
り、かつ前記イソシアネート化合物のイソシアネ
ート基対ポリオール樹脂の水酸基の当量比
（NCO／OH）が（0.15〜1.5／１）になるように
配合してなる特許請求の範囲第１項記載の塗料用
樹脂組成物。 ３ 前記多価イソシアネート化合物がブロツクイ
ソシアネート化合物である特許請求の範囲第２項
記載の塗料用樹脂組成物。 ４ 前記硬化剤がアミノプラスト化合物であり、
かつ前記ポリオール樹脂とアミノプラスト化合物
の混合比（重量基準）が（95：５〜60：40）であ
る特許請求の範囲第１項記載の塗料用樹脂組成
物。 ５ 前記α，β−エチレン性不飽和単量体は、該
単量体中にアクリル酸及び／又はメタクリル酸の
炭素数２〜４のアルキルエステルを40重量％以上
含む特許請求の範囲第１項記載の塗料用樹脂組成
物。[Scope of Claims] 1 (i) (a) 100 parts by weight of a fluorine-containing copolymer having a hydroxyl group, in which a fluorine atom is bonded to the main chain obtained by using fluoroolefin as an essential component, an amine-methacrylimide, and /Or a reaction product with 3 to 60 parts by weight of acrylamide...
(b) an α,β-ethylenically unsaturated monomer selected from the group consisting of alkyl and/or cycloalkyl esters of acrylic acid and/or methacrylic acid...3 to 90% by weight; A resin composition for coatings comprising a polyol resin having a hydroxyl value of 5 to 150 and (ii) a curing agent. 2. A patent claim in which the curing agent is a polyvalent isocyanate compound, and the equivalent ratio (NCO/OH) of the isocyanate groups of the isocyanate compound to the hydroxyl groups of the polyol resin is (0.15 to 1.5/1). The resin composition for coating according to item 1. 3. The resin composition for paint according to claim 2, wherein the polyvalent isocyanate compound is a blocked isocyanate compound. 4 the curing agent is an aminoplast compound,
The resin composition for paint according to claim 1, wherein the mixing ratio (by weight) of the polyol resin and the aminoplast compound is from 95:5 to 60:40. 5. Claim 1, wherein the α,β-ethylenically unsaturated monomer contains 40% by weight or more of an alkyl ester of acrylic acid and/or methacrylic acid having 2 to 4 carbon atoms. The resin composition for paint described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23787584A JPS61115967A (en) | 1984-11-12 | 1984-11-12 | Paint resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23787584A JPS61115967A (en) | 1984-11-12 | 1984-11-12 | Paint resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61115967A JPS61115967A (en) | 1986-06-03 |
| JPH0586434B2 true JPH0586434B2 (en) | 1993-12-13 |
Family
ID=17021707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23787584A Granted JPS61115967A (en) | 1984-11-12 | 1984-11-12 | Paint resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61115967A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0811761B2 (en) * | 1985-07-24 | 1996-02-07 | 関西ペイント株式会社 | Method for producing stable dispersion of vinyl polymer |
| JP2667821B2 (en) * | 1987-02-03 | 1997-10-27 | 関西ペイント株式会社 | Top coating method |
| JP6146314B2 (en) * | 2011-12-16 | 2017-06-14 | 宇部興産株式会社 | Amino resin composition and cured product obtained therefrom |
-
1984
- 1984-11-12 JP JP23787584A patent/JPS61115967A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61115967A (en) | 1986-06-03 |
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