JPH0527666B2 - - Google Patents
Info
- Publication number
- JPH0527666B2 JPH0527666B2 JP59240246A JP24024684A JPH0527666B2 JP H0527666 B2 JPH0527666 B2 JP H0527666B2 JP 59240246 A JP59240246 A JP 59240246A JP 24024684 A JP24024684 A JP 24024684A JP H0527666 B2 JPH0527666 B2 JP H0527666B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- containing resin
- acrylate
- parts
- methacrylate
- 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 - Lifetime
Links
- 229910052731 fluorine Inorganic materials 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 32
- 239000011737 fluorine Substances 0.000 claims description 32
- 239000008199 coating composition Substances 0.000 claims description 22
- 125000001153 fluoro group Chemical group F* 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 18
- 150000003077 polyols Chemical class 0.000 claims description 18
- 150000001451 organic peroxides Chemical class 0.000 claims description 11
- 238000000576 coating method Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 16
- -1 diisocyanate compound Chemical class 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 239000007788 liquid Substances 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 239000003085 diluting agent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 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
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 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
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 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 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 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 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-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
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- WFTWWOCWRSUGAW-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CCOCCOCCOC(=O)C(C)=C WFTWWOCWRSUGAW-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-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
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-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
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-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
- GBUKDQIDVINLOX-UHFFFAOYSA-N C(CCCOOCCCCCCO)CCO Chemical compound C(CCCOOCCCCCCO)CCO GBUKDQIDVINLOX-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- ZCGHEBMEQXMRQL-UHFFFAOYSA-N benzyl 2-carbamoylpyrrolidine-1-carboxylate Chemical compound NC(=O)C1CCCN1C(=O)OCC1=CC=CC=C1 ZCGHEBMEQXMRQL-UHFFFAOYSA-N 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001723 curing Methods 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- AVGYVDOSBJFXFR-UHFFFAOYSA-N diphenyl sulfite Chemical compound C=1C=CC=CC=1OS(=O)OC1=CC=CC=C1 AVGYVDOSBJFXFR-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 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
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Description
〔産業上の利用分野〕
本発明は耐候性、耐食性、耐薬品性等に優れた
塗膜を与える含フツ素樹脂被覆組成物に関するも
のである。
〔従来の技術〕
従来、有機過酸化物により硬化可能な被覆組成
物として、ポリエステルアクリレート樹脂系、エ
ポキシアクリレート樹脂系、ウレタンアクリレー
ト樹脂系、ポリエーテルアクリレート樹脂系、シ
リコンアクリレート樹脂系等が主なものとして知
られている。
〔発明が解決しようとする問題点〕
近年、カーテンウオール、プレコートメタル等
の金属塗装分野、プラスチツク塗装分野等に於て
塗膜の高寿命化が要求されるようになつてきてい
るが、前記被覆組成物は長期間に亘る耐候性、耐
食性、耐薬品性に優れた塗膜を得ることが困難
で、前記要求を満足しないものであつた。
そこで、長期耐候性等に優れたフツ素樹脂系被
覆組成物が注目されてきている。
しかしながら、従来知られているフツ素樹脂系
被覆組成物は、一般に有機希釈剤に対する溶解性
が悪く、また得られる塗膜は前記従来の被覆組成
物に比較し、光沢、鮮映性、透明性等が劣るとい
う欠点があつた。
このような欠点があるため、フツ素樹脂系被覆
組成物は初期の塗料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、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、水酸基価30〜200のフツ素原子含有ポリオー
ルの水酸基30〜100％に対し、ウレタン結合を介
し、α、β−エチレン性不飽和基を結合せしめた
含フツ素樹脂(i)100重量部に対し、有機過酸化物
(ii)を0.1〜３重量部含有させた含フツ素樹脂被覆
組成物に関するものである。
以下、本発明を詳細に説明する。
本発明において使用する含フツ素樹脂(i)は、フ
ツ素原子含有ポリオールとジイソシアネート化合
物とを反応させ、次いで反応生成物中に含まれる
遊離のイソシアネート基に対し、さらに水酸基を
有するアクリレート及び／又はメタクリレートを
反応させることによつて得られる。すなわち、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、水酸基価約30〜200、
重量平均分子量約1000〜500000のフツ素原子含有
ポリオールに、該フツ素原子含有ポリオールの水
酸基１当量に対し約1.5〜2.5当量のジイソシアネ
ート化合物を反応させ、得られた反応生成物に、
該反応生成物の遊離イソシアネート基に対し、ほ
ぼ当量の水酸基を有するアクリレート及び／又は
メタクリレートを混合し反応させることによつて
得られる。
このようにして得られた含フツ素樹脂(i)は、フ
ツ素原子含有ポリオールの水酸基のほぼ100％に
対し、ウレタン結合を介し、α、β−エチレン性
不飽和基が結合した樹脂となる。
なお、前記フツ素原子含有ポリオールとしては
好適には特開昭57−34107号公報に記載される共
重合体が挙げられる。すなわち、該共重合体は、
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およびヒドロキシ
アルキルビニルエーテルを構成成分として夫々40
〜60モル％、５〜45モル％、５〜45モル％および
３〜25モル％の割合、好ましくは夫々45〜55モル
％、10〜30モル％、10〜35モル％および５〜20モ
ル％の割合で含有するものである。
フルオロオレフイン含量の低すぎるものは耐候
性の点から好ましくないばかりでなく製造面で不
都合を生ずる。またフルオロオレフイン含量の高
すぎるものも製造面で難がある。一方、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
のでいずれも好ましくない。
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ものであることが、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では、溶解性が変化し、ア
ルコール類などの特定のものにしか溶解しなくな
り、また硬化塗膜の可撓性を減少させるので好ま
しくない。また、該含量の低すぎるものでは、架
橋密度が低く硬化塗膜の耐溶剤性等が劣るので好
ましくない。
前記共重合体の原料の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を
使用することが好ましい。また、アルキルビニル
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であるものを使用すること
が好ましい。
前記共重合体は、30モル％をこえない範囲で上
記４種の必須構成成分以外の他の共単量体を含有
することができる。かかる共単量体としてはエチ
レン、プロピレン、イソブチレン等のオレフイン
類、塩化ビニル、塩化ビニリデン等のハロオレフ
イン類、メタクリル酸メチル等の不飽和カルボン
酸エステル類、酢酸ビニル、ｎ−酪酸ビニル等の
カルボン酸ビニル類、フマル酸、マレイン酸、ア
クリル酸、メタクリル酸等の不飽和カルボン酸類
等が挙げられる。
前記のごとき共重合体は、所定割合の単量体混
合物に重合媒体の共存下あるいは非共存下に水溶
性開始剤や油溶性開始剤等の重合開始剤あるいは
電離性放射線などの重合開始源を作用せしめて共
重合反応を行わしめることにより製造される。
前記共重合体すなわちフツ素原子含有ポリオー
ルとして例えばルミフロンLF100、ルミフロン
LF200、ルミフロンLF210、ルミフロンLF300、
ルミフロンLF400（いずれも旭硝子社製商品名）
等が市販されている。
また前記ジイソシアネート化合物としては、ト
リレンジイソシアネート、ジフエニルジイソシア
ネート、ｐ−フエニレンジイソシアネート、キシ
リレンジイソシアネー、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、水添ジフエニレンジ
イソシアネート、水添キシリレンジイソシアネー
ト等が挙げられる。特に、耐候性のよい脂肪族も
しくは脂環族系ジイソシアネート化合物が好適で
ある。
また前記水酸基を有するアクリレート及び／又
はメタクリレートとしては、２−ヒドロキシエチ
ルアクリレート、２−ヒドロキシエチルメタクリ
レート、２−ヒドロキシプロピルアクリレート、
２−ヒドロキシプロピルメタクリレート、２−ヒ
ドロキシブチルアクリレート、２−ヒドロキシブ
チルメタクリレート等が挙げられる。
また本発明において使用する含フツ素樹脂(i)
は、別法としてフツ素原子含有ポリオールとイソ
シアネート基を有するアクリレート及び／又はメ
タクリレートを反応させることによつても得られ
る。すなわち、フツ素原子含有ポリオールに、該
ポリオールの水酸基１当量に対し、0.3〜１当量
のイソシアネート基を有するアクリレート及び／
又はメタクリレートを反応させることにより得ら
れる。
なお、イソシアネート基対水酸基の当量比が
0.3未満になると架橋密度が低く、硬化塗膜の耐
溶剤性等が劣り、逆に１を越えると遊離イソシア
ネート基が残り、塗料として不安定になるのでい
ずれも好ましくない。
またフツ素原子含有ポリオールとしては前記共
重合体が好適に使用出来る。またイソシアネート
基を有するアクリレート及び／又はメタクリレー
トとしては、水酸基を有するアクリレート又はメ
タクリレートとジイソシアネート化合物との反応
生成物あるいはイソシアネートエチルアクリレー
ト、イソシアネートエチルメタクリレート等が挙
げられる。
このようにして得られた含フツ素樹脂(i)は、フ
ツ素原子含有ポリオールの水酸基の30〜100％に
対し、ウレタン結合を介し、α、β−エチレン性
不飽和基が結合した樹脂となる。
本発明の含フツ素樹脂被覆組成物は、前記含フ
ツ素樹脂(i)及び有機過酸化物(ii)を必須成分とする
ものである。
本発明において使用する有機過酸化物(ii)として
はベンゾイルパーオキサイド、ラウロイルパーオ
キサイド、メチルエチルケトンパーオキサイド、
シクロヘキサノンパーオキサイド、ヒドロキシヘ
キシルパーオキサイド、ターシヤリイブチルパー
オキサイド、クメンハイドロパーオキサイド等が
挙げられる。
有機過酸化物(ii)は、含フツ素樹脂(i)を架橋反応
させるために、配合するものであり、その添加量
は含フツ素樹脂(i)100重量部に対し0.1〜３重量部
程度が適当である。なお、添加量が前記範囲より
少ないと得られる塗膜の硬化性が十分でなく、逆
に多過ぎると塗膜が脆くなるのでいずれも好まし
くない。
また、本発明においては、前記有機過酸化物(ii)
の分解を調節し、常温硬化から焼付硬化までの硬
化速度を調節するため、反応促進剤を含フツ樹脂
(i)100重量部に対し３重量部以下の量にて併用す
ることが望ましい。
反応促進剤としては、ラウリルメルカプタン、
ジフエニルサルフアイト、ナフテン酸コバルト、
オクトエ酸コバルト、ナフテン酸マンガン、オク
トエ酸バナジル、ナフテン酸銅、ナフテン酸カル
シウム、ナフテン酸バリウム、ナフテン酸亜鉛、
ナフテン酸ジルコニウム、ジメチルアニリン、ジ
エタノールアニリン等が挙げられる。
本発明の含フツ素樹脂被覆組成物は、さらに適
宜反応性希釈剤を配合することも出来る。反応性
希釈剤としては、ラジカル重合性二重結合を有す
る化合物が利用可能であるが、特に耐候性等を考
慮して、モノアクリレート、モノメタクリレー
ト、ポリアクリレート、ポリメタクリレートが好
適である。具体的にはシクロヘキシルアクリレー
ト、シクロヘキシルメタクリレート、ベンジルア
クリレート、ベンジルメタクリレート、カルビト
ールアクリレート、カルビトールメタクリレー
ト、２−エチルヘキシルアクリレート、２−エチ
ルヘキシルメタクリレート、２−ヒドロキシエチ
ルアクリレート、２−ヒドロキシエチルメタクリ
レート、エチレングリコールジアクリレート、エ
チレングリコールジメタクリレート、ジエチレン
グリコールジアクリレート、ジエチレングリコー
ルジメタクリレート、トリエチレングリコールジ
アクリレート、トリエチレングリコールジメタク
リレート、ネオペンチルグリコールジアクリレー
ト、ネオペンチルグリコールジメタクリレート、
１，６−ヘキサンジオールジアクリレート、１，
６−ヘキサンジオールジメタクリレート、ポリエ
チレングリコールジアクリレート、ポリエチレン
グリコールジメタクリレート、ポリプロピレング
リコールジアクリレート、ポリプロピレングリコ
ールジメタクリレート、トリメチロールプロパン
トリアクリレート、トリメチロールプロパントリ
メタクリレート、ペンタエリスリトールトリアク
リレート、ペンタエリスリトールトリメタクリレ
ート、トリス（２−アクリロキシエチル）イソシ
アヌレート等が挙げられる。
これら反応性希釈剤は必ずしも配合する必要が
ないが、前記含フツ素樹脂(i)は一般に高粘度とな
るため塗装作業性等を考慮して含フツ素樹脂(i)
100重量部に対し150重量部以下、好ましくは10〜
50重量部配合される。
本発明の含フツ素樹脂被覆組成物は、その他必
要に応じ各種顔料；有機溶剤；エポキシアクリレ
ート、ウレタンアクリレート、ポリエステルアク
リレート、シリコン樹脂、ポリアミド樹脂等の改
質剤；シランカツプリング剤、チタンカツプリン
グ剤、消泡剤、レベリング剤等の添加剤を配合す
ることも可能である。
〔発明の効果〕
以上説明した通り、本発明の含フツ素樹脂被覆
組成物は、従来公知の有機過酸化物硬化型被覆組
成物に比較し、長期耐候性、耐食性、耐薬品性等
に優れ、また従来公知の含フツ素樹脂被覆組成物
の欠点である有機希釈剤に対する溶解性の悪さ、
得られる塗膜の光沢、鮮映性、透明性等の悪さを
解消した画期的なものである。
従つて、本発明の含フツ素樹脂被覆組成物は、
各種金属製品、プラスチツク製品等の保護被覆と
して、また光フアイバーIC基板等の保護被覆と
して非常に優れた特性を示すものである。
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。
＜含フツ素樹脂液Ａの調製＞
撹拌機及び還流冷却器を備えた反応装置に、フ
ツ素原子含有ポリオール〔ルミフロンLF200（旭
硝子社製商品名）；溶剤キシロール、不揮発分50
％、水酸基価52（固形分換算）〕200部とヘキサメ
チレンジイソシアネート17部を仕込み、60℃、３
時間反応させた後、さらに２−ヒドロキシエチル
アクリレートを12部添加し、70℃、２時間反応さ
せ、含フツ素樹脂液Ａを調製した。
なお、得られた含フツ素樹脂は、フツ素原子含
有ポリオールの水酸基の90％にアクリレート基が
ウレタン結合を介して結合していた。
＜含フツ素樹脂液Ｂの調製＞
前記と同様の反応装置に、フツ素原子含有ポリ
オール〔ルミフロンLF210（旭硝子社製商品名〕；
溶剤キシロール、不揮発分50％、水酸基価100（固
形分換算）〕300部とイソシアネートエチルメタク
リレート20部を仕込み、60℃、３時間反応させ、
含フツ素樹脂液Ｂを調製した。
なお、得られた含フツ素樹脂は、フツ素原子含
有ポリオールの水酸基の48％にメタクリレート基
がウレタン結合を介して結合していた。
＜含フツ素樹脂液Ｃの調製＞
前記と同様の反応装置にイソホロンジイソシア
ネート51部を入れ60℃に加温し、アクリル酸β−
ヒドロキシプロピル33部を１時間にわたり滴下し
た後、さらに３時間反応する。次いでフツ素含有
ポリオール〔ルミフロンLF210〕300部を添加し、
70℃、２時間反応させ、含フツ素樹脂液Ｃを調製
した。
なお、得られた含フツ素樹脂は、フツ素原子含
有ポリオールの水酸基の79％にアクリレート基が
ウレタン結合を介して結合していた。
＜ウレタンアクリレート樹脂液の調製＞
前記と同様の反応装置に、数平均分子量1000の
ポリプロピレングリコール250部とヘキサメチレ
ンジイソシアネート84部を仕込み、70℃、２時間
反応させた後、さらに２−ヒドロキシエチルメタ
クリレート65部を添加し、70℃、２時間反応さ
せ、ウレタンアクリレート樹脂液を調整した。
＜アクリル化ポリエステル樹脂液の調製＞
前記と同様の反応装置に、トリメチロールプロ
パン、トリエチレングリコール、１，６−ヘキサ
ンジオールからなる多価アルコールとアジピン酸
から常法により合成したポリエステルポリオール
（数平均分子量800、水酸基価100）67.5部、アク
リル酸16.2部及びメタンスルフオン酸0.4部を仕
込み、95℃、８時間反応させ、アクリル化ポリエ
ステル樹脂液を調製した。
実施例１〜５及び比較１〜２
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、第１表に示す被覆組成物（単位：
部）をナイフコーターにて膜厚が25μになるよう
塗布し、１週間常温乾燥させた。
得られた塗膜につき塗膜性能試験を行ない、そ
の結果を第１表下欄に示した。
第１表より明らかの通り、本発明の含フツ素樹
脂被覆組成物は、初期光沢が比較例１〜２の従来
の被覆組成物と同様高光沢を有しており、促進耐
候性試験後も光沢低下率が小さく、従来の被覆組
成物に比較し耐候性が非常に優れていた。また屈
折性、耐アルカリ性、耐酸性、耐ラビング性も優
れていた。
実施例 ６
実施例１において硬化手段として、120℃、30
分間焼付硬化させる以外は、同様にして第１表に
示す被覆組成物を塗布し、得られた塗膜性能試験
結果を第１表下欄に示した。
第１表より明らかの通り、本発明の含フツ素樹
脂被覆組成物は耐候性、耐アルカリ性、耐酸性と
も従来の被覆組成物に比較し、非常に優れてい
た。
[Industrial Application Field] The present invention relates to a fluorine-containing resin coating composition that provides a coating film with excellent weather resistance, corrosion resistance, chemical resistance, etc. [Prior Art] Conventionally, the main coating compositions curable with organic peroxides include polyester acrylate resins, epoxy acrylate resins, urethane acrylate resins, polyether acrylate resins, silicone acrylate resins, etc. known as. [Problems to be solved by the invention] In recent years, there has been a demand for longer lifespans of coating films in the fields of metal coatings such as curtain walls and precoated metal, and plastic coatings. It was difficult to obtain a coating film with excellent long-term weather resistance, corrosion resistance, and chemical resistance with the composition, and the composition did not satisfy the above requirements. Therefore, fluororesin-based coating compositions with excellent long-term weather resistance are attracting attention. However, conventionally known fluororesin-based coating compositions generally have poor solubility in organic diluents, and the resulting coating films have poor gloss, sharpness, and transparency compared to the conventional coating compositions. The disadvantage was that the quality was inferior. Due to these drawbacks, fluororesin-based coating compositions still do not have sufficient commercial value in the field of coatings, where initial coating appearance and aesthetics are important, and therefore, they cannot be said to have sufficient commercial value. While acknowledging the nature of the problem, early improvements were requested. [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, in the present invention, fluorine atoms are bonded to the main chain obtained by using fluoroolefin as an essential component, and α , organic peroxide per 100 parts by weight of fluorine-containing resin (i) bonded with β-ethylenically unsaturated groups.
The present invention relates to a fluorine-containing resin coating composition containing 0.1 to 3 parts by weight of (ii). The present invention will be explained in detail below. The fluorine-containing resin (i) used in the present invention is prepared by reacting a fluorine atom-containing polyol with a diisocyanate compound, and then reacting the free isocyanate group contained in the reaction product with an acrylate having a hydroxyl group and/or a diisocyanate compound. Obtained by reacting methacrylate. That is, a fluorine atom is bonded to the main chain obtained by using fluoroolefin as an essential component, and the hydroxyl value is approximately 30 to 200.
A fluorine atom-containing polyol having a weight average molecular weight of about 1,000 to 500,000 is reacted with about 1.5 to 2.5 equivalents of a diisocyanate compound per equivalent of hydroxyl group in the fluorine atom-containing polyol, and the resulting reaction product is
It is obtained by mixing and reacting an approximately equivalent amount of acrylate and/or methacrylate having a hydroxyl group with the free isocyanate group of the reaction product. The thus obtained fluorine-containing resin (i) is a resin in which α,β-ethylenically unsaturated groups are bonded to almost 100% of the hydroxyl groups of the fluorine atom-containing polyol via urethane bonds. . The fluorine atom-containing polyol is preferably a copolymer described in JP-A-57-34107. That is, the copolymer is
Fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether as constituent components
Proportions of ~60 mol%, 5-45 mol%, 5-45 mol% and 3-25 mol%, preferably 45-55 mol%, 10-30 mol%, 10-35 mol% and 5-20 mol%, respectively %. Too low a fluoroolefin content is not only unfavorable from the viewpoint of weather resistance, but also causes problems in production. Also, those containing too high a fluoroolefin content are also difficult to manufacture. On the other hand, 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, so both are not preferred. Furthermore, it is particularly important that the composition contains 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. That is, if the hydroxyalkyl vinyl ether content is too high, the solubility will change and it will become soluble only in specific substances such as alcohols, and the flexibility of the cured coating film will be reduced, which is not preferable. On the other hand, if the content is too low, the crosslinking density will be low and the solvent resistance of the cured coating film will be poor, which is not preferable. As the fluoroolefin as a raw material for the copolymer, it is preferable to use perhaloolefin, particularly chlorotrifluoroethylene or tetrafluoroethylene. Further, as the alkyl vinyl ether, it is preferable to use one containing a linear or branched alkyl group having 2 to 8 carbon atoms, particularly one in which the alkyl group has 2 to 4 carbon atoms. The copolymer may contain comonomers other than the above four essential components in an amount not exceeding 30 mol%. Examples of such comonomers include olefins such as ethylene, propylene, and isobutylene, haloolefins such as vinyl chloride and vinylidene chloride, unsaturated carboxylic acid esters such as methyl methacrylate, and carboxylates such as vinyl acetate and vinyl n-butyrate. Examples include unsaturated carboxylic acids such as acid vinyls, fumaric acid, maleic acid, acrylic acid, and methacrylic acid. The above copolymer is produced by adding a polymerization initiator such as a water-soluble initiator or an oil-soluble initiator or a polymerization initiation source such as ionizing radiation to a monomer mixture in a predetermined proportion in the presence or absence of a polymerization medium. It is produced by causing a copolymerization reaction to occur. Examples of the copolymer, ie, fluorine atom-containing polyol, include Lumiflon LF100 and Lumiflon.
LF200, Lumiflon LF210, Lumiflon LF300,
Lumiflon LF400 (all product names manufactured by Asahi Glass Co., Ltd.)
etc. are commercially available. Examples of the diisocyanate compounds include tolylene diisocyanate, diphenyl diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenyl diisocyanate, hydrogenated xylylene diisocyanate, and the like. can be mentioned. Particularly suitable are aliphatic or alicyclic diisocyanate compounds which have good weather resistance. Further, as the acrylate and/or methacrylate having a hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
Examples include 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, and 2-hydroxybutyl methacrylate. Also, fluorine-containing resin (i) used in the present invention
can alternatively be obtained by reacting a fluorine atom-containing polyol with an acrylate and/or methacrylate having an isocyanate group. That is, in a fluorine atom-containing polyol, an acrylate and/or having an isocyanate group in an amount of 0.3 to 1 equivalent per 1 equivalent of a hydroxyl group in the polyol is added.
Alternatively, it can be obtained by reacting methacrylate. Note that the equivalent ratio of isocyanate groups to hydroxyl groups is
If it is less than 0.3, the crosslinking density will be low and the solvent resistance of the cured coating film will be poor, while if it exceeds 1, free isocyanate groups will remain and the coating will become unstable, so both are not preferred. Moreover, the above copolymers can be suitably used as the fluorine atom-containing polyol. Examples of the acrylate and/or methacrylate having an isocyanate group include reaction products of acrylate or methacrylate having a hydroxyl group and a diisocyanate compound, isocyanate ethyl acrylate, isocyanate ethyl methacrylate, and the like. The thus obtained fluorine-containing resin (i) is a resin in which α,β-ethylenically unsaturated groups are bonded to 30 to 100% of the hydroxyl groups of the fluorine atom-containing polyol via urethane bonds. Become. The fluorine-containing resin coating composition of the present invention contains the above-mentioned fluorine-containing resin (i) and organic peroxide (ii) as essential components. Examples of the organic peroxide (ii) used in the present invention include benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide,
Examples thereof include cyclohexanone peroxide, hydroxyhexyl peroxide, tert-butyl peroxide, and cumene hydroperoxide. Organic peroxide (ii) is blended in order to cause a crosslinking reaction in fluorine-containing resin (i), and the amount added is 0.1 to 3 parts by weight per 100 parts by weight of fluorine-containing resin (i). The degree is appropriate. Incidentally, if the amount added is less than the above range, the resulting coating film will not have sufficient curability, while if it is too large, the coating film will become brittle, so both are not preferred. Further, in the present invention, the organic peroxide (ii)
In order to control the decomposition of
(i) It is desirable to use them in an amount of 3 parts by weight or less per 100 parts by weight. As a reaction accelerator, lauryl mercaptan,
Diphenyl sulfite, cobalt naphthenate,
Cobalt octoate, manganese naphthenate, vanadyl octoate, copper naphthenate, calcium naphthenate, barium naphthenate, zinc naphthenate,
Examples include zirconium naphthenate, dimethylaniline, diethanolaniline, and the like. The fluorine-containing resin coating composition of the present invention may further contain an appropriate reactive diluent. Compounds having radically polymerizable double bonds can be used as the reactive diluent, but monoacrylates, monomethacrylates, polyacrylates, and polymethacrylates are preferable, especially considering weather resistance. Specifically, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, carbitol acrylate, carbitol methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol diacrylate. , ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate,
1,6-hexanediol diacrylate, 1,
6-Hexanediol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, Tris (2-acryloxyethyl)isocyanurate and the like. These reactive diluents do not necessarily need to be blended, but since the fluorine-containing resin (i) generally has a high viscosity, the fluorine-containing resin (i) should be added in consideration of painting workability, etc.
150 parts by weight or less, preferably 10 to 100 parts by weight
Contains 50 parts by weight. The fluorine-containing resin coating composition of the present invention includes various other pigments as required; organic solvent; modifiers such as epoxy acrylate, urethane acrylate, polyester acrylate, silicone resin, and polyamide resin; silane coupling agent, titanium coupling agent; It is also possible to incorporate additives such as antifoaming agents, antifoaming agents, and leveling agents. [Effects of the Invention] As explained above, the fluorine-containing resin coating composition of the present invention has excellent long-term weather resistance, corrosion resistance, chemical resistance, etc. compared to conventionally known organic peroxide-curable coating compositions. , as well as poor solubility in organic diluents, which is a drawback of conventionally known fluorine-containing resin coating compositions.
This is an epoch-making product that eliminates the poor gloss, sharpness, and transparency of the resulting coating film. Therefore, the fluorine-containing resin coating composition of the present invention
It exhibits excellent properties as a protective coating for various metal products, plastic products, etc., and as a protective coating for optical fiber IC boards, etc. Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, "parts" and "%" are based on weight. <Preparation of fluorine-containing resin liquid A> In a reaction apparatus equipped with a stirrer and a reflux condenser, a fluorine atom-containing polyol [Lumiflon LF200 (trade name, manufactured by Asahi Glass Co., Ltd.); solvent xylol, non-volatile content 50
%, hydroxyl value 52 (solid content equivalent)] and 17 parts of hexamethylene diisocyanate, and heated at 60°C for 30 minutes.
After reacting for an hour, 12 parts of 2-hydroxyethyl acrylate was further added and reacted at 70°C for 2 hours to prepare fluorine-containing resin liquid A. In addition, in the obtained fluorine-containing resin, acrylate groups were bonded to 90% of the hydroxyl groups of the fluorine atom-containing polyol via urethane bonds. <Preparation of fluorine-containing resin liquid B> In a reaction apparatus similar to the above, a fluorine atom-containing polyol [Lumiflon LF210 (trade name manufactured by Asahi Glass Co., Ltd.)];
300 parts of the solvent xylol, nonvolatile content 50%, hydroxyl value 100 (solid content equivalent)] and 20 parts of isocyanate ethyl methacrylate were reacted at 60°C for 3 hours.
Fluorine-containing resin liquid B was prepared. In the obtained fluorine-containing resin, methacrylate groups were bonded to 48% of the hydroxyl groups of the fluorine atom-containing polyol via urethane bonds. <Preparation of fluorine-containing resin liquid C> 51 parts of isophorone diisocyanate was placed in the same reactor as above and heated to 60°C, and acrylic acid β-
After dropping 33 parts of hydroxypropyl over 1 hour, the reaction is continued for an additional 3 hours. Next, 300 parts of fluorine-containing polyol [Lumiflon LF210] was added,
The reaction was carried out at 70°C for 2 hours to prepare fluorine-containing resin liquid C. In addition, in the obtained fluorine-containing resin, acrylate groups were bonded to 79% of the hydroxyl groups of the fluorine atom-containing polyol via urethane bonds. <Preparation of urethane acrylate resin liquid> 250 parts of polypropylene glycol with a number average molecular weight of 1000 and 84 parts of hexamethylene diisocyanate were charged into the same reaction apparatus as above, and after reacting at 70°C for 2 hours, 2-hydroxyethyl methacrylate was added. 65 parts were added and reacted at 70°C for 2 hours to prepare a urethane acrylate resin liquid. <Preparation of acrylated polyester resin liquid> In a reaction apparatus similar to the above, a polyester polyol (number average 67.5 parts (molecular weight: 800, hydroxyl value: 100), 16.2 parts of acrylic acid, and 0.4 parts of methanesulfonic acid were charged and reacted at 95°C for 8 hours to prepare an acrylated polyester resin liquid. Examples 1 to 5 and Comparisons 1 to 2 A coating composition shown in Table 1 (unit:
Part) was applied using a knife coater to a film thickness of 25 μm, and dried at room temperature for one week. A coating film performance test was conducted on the obtained coating film, and the results are shown in the lower column of Table 1. As is clear from Table 1, the fluorine-containing resin coating composition of the present invention has a high initial gloss similar to that of the conventional coating compositions of Comparative Examples 1 and 2, and even after the accelerated weathering test. The gloss reduction rate was small and the weather resistance was extremely superior compared to conventional coating compositions. It also had excellent refractive properties, alkali resistance, acid resistance, and rubbing resistance. Example 6 In Example 1, the curing method was 120°C, 30°C.
The coating compositions shown in Table 1 were applied in the same manner except that they were cured by baking for a minute, and the obtained coating film performance test results are shown in the lower column of Table 1. As is clear from Table 1, the fluorine-containing resin coating composition of the present invention was extremely superior in weather resistance, alkali resistance, and acid resistance compared to conventional coating compositions.
【表】【table】
Claims (1)
る主鎖にフツ素原子が結合した、水酸基価30〜
200のフツ素原子含有ポリオールの水酸基30〜100
％に対し、ウレタン結合を介し、α、β−エチレ
ン性不飽和基を結合せしめた含フツ素樹脂(i)100
重量部に対し、有機過酸化物(ii)を0.1〜３重量部
含有させたことを特徴とする含フツ素樹脂被覆組
成物。1 Fluorine atoms are bonded to the main chain obtained with fluoroolefin as an essential component, and the hydroxyl value is 30~
200 fluorine atom-containing polyols with 30 to 100 hydroxyl groups
%, fluorine-containing resin (i) with α, β-ethylenically unsaturated groups bonded via urethane bonds (i) 100
A fluorine-containing resin coating composition containing 0.1 to 3 parts by weight of organic peroxide (ii).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59240246A JPS61118466A (en) | 1984-11-14 | 1984-11-14 | Fluorine-containing resin coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59240246A JPS61118466A (en) | 1984-11-14 | 1984-11-14 | Fluorine-containing resin coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61118466A JPS61118466A (en) | 1986-06-05 |
| JPH0527666B2 true JPH0527666B2 (en) | 1993-04-21 |
Family
ID=17056629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59240246A Granted JPS61118466A (en) | 1984-11-14 | 1984-11-14 | Fluorine-containing resin coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61118466A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0742331B2 (en) * | 1985-07-26 | 1995-05-10 | 旭硝子株式会社 | Process for producing fluorine-containing polymer containing unsaturated group |
| GB8621793D0 (en) * | 1986-09-10 | 1986-10-15 | Ici Plc | Coating compositions |
| US5311500A (en) * | 1988-01-22 | 1994-05-10 | Fuji Photo Film Co., Ltd. | Magneto-optical disk |
| JP3888653B2 (en) * | 1998-06-09 | 2007-03-07 | 日本化薬株式会社 | Resin composition and cured product |
| JP4534341B2 (en) * | 2000-11-07 | 2010-09-01 | Ｊｓｒ株式会社 | Curable resin composition and antireflection film |
| JP4709942B2 (en) * | 2008-11-28 | 2011-06-29 | 新日本製鐵株式会社 | Chromate-free surface-treated metal material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55139414A (en) * | 1979-04-11 | 1980-10-31 | Minnesota Mining & Mfg | Irradiation ray hardening composition containing fluorocarbon substituted polyetherurethaneacrylate |
| JPS5941315A (en) * | 1982-09-01 | 1984-03-07 | Hitachi Chem Co Ltd | Preparation of graft copolymer |
| JPS59189108A (en) * | 1983-04-11 | 1984-10-26 | Daikin Ind Ltd | Fluorine-containing copolymer and its composition |
-
1984
- 1984-11-14 JP JP59240246A patent/JPS61118466A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55139414A (en) * | 1979-04-11 | 1980-10-31 | Minnesota Mining & Mfg | Irradiation ray hardening composition containing fluorocarbon substituted polyetherurethaneacrylate |
| JPS5941315A (en) * | 1982-09-01 | 1984-03-07 | Hitachi Chem Co Ltd | Preparation of graft copolymer |
| JPS59189108A (en) * | 1983-04-11 | 1984-10-26 | Daikin Ind Ltd | Fluorine-containing copolymer and its composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61118466A (en) | 1986-06-05 |
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