JPH02300253A - Curable fluorinated resin coating material - Google Patents
Curable fluorinated resin coating materialInfo
- Publication number
- JPH02300253A JPH02300253A JP12041689A JP12041689A JPH02300253A JP H02300253 A JPH02300253 A JP H02300253A JP 12041689 A JP12041689 A JP 12041689A JP 12041689 A JP12041689 A JP 12041689A JP H02300253 A JPH02300253 A JP H02300253A
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- paint
- curable
- hydroxyl group
- vinyl monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 29
- 238000000576 coating method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 title abstract description 12
- 239000011347 resin Substances 0.000 title abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 229920002545 silicone oil Polymers 0.000 claims abstract description 17
- 229920003180 amino resin Polymers 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims description 61
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 27
- 229920002554 vinyl polymer Polymers 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 150000007519 polyprotic acids Polymers 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 19
- 239000000126 substance Substances 0.000 description 14
- -1 trifluoroethylene, tetrafluoroethylene Chemical group 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229920000180 alkyd Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920001567 vinyl ester resin Polymers 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229920003270 Cymel® Polymers 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000004381 surface treatment Methods 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
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- YOCPOKXCVPDDJX-UHFFFAOYSA-N 10-ethenoxy-10-oxodecanoic acid Chemical compound OC(=O)CCCCCCCCC(=O)OC=C YOCPOKXCVPDDJX-UHFFFAOYSA-N 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical group C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- JWCDUUFOAZFFMX-UHFFFAOYSA-N 2-ethenoxy-n,n-dimethylethanamine Chemical compound CN(C)CCOC=C JWCDUUFOAZFFMX-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- NZZPNEOLSOMDBS-UHFFFAOYSA-N 3-ethenoxy-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCOC=C NZZPNEOLSOMDBS-UHFFFAOYSA-N 0.000 description 1
- OJXVWULQHYTXRF-UHFFFAOYSA-N 3-ethenoxypropan-1-ol Chemical compound OCCCOC=C OJXVWULQHYTXRF-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- PRQREXSTQVWUGV-UHFFFAOYSA-N 6-ethenoxy-6-oxohexanoic acid Chemical compound OC(=O)CCCCC(=O)OC=C PRQREXSTQVWUGV-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CBCZZTQJJPZKTD-UHFFFAOYSA-N CCCCCC(C(=O)OC=C)(Cl)Cl Chemical compound CCCCCC(C(=O)OC=C)(Cl)Cl CBCZZTQJJPZKTD-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 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
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 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
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 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
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- XMYLSWOTJKUSHE-UHFFFAOYSA-N cyanamide;lead Chemical compound [Pb].NC#N XMYLSWOTJKUSHE-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- LZWYWAIOTBEZFN-UHFFFAOYSA-N ethenyl hexanoate Chemical compound CCCCCC(=O)OC=C LZWYWAIOTBEZFN-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- QBDADGJLZNIRFQ-UHFFFAOYSA-N ethenyl octanoate Chemical compound CCCCCCCC(=O)OC=C QBDADGJLZNIRFQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 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
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 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
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate 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
- 239000011133 lead Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 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
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、硬化性フッ素樹脂塗料に関し、更に詳しくは
、塗料成分中にシリコンオイルで表面処理したシリカ微
粉末を含有し、型子地模様の塗膜が得られるようにした
常温硬化性又は熱硬化性フッ素樹脂塗料に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a curable fluororesin paint, and more specifically, the present invention relates to a curable fluororesin paint, and more specifically, the paint component contains fine silica powder that has been surface-treated with silicone oil, and has a mold base pattern. The present invention relates to a room-temperature-curable or thermosetting fluororesin paint that provides a coating film.
フッ素樹脂塗料は、その優れた耐候性、耐蝕性、耐薬品
性、ｆΩ水性等を活かして、建材のみならず、最近は家
具、什器、車輌等広範な分野で利用されるようになった
。また、例えば家具等に用いられる金、＠化粧板等に対
する市場ニーズの多様化に伴ない、従来からの汎用餌料
を用いた平滑な塗膜に加えて、型子地模様に代表される
意匠性を際立たせることができる塗料が要求されている
。Fluororesin paints have recently come to be used not only as building materials but also in a wide range of fields such as furniture, fixtures, and vehicles, taking advantage of their excellent weather resistance, corrosion resistance, chemical resistance, fΩ water resistance, etc. In addition, with the diversification of market needs for, for example, gold used in furniture, decorative boards, etc., in addition to smooth coating films using conventional general-purpose feeds, we are also adding designs such as patterns on molded surfaces. There is a demand for paints that can make the colors stand out.
現在、汎用顔料を用いた平滑な塗膜のほかに、被塗物に
模様を賦与する塗料としては、アルミニウムの鱗片状粉
末を顔料として使用したメタリック調の模様塗膜や、シ
リカ粉末、ガラス繊維、あるいはテフロン粒子等を餌料
として使用した低光沢の模様塗膜等が挙げられるが、い
ずれも型子地模様に代表される高度の意匠性を表現する
ことは出来ない。Currently, in addition to smooth paint films using general-purpose pigments, there are also paints that give patterns to the object being coated, such as metallic pattern paint films using aluminum flake powder as a pigment, silica powder, and glass fiber paints. , or a low-gloss patterned coating film using Teflon particles as bait, but none of them can express the high level of design typified by the molded pattern.
本発明が解決しようとする課題は、耐候性、耐蝕性、耐
薬品性、撥水性を損なわずに、型子地模様に代表される
意匠性の有る塗膜を形成することが出来る硬化性フッ素
樹脂塗料を提供することにある。The problem to be solved by the present invention is to use a curable fluorocarbon that can form a coating film with a design characteristic, typified by a mold pattern, without impairing weather resistance, corrosion resistance, chemical resistance, or water repellency. Our goal is to provide resin paints.
本発明は、上記課題を解決するために、（ａ）水酸基を
有するフッ素樹脂、
（ｂ）硬化剤及び
（ｃ）シリコンオイルで表面処理したシリカ微粉末
を含有することを特徴とする硬化性フッ素樹脂塗料を提
供するものである。この際、シリコンオイルで表面処理
したシリカ微粉末の粒径が５〜３００μｍの範囲にある
ことも好ましく、水酸基を有するフッ素樹脂が含フッ素
ビニルモノマー、水酸基を有する共重合性ビニルモノマ
ー及び他の共重合可能なビニルモノマーから成る重合性
ビニルモノマーを共重合させて得た共重合体であり、水
酸基を有する共重合性ビニルモノマーの使用量が水酸基
を有するフッ素樹脂の水酸基価が固形分換算で３０〜７
０■ＫＯＨ／ｇの範囲となる量であることも好ましい、
また、硬化剤がアミノプラスト、ポリイソシアネート、
ブロックポリイソシアネート、多塩基酸、多塩基酸無水
物、ポリエポキシ化合物、エポキシ基又はイソシアネー
ト基を含有するシランカンブリング剤から成る群から選
ばれる少なくとも１つであることも好ましい。In order to solve the above-mentioned problems, the present invention provides a curable fluorine resin containing (a) a fluororesin having a hydroxyl group, (b) a curing agent, and (c) a fine silica powder surface-treated with silicone oil. The company provides resin paints. At this time, it is also preferable that the particle size of the silica fine powder surface-treated with silicone oil is in the range of 5 to 300 μm, and the fluororesin having a hydroxyl group is a fluorine-containing vinyl monomer, a copolymerizable vinyl monomer having a hydroxyl group, and other copolymerizable vinyl monomers. It is a copolymer obtained by copolymerizing a polymerizable vinyl monomer consisting of a polymerizable vinyl monomer, and the amount of copolymerizable vinyl monomer having a hydroxyl group used is such that the hydroxyl value of the fluororesin having a hydroxyl group is 30 in terms of solid content. ~7
It is also preferable that the amount is in the range of 0 KOH/g.
In addition, the curing agent is aminoplast, polyisocyanate,
It is also preferably at least one selected from the group consisting of blocked polyisocyanates, polybasic acids, polybasic acid anhydrides, polyepoxy compounds, and silane cambling agents containing epoxy groups or isocyanate groups.
次に本発明の詳細な説明する。Next, the present invention will be explained in detail.
本発明で使用する水酸基を有するフッ素樹脂は例えば、
含フツ素ビニルモノマーと水酸基を有する共重合性ビニ
ルモノマーと他の共重合可能なビニルモノマーヲ含有ス
る重合性ビニルモノマーを、ラジカル重合開始剤を用い
て、塊状重合、溶液重合、乳化重合法等の重合方法で重
合させることによって製造することができる。The fluororesin having a hydroxyl group used in the present invention is, for example,
A fluorine-containing vinyl monomer, a copolymerizable vinyl monomer having a hydroxyl group, and a polymerizable vinyl monomer containing other copolymerizable vinyl monomers are subjected to bulk polymerization, solution polymerization, and emulsion polymerization using a radical polymerization initiator. It can be produced by polymerization using a polymerization method such as
含フツ素ビニルモノマーとしては、例えば、フン化ヒニ
ル、フッ化ビニリデン、トリフルオロエチレン、テトラ
フルオロエチレン、プロモトリフルオロエチレン、クロ
ロトリフルオロエチレン、ペンタフルオロプロピレン、
ヘキサフルオロプロピレン、（バー）フルオロアルキル
トリフルオロビニルエーテル（但し、（バー）フルオロ
アルキル基の炭素原子数は、１〜１８の整数である。）
等が挙げられる。Examples of fluorine-containing vinyl monomers include hinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, promotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene,
Hexafluoropropylene, (bar)fluoroalkyl trifluorovinyl ether (however, the number of carbon atoms in the (bar)fluoroalkyl group is an integer from 1 to 18).
etc.
含フツ素ビニルモノマーの使用量は、重合性ビニルモノ
マーの１０〜９０重量％の範囲が好ましく、２０〜８５
重量％の範囲が特に好ましい。The amount of the fluorine-containing vinyl monomer used is preferably in the range of 10 to 90% by weight, and 20 to 85% by weight of the polymerizable vinyl monomer.
A range of % by weight is particularly preferred.
水酸基を有する共重合性ビニルモノマーとしては、例え
ば、ヒドロキシエチルビニルエーテル、ヒドロキシプロ
ピルビニルエーテル、ヒドロキシブチルビニルエーテル
の如きヒドロキシアルキルビニルエーテル；２−ヒドロ
キシエチル（メタ）アクリレート、２−ヒドロキシプロ
ピルアクリレートの如きヒドロキシアルキル（メタ）ア
クリレート等が挙げられる。Examples of the copolymerizable vinyl monomer having a hydroxyl group include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, and hydroxybutyl vinyl ether; ) acrylate, etc.
水酸基を有する共重合性ビニルモノマーの使用量は、水
酸基を有するフッ素樹脂の水酸基価が固形分換算で３０
〜７０ ｎｖＫｏ）！／ｇの範囲となる量が好ましい。The amount of the copolymerizable vinyl monomer having a hydroxyl group to be used is such that the hydroxyl value of the fluororesin having a hydroxyl group is 30 in terms of solid content.
~70 nvKo)! An amount in the range of /g is preferred.
他の共重合可能なビニルモノマーとしては、例えば、酢
酸ビニル、プロピオン酸ビニル、酪酸ビニル、ピバリン
酸ビニル、カプロン酸ビニル、カプリン酸ビニル、カプ
リル酸ビニル、バーサティツク酸ビニル、ラウリル酸ビ
ニル、ステアリン酸ビニルの如き直鎖状又は分類状の脂
肪族カルボン酸のビニルエステル；ジクロヘキサンカル
ボン酸ビニルエステルの如き脂環式カルボン酸ビニルエ
ステル；安息香酸ビニルエステル、ｐ−ｔ−ブチル安息
香酸ビニルエステル、サリチル酸ビニルエステルの如き
芳香族カルボン酸ビニルエステル；グリシジルビニルエ
ーテル、グリシジルメタアクリレートの如きエポキシ基
を有するビニル七ツマー；アクリル酸、メタクリル酸、
マレイン酸、無水マレイン酸、イタコン酸、無水イタコ
ン酸、フマル酸、マレイン酸モノエチル、マレイン酸モ
ノブチル、フマル酸モノブチル、イタコン酸モノブチル
、アジピン酸モノビニル、セバシン酸モノビニル等のカ
ルボキシル基を含有するビニルモノマー；ジメチルアミ
ノエチルビニルエーテル、ジメチルアミノプロピルビニ
ルエーテル、Ｎ、Ｎ−ジメチルアミノプロピル（メタ）
アクリルアミド、ジメチルアミノエチル（メタ）アクリ
レートの如きアミノ基を含有するビニルモノマー；塩化
ビニル、塩化ビニリデンの如き、フッ素を除く含ハロゲ
ンビニルモノマー；スチレン、α−メチルスチレン、ビ
ニルトルエンの如き芳香族ビニルモノマー；メチル（メ
タ）アクリレート、エチル（メタ）アクリレート、ブチ
ル（メタ）アクリレート、シクロヘキシル（メタ）アク
リレート、β−ヒドロキシエチル（メタ）アクリレート
の如き（メタ）アクリル酸エステル； （メタ）アクリ
ロニトリル、（メタ）アクリルアミド、Ｎ−メチロール
（メタ）アクリルアミド等が挙げられる。Other copolymerizable vinyl monomers include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprate, vinyl caprylate, vinyl versatate, vinyl laurate, and vinyl stearate. Vinyl esters of linear or classified aliphatic carboxylic acids such as; alicyclic carboxylic acid vinyl esters such as dichlorohexane carboxylic acid vinyl ester; benzoic acid vinyl ester, pt-butylbenzoic acid vinyl ester, vinyl salicylate Aromatic carboxylic acid vinyl esters such as esters; vinyl septamers having epoxy groups such as glycidyl vinyl ether and glycidyl methacrylate; acrylic acid, methacrylic acid,
Carboxyl group-containing vinyl monomers such as maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, monoethyl maleate, monobutyl maleate, monobutyl fumarate, monobutyl itaconate, monovinyl adipate, monovinyl sebacate; Dimethylaminoethyl vinyl ether, dimethylaminopropyl vinyl ether, N,N-dimethylaminopropyl (meth)
Vinyl monomers containing amino groups such as acrylamide and dimethylaminoethyl (meth)acrylate; halogen-containing vinyl monomers excluding fluorine such as vinyl chloride and vinylidene chloride; aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene. ; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, β-hydroxyethyl (meth)acrylate; (meth)acrylonitrile, (meth) Examples include acrylamide, N-methylol (meth)acrylamide, and the like.
水酸基を有するフッ素樹脂の数平均分子量は、１ 、０
００〜３００，０００の範囲が好ましく 、５，０００
〜２００．０００の範囲が特に好ましい。The number average molecular weight of the fluororesin having hydroxyl groups is 1,0
The range is preferably from 00 to 300,000, and 5,000
A range of ˜200.000 is particularly preferred.
水酸基を有するフッ素樹脂の代表的な市販品としては、
例えば、大日本インキ化学工業■製の［フルオネートに
７００Ｊ、「フルオネートに７０１ Ｊ、旭硝子■製の
「ルミフロンＬＦ１００Ｊ、ｒルミフロンＬＦ２００Ｊ
、「ルミフロンＬＦ４００Ｊ、「ルミフロンＬＦ６０１
Ｊ、「ルミフロンＬＦ７００」等が挙げられる。Typical commercially available fluororesins with hydroxyl groups include:
For example, Fluonate 700J and Fluonate 701J manufactured by Dainippon Ink and Chemicals, Lumiflon LF100J and Lumiflon LF200J manufactured by Asahi Glass.
, ``Lumiflon LF400J, ``Lumiflon LF601
J, "Lumiflon LF700", etc.
水酸基を有するフッ素樹脂の使用量は、本発明のフッ素
樹脂塗料の固形分の２０〜７０重量％の範囲が好ましい
。The amount of the fluororesin having a hydroxyl group used is preferably in the range of 20 to 70% by weight of the solid content of the fluororesin paint of the present invention.
本発明で使用する硬化剤としては、例えば、アミノプラ
スト、ポリイソシアネート、ブロックポリイソシアネー
ト、多塩基酸、多塩基酸無水物、ポリエポキシ化合物、
エポキシ基又はイソシアネート基含有シランカップリン
グ剤等を挙げることができる。Examples of the curing agent used in the present invention include aminoplast, polyisocyanate, block polyisocyanate, polybasic acid, polybasic acid anhydride, polyepoxy compound,
Examples include epoxy group- or isocyanate group-containing silane coupling agents.
アミノブラストとしては、例えば、メラミン、采素、ア
セトグアナミン、ベンゾグアナミン、スピログアナミン
等の如きアミノ基含有化合物と、ホルムアルデヒド、ア
セトアルデヒド、グリオキザールの如きアルデヒド基含
有化合物とを反応させて得られる縮合物、又は、これら
の縮合物とアルコールとを反応させて得られるエーテル
化物が挙げられる６、特に、フッ素樹脂との相溶性の観
点から、メチルエーテル化メチロールメラミンの使用が
望ましい。Examples of aminoblasts include condensates obtained by reacting amino group-containing compounds such as melamine, phosphorus, acetoguanamine, benzoguanamine, and spiroguanamine with aldehyde group-containing compounds such as formaldehyde, acetaldehyde, and glyoxal; , and etherified products obtained by reacting these condensates with alcohols6. In particular, from the viewpoint of compatibility with fluororesins, it is desirable to use methyl etherified methylolmelamine.
前記メチルエーテル化メチロールメラミンの代表的な市
販品としては、大日本インキ化学工業■製の「スーパー
ベッカミンＬ１０５Ｊ、三井東圧化学■製の「サイメル
３０３」、「サイメル３７０」、三相ケミカル■製の［
ニカラソクＭＷ２４ＸＪ等が挙げられる。Typical commercially available products of the methyl etherified methylol melamine include "Super Beckamine L105J" manufactured by Dainippon Ink and Chemicals, "Cymel 303" and "Cymel 370" manufactured by Mitsui Toatsu Chemical, and Three Phase Chemical ■. Manufactured by [
Examples include Nikarasoku MW24XJ.
ポリイソシアネートとしては、例えば、ヘキサメチレン
ジイソシアネート、トリメチルへキサメチレンジイソシ
アネートの如き脂肪族ジイソシアネート類；キシレンジ
イソシアネート、イソホロンジイソシアネートの如き環
状脂肪族ジイソシアネート類；トリレンジイソシアネー
）、４．４’−ジフェニルメタンジイソシアネートの如
き芳香族ジイソシアネート類などの有機ジイソシアネー
ト、又はこれら有機ジイソシアネートと、多価アルコー
ル、低分子ポリエステル樹脂又は水などとの付加物、有
機ジイソシアネート同士の重合体やイソシアネート・ビ
ウレット体等が挙げられる。Examples of the polyisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as xylene diisocyanate and isophorone diisocyanate; Examples include organic diisocyanates such as aromatic diisocyanates, adducts of these organic diisocyanates with polyhydric alcohols, low-molecular polyester resins, water, etc., polymers of organic diisocyanates, and isocyanate biuret forms.
前記ポリイソシアネートの代表的な市販品としては、例
えば、大日本インキ化学工業■製の「バーノックＤＮ−
９５０Ｊ、［パーノックＤＮ−９８０」、武田薬品工業
■製の［タケネートＤ１４ＯＮＪ、「タケネートＤ１７
０Ｊ、日本ポリウレタン工業＠製の「コロ２−トＨＬＪ
、ｒコロネートＥＨ」等が挙げられる。As a typical commercial product of the polyisocyanate, for example, "Burnock DN-" manufactured by Dainippon Ink and Chemicals
950J, [Parnock DN-980], [Takenate D14ONJ, "Takenate D17" manufactured by Takeda Pharmaceutical Company Ltd.
0J, "Koro 2-to HLJ" manufactured by Nippon Polyurethane Industry @
, rCoronate EH", etc.
ブロックポリイソシアネートとしては、前記ポリイソシ
アネートを公知のブロック化剤と反応させて得られたも
のが挙げられる。Examples of the blocked polyisocyanate include those obtained by reacting the above polyisocyanate with a known blocking agent.
多塩基酸としては、例えば−分子中に２個以上のカルボ
キシル基を有するアクリル樹脂もしくはポリエステル樹
脂、又は、ピロメリット酸、トリメリット酸等が挙げら
れる。Examples of polybasic acids include acrylic resins or polyester resins having two or more carboxyl groups in the molecule, pyromellitic acid, trimellitic acid, and the like.
多塩基酸無水物としては、例えば、−分子中に２個以上
の酸無水基を有するアクリル樹脂、無水トリメリット酸
、無水ピロメリット酸等が挙げられる。Examples of polybasic acid anhydrides include acrylic resins having two or more acid anhydride groups in the molecule, trimellitic anhydride, pyromellitic anhydride, and the like.
ポリエポキシ化合物としては、例えば、エチレングリコ
ール、グリセリン、ペンタエリスリトール、ソルビトー
ルの如き多価アルコールのポリグリシジルエーテル、−
分子中に２個以上のエポキシ基を存するアクリル樹脂等
が挙げられる。Examples of polyepoxy compounds include polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, glycerin, pentaerythritol, and sorbitol;
Examples include acrylic resins having two or more epoxy groups in the molecule.
硬化剤の使用量は、水酸基を有するフッ素樹脂の２〜５
０重量％の範囲が好ましい。The amount of curing agent used is 2 to 5 of the fluororesin having hydroxyl groups.
A range of 0% by weight is preferred.
硬化剤としてアミノプラスト、ポリイソシアネート又は
ブロックポリイソシアネートを用いる場合には、硬化触
媒を配合することができる。When using aminoplast, polyisocyanate or block polyisocyanate as a curing agent, a curing catalyst can be blended.
硬化剤がアミノプラストである場合の硬化触媒としては
、例えば、り−）ルエンスルホン酸、リン酸、リン酸の
モノアルキルエステル、リン酸のジアルキルエステル、
ジノニルナフタレンジスルホン酸、ドデシルベンゼンス
ルホン酸、又は、これらの化合物の有機アミンブロック
化物等が挙げられる。When the curing agent is an aminoplast, examples of the curing catalyst include ly-)luenesulfonic acid, phosphoric acid, monoalkyl ester of phosphoric acid, dialkyl ester of phosphoric acid,
Examples include dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid, and organic amine-blocked products of these compounds.
硬化剤がポリイソシアネート又はブロックポリイソシア
ネートである場合の硬化触媒としては、例えば、ジプチ
ル錫ジアセテート、ジブチル錫ジオクテート、ジブチル
錫シラウリレート、トリエチルアミン、ジメチルアミノ
エタノール等が挙げられる。Examples of the curing catalyst when the curing agent is polyisocyanate or block polyisocyanate include diptyltin diacetate, dibutyltin dioctate, dibutyltin silaurylate, triethylamine, dimethylaminoethanol, and the like.
本発明のフッ素樹脂塗料は、硬化剤として遊離のイソシ
アネート基を有する化合物を使用する場合等には常温硬
化性二液型塗料として、その他のイソシアネート基をブ
ロックしたもの等の場合には熱硬化性−成型塗料として
使用できる。The fluororesin paint of the present invention is a two-component paint that cures at room temperature when a compound having free isocyanate groups is used as a curing agent, and a thermosetting two-component paint when other isocyanate groups are blocked. -Can be used as a molding paint.
本発明で使用するシリコンオイルで表面処理したシリカ
微粉末は粒径が５〜３００μ−の範囲にあり、特に均一
な型子地模様を得るために、１０〜１００μ鋼が好まし
い。表面処理の仕方としては多孔質のシリカ微粉末をシ
リコンオイル中に混入し、攪拌機で攪拌する方法がある
。The particle size of the silica fine powder surface-treated with silicone oil used in the present invention is in the range of 5 to 300 .mu.m, and in particular, 10 to 100 .mu.m steel is preferred in order to obtain a uniform mold pattern. One method of surface treatment is to mix porous silica fine powder into silicone oil and stir it with a stirrer.
フッ素樹脂塗料を用いた塗膜の膜厚は、通常２０〜７０
μｍの範囲にあるので、シリカ微粉末が１０μｍより小
さい場合、シリカ微粉末が塗膜中に埋れてしまい型子地
模様を得ることが困難になる傾向にあり、１００μｍよ
り大きい場合、フッ素樹脂塗料中にシリカ微粉末を均一
に分散しにくくなる傾向があり、又、塗膜表面にシリカ
微粉末が突出し、塗膜に亀裂が発生したり、シリカ微粉
末が塗膜から脱落し易くなる傾向にある。The film thickness of the coating film using fluororesin paint is usually 20 to 70 mm.
If the silica fine powder is smaller than 10 μm, it will tend to be buried in the coating film and it will be difficult to obtain a patterned pattern.If it is larger than 100 μm, the fluororesin paint It tends to be difficult to uniformly disperse the fine silica powder in the paint, and the fine silica powder tends to protrude on the surface of the paint film, causing cracks in the paint film, and the fine silica powder tends to fall off from the paint film. be.
シリカ微粉末を表面処理するためのシリコンオイルは、
ジメチルモノ又はジクロロシランの加水分解物の縮重合
体であって、例えばジメチルシリコンオイルが好ましく
、特に重合度の高いジメチルシリコンオイルを使用した
場合に、型子地模様が出やすい傾向にあるので特に好ま
しい。Silicone oil for surface treatment of silica fine powder is
A condensation polymer of a hydrolyzate of dimethyl mono or dichlorosilane, for example, dimethyl silicone oil is preferable, especially when dimethyl silicone oil with a high degree of polymerization is used, since it tends to cause patterns on the mold surface. preferable.
シリコンオイルで表面処理したシリカ微粉末の使用量は
、本発明のフッ素樹脂塗料の固形分の１０〜５０重景％
の間外が好ましい。該シリカ微粉末の使用量が１０重量
％より少ない場合、シリカ微粉末は均一に分散している
にもかかわらず、その大部分が塗膜中に埋没してしまい
、型子地模様を得ることは困難な傾向にあり、５０重量
％より多い場合、塗膜に亀裂が発生し、塗膜自体が非常
に跪くなる傾向にある。The amount of silica fine powder surface-treated with silicone oil used is 10 to 50% of the solid content of the fluororesin paint of the present invention.
Preferably between. If the amount of the silica fine powder used is less than 10% by weight, most of the silica fine powder will be buried in the coating film even though it is uniformly dispersed, resulting in a mold pattern. If the amount is more than 50% by weight, cracks will occur in the coating film, and the coating film itself will tend to be very weak.
本発明で使用するシリコンオイルで表面処理した代表的
な市販品としては、例えば、トーレ・シリコーン■製の
［トレフィルＦ−２００Ｊ、「トレフィルＦ−２０１Ｊ
、「トレフィルＦ−２０２」、「トレフィルＦ−２０３
４、「トレフィルＦ−２５０Ｊ、「トレフィルＦ−４０
０Ｊ等が挙げられる。Typical commercially available products surface-treated with silicone oil used in the present invention include, for example, [Torefil F-200J, "Torefill F-201J" manufactured by Toray Silicone ■.
, “Trefil F-202”, “Trefill F-203”
4. ``Trefil F-250J, ``Trefil F-40
0J etc. are mentioned.
本発明のフッ素樹脂塗料を得るためには、上記した水酸
基を有するフッ素樹脂と、必要に応じて硬化剤及び着色
剤とをサンドミル、ボールミル等の分散混合機で有機溶
剤中に分散又は、溶解させ、その後、上記シリコンオイ
ルで表面処理したシリカ微粉末を添加、分散させればよ
い、常温硬化性二液型塗料を得ろ場合には、硬化剤は塗
装置前に分散又は溶解させればよい、不揮発分濃度は、
塗料全量に対し、３０〜７５重量％の範囲が好ましく、
３５〜７０重量％の範囲が特に好ましい。In order to obtain the fluororesin paint of the present invention, the above-mentioned fluororesin having a hydroxyl group and, if necessary, a curing agent and a coloring agent are dispersed or dissolved in an organic solvent using a dispersion mixer such as a sand mill or a ball mill. Then, fine silica powder surface-treated with the above-mentioned silicone oil may be added and dispersed.If a two-component paint curable at room temperature is to be obtained, the curing agent may be dispersed or dissolved before coating. The nonvolatile concentration is
It is preferably in the range of 30 to 75% by weight based on the total amount of the paint,
A range of 35 to 70% by weight is particularly preferred.
本発明のフン素樹脂塗料を塗装する前に、耐蝕性及び基
材との密着性等を補うために、先ず、基材にブライマー
塗料を塗装することが一般的になされている。ブライマ
ー塗料の樹脂成分としては、例えば、アルキッド樹脂、
エポキシ樹脂、アクリル樹脂等が挙げられるが、基材と
の密着性の向上をはかり、また、耐蝕性を改善するため
に、アルキッド樹脂としては、エポキシ変性アルキッド
樹脂、フェノール変性アルキッド樹脂、アクリル変性ア
ルキッド樹脂を用いることが好ましい。また、エポキシ
樹脂又はアクリル樹脂を用いる場合には、硬化剤と併用
することが好ましい。Before applying the fluorine resin paint of the present invention, it is common practice to first apply a brimer paint to the base material in order to improve corrosion resistance and adhesion to the base material. Examples of the resin components of the brimer paint include alkyd resin,
Examples of alkyd resins include epoxy resins and acrylic resins, but in order to improve adhesion to the base material and improve corrosion resistance, alkyd resins include epoxy-modified alkyd resins, phenol-modified alkyd resins, acrylic-modified alkyd resins, etc. Preferably, resin is used. Moreover, when using an epoxy resin or an acrylic resin, it is preferable to use it together with a curing agent.
ブライマー塗料に用いるエポキシ樹脂の硬化剤としては
、例えば、アミノプラスト、ポリイソシアネート、ブロ
ックポリイソシアネート、ポリアミン等が挙げられる。Examples of curing agents for epoxy resins used in brimer paints include aminoplasts, polyisocyanates, block polyisocyanates, and polyamines.
ブライマー塗料に用いるアクリル樹脂の硬化剤としては
、例えば、アミノプラスト、ポリイソシアネート、ブロ
ックポリイソシアネート等が挙げられる。Examples of the curing agent for the acrylic resin used in the brimer paint include aminoplast, polyisocyanate, block polyisocyanate, and the like.
ブライマー塗料に用いる顔料成分としては、基材の種類
により異なるが、基材が鉄材又は亜鉛メッキ鋼板である
場合には、鉛丹、シアナミド鉛の如き鉛系顔料；クロム
酸亜鉛、クロム酸ストロンチウムの如きクロム酸塩系顔
料等の防錆顔料が好ましい。Pigment components used in brimer paints vary depending on the type of base material, but if the base material is iron or galvanized steel, lead-based pigments such as red lead and cyanamide lead; zinc chromate and strontium chromate are used. Rust-preventive pigments such as chromate pigments are preferred.
ブライマー塗料の組成は、上記樹脂１０〜６０重量％、
顔料０〜５０重量％及び溶剤１０〜４０重量％の範囲が
好ましい。The composition of the brimer paint is 10 to 60% by weight of the above resin,
A range of 0 to 50% by weight of pigment and 10 to 40% by weight of solvent is preferred.
ブライマー塗料は刷毛、羊毛ローラー、スプレー、ロー
ルコータ−等で基材に塗布され、２０℃〜２００℃の温
度で４０秒〜７日間硬化させる。The brimer paint is applied to a substrate with a brush, wool roller, spray, roll coater, etc., and cured at a temperature of 20° C. to 200° C. for 40 seconds to 7 days.
乾燥塗膜厚は５〜８０μ−の範囲が適当である。The dry coating thickness is suitably in the range of 5 to 80 microns.
尚、塗膜性能に更なる向上をはかるため、同種または異
種のブライマー塗料を重ね塗りすることも行なわれてい
る。また、待に基材がアルミニウム材であり、その表面
に総クロム量で５０■／ｄ以上のクロム酸処理が施され
ている場合に限り、敢えてブライマー塗装を省くことも
できる。Incidentally, in order to further improve the coating film performance, it is also practiced to overcoat the same or different types of brimer paints. Moreover, only when the base material is an aluminum material and the surface thereof has been subjected to chromic acid treatment with a total chromium content of 50 μ/d or more, the brimer coating can be intentionally omitted.
本発明のフッ素樹脂塗料は、スプレー塗装、刷毛塗り、
ローラー塗装、ロールコータ−等の公知慣用の方法によ
って必要に応じてプライマー塗装を施された基体上に塗
膜を形成することができる。The fluororesin paint of the present invention can be applied by spray painting, brush painting,
A coating film can be formed on a substrate coated with a primer, if necessary, by a known and commonly used method such as roller coating or a roll coater.
遊離のイソシアネート基を有する化合物を用いた常温硬
化性の本発明のフッ素樹脂塗料における塗膜の硬化は、
室温で１日〜７日、又は、５０〜１２０℃で１・分〜６
０分間の条件で硬化し得る。Curing of the coating film in the room temperature curable fluororesin paint of the present invention using a compound having a free isocyanate group is as follows:
1 to 7 days at room temperature or 1 to 6 minutes at 50 to 120℃
It can be cured for 0 minutes.
その他のイソシアネート基をブロックした物等の硬化剤
を用いた本発明のフッ素樹脂塗料の塗膜の硬化は、６０
〜２５０℃で５秒間〜４０分間の条件で硬化し得る。The curing of the coating film of the fluororesin paint of the present invention using other curing agents such as those with blocked isocyanate groups is as follows:
It can be cured at ~250°C for 5 seconds to 40 minutes.
本発明のフッ素樹脂塗料は、建築物、瓦、プレコートメ
タル（ＰＣＭ）の如き外装用塗料；事務機器用エナメル
塗料又はクリヤー塗料；セラミック製品、ＦＲＰの表面
保護塗料等として使用できる。The fluororesin paint of the present invention can be used as an exterior paint for buildings, roof tiles, pre-coated metal (PCM), enamel paint or clear paint for office equipment, surface protection paint for ceramic products, FRP, etc.
次に本発明を実施例、比較例により説明するが本発明は
これらの例に何ら限定されるものではない、なお、以降
において部および％はすべで重量基準である。Next, the present invention will be explained with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way. Note that hereinafter all parts and percentages are based on weight.
実施例１
（本発明のフッ素樹脂塗料の調整）
（１）「フルオネートに７００ Ｊ ６
１．０部（大日本インキ化学工業側製の水酸基を有する
フッ素樹脂の５０％溶液）
（２）酸化チタン １５．５部（
３） キシレン ４．０部
（４） ｒ Ｉ−レ・フィルＦ−４００Ｊ
１０．０部（トーレ・シリコン■製のジメチルシリコ
ンオイルで表面処理したシリカ微粉末）
（５）酢酸ブチル ２．０部（
６） ジブチル錫シラウリレート０．０５％溶液０．
５部（７）「パーノックＤＮ９８０Ｊ
７．０部（大日本インキ化学工業■製のポリイソシ
アネート７５％溶液）
（１）〜（３）をボールミルにて十分に練肉した後、（
４）〜（６）の混合物を十分に攪拌しながら加え、更に
塗装置前に（７）を添加、攪拌することによって、硬化
性フッ素樹脂塗料を得た。Example 1 (Preparation of fluororesin paint of the present invention) (1) Fluonate 700 J 6
1.0 parts (50% solution of fluororesin having hydroxyl group manufactured by Dainippon Ink and Chemicals) (2) Titanium oxide 15.5 parts (
3) Xylene 4.0 parts (4) r I-Le Fill F-400J
10.0 parts (fine silica powder surface treated with dimethyl silicone oil manufactured by Toray Silicone) (5) Butyl acetate 2.0 parts (
6) Dibutyltinsilaurylate 0.05% solution 0.
Part 5 (7) “Parnock DN980J
7.0 parts (75% polyisocyanate solution manufactured by Dainippon Ink & Chemicals ■) (1) to (3) were thoroughly kneaded in a ball mill, and then (
A curable fluororesin paint was obtained by adding the mixture of 4) to (6) with sufficient stirring, and then adding and stirring (7) before coating.
実施例２
（ｌ）「ルミフロンＬＰ−２００４６１，０部（旭硝子
■製の水酸基を有するフッ素樹脂の６０％溶液）
（２）酸化チタン １５．５部（
３）キシレン ４．０部（４
） ｒ トレ・フンルＦ−４ＱＯＪ ＩＱ
、０部（トーレ・シリコン■製のジメチルシリコンオイ
ルを含浸あるいは部分的に反応させたシリカ微粉末）
（５）酢酸ブチル ２．０部（
６） ジブチル錫シラウリレート０．０５％溶液０．
５部（７）「コロネートＥＨＪ
７．０部（日本ポリウレタン工業■製のポリイソシアネ
ート）
上記（１１〜（７）を実施例１と同様に処理して、硬化
性フッ素樹脂塗料を得た。Example 2 (l) Lumiflon LP-200461, 0 parts (60% solution of fluororesin having hydroxyl group manufactured by Asahi Glass ■) (2) Titanium oxide 15.5 parts (
3) Xylene 4.0 parts (4
) r Tre Hunru F-4QOJ IQ
, 0 parts (fine silica powder impregnated with or partially reacted with dimethyl silicone oil manufactured by Toray Silicone) (5) Butyl acetate 2.0 parts (
6) Dibutyltinsilaurylate 0.05% solution 0.
Part 5 (7) “Coronate EHJ
7.0 parts (polyisocyanate manufactured by Nippon Polyurethane Industry ■) The above (11 to (7)) were treated in the same manner as in Example 1 to obtain a curable fluororesin paint.
比較例１ （汎用閉料のみを使用した高光沢フッ素樹脂
塗料）
実施例１において、「トレ・フィルＦ−４００Ｊを添加
しないこと以外は、実施例１と同様にして、硬化性フッ
素樹脂塗料を得た。Comparative Example 1 (High-gloss fluororesin paint using only a general-purpose sealant) In Example 1, a curable fluororesin paint was applied in the same manner as in Example 1, except that ``Toray Fil F-400J'' was not added. Obtained.
比較例２（シリカ添加低光沢フッ素樹脂塗料）実施例１
において、［トレ・フィルＦ−４００Ｊに代えて「サイ
ロイド＃４０４Ｊ（富士デビソン化学■製無水シリカ）
２．５部を使用した以外は、実施例１と同様にして、硬
化性フッ素樹脂塗料を得た。Comparative Example 2 (Silica-added low gloss fluororesin paint) Example 1
[In place of Tore Fill F-400J, "Thyroid #404J (anhydrous silica manufactured by Fuji Davison Chemical ■)"
A curable fluororesin paint was obtained in the same manner as in Example 1, except that 2.5 parts were used.
（プライマー塗料の調製）
［エピクロン１０５０−７０ＸＪ （大日本インキ化
学工業■製エポキシ樹脂７０％溶液）２０部に酸化チタ
ン１８部を加えて分散させた後、「ランカマイｌ’ＴＤ
Ｑ６６Ｊ （大日本インキ化学工業■製ポリアミド樹
脂）１１部とブチルセロソルブ６部を加え、攪拌するこ
とによって、ブライマー塗料を得た。(Preparation of primer paint) After adding 18 parts of titanium oxide to 20 parts of Epiclon 1050-70XJ (70% epoxy resin solution manufactured by Dainippon Ink & Chemicals) and dispersing it,
A brimer paint was obtained by adding and stirring 11 parts of Q66J (polyamide resin manufactured by Dainippon Ink & Chemicals) and 6 parts of butyl cellosolve.
（試験用塗装板の作成）
アルミニウム板ＣＪＩＳ Ａｌ １００ Ｘ）を脱脂液
（日本バーカライジング社１！［ファインクリーナー３
１５ｊ）に１０分間浸漬した後、乾燥した。(Creation of painted board for test) Aluminum board CJIS Al 100
15j) for 10 minutes and then dried.
次いで、脱脂したアルミニウム板を化成処理液（日本パ
ーカライジング社製「ボンデラント７１３Ｊ）に２分間
浸漬した後、乾燥した。化成処理を施したアルミニウム
板に、上記ブライマー塗料をエアスプレーにて乾燥膜厚
が５μｍとなるように塗装し、常温（２０℃）にて４８
時間乾燥させた。Next, the degreased aluminum plate was immersed in a chemical conversion treatment solution (Bonderant 713J, manufactured by Nippon Parkerizing Co., Ltd.) for 2 minutes, and then dried. Painted to a thickness of 5μm and 48cm thick at room temperature (20℃)
Let dry for an hour.
このプライマーを施したアルミニウム板に、各実施例及
び各比較例で得た各硬化性フッ素樹脂塗料をエアスプレ
ーにて乾燥膜厚が３０μ−となるように塗装し、常温（
２０℃）にて７時間乾燥させて試験用塗装板を各々得た
。Each of the curable fluororesin paints obtained in each Example and each Comparative Example was applied to the aluminum plate coated with this primer using air spray so that the dry film thickness was 30μ.
After drying at 20° C. for 7 hours, coated test plates were obtained.
（試験用塗装板の評価） （１）外観 塗膜の風合いを観察し、型子地模様性をみた。(Evaluation of test coated board) (1) Appearance The texture of the paint film was observed and the texture of the mold pattern was examined.
（２）耐候性試験
上記試験用塗装板の塗膜に、ＡＳＴＭ （米国材料試験
協会）Ｇ２３の試験規格に準拠した装置を用いて、促進
耐候試験を５００時間行なった後、光沢保持率及び色差
を求めた。(2) Weather resistance test After conducting an accelerated weather resistance test for 500 hours on the coating film of the test coated board using an apparatus compliant with ASTM (American Society for Testing and Materials) G23 test standards, the gloss retention rate and color difference were evaluated. I asked for
（３）耐光性試験
上記試験用塗装板の塗膜に、東芝製殺菌ランプを用い、
１５０の距離から紫外線を１，０００時間照射した後、
光沢保持率及び色差を求めた。(3) Light resistance test A Toshiba germicidal lamp was used on the coating film of the above test coated board.
After irradiating with ultraviolet rays for 1,000 hours from a distance of 150,
Gloss retention and color difference were determined.
〔光沢保持率（ＯＲ））
ＪＩＳ−Ｋ ５４００の試験規格に準拠して、６０”鏡
面光沢度を促進耐候試験又は紫外線照射試験の前後で測
定し、試験前の値に対する試験後の値を百分率で表わ′
したものである。[Gloss retention rate (OR)] In accordance with the JIS-K 5400 test standard, the 60" specular gloss was measured before and after the accelerated weathering test or ultraviolet irradiation test, and the value after the test was expressed as a percentage of the value before the test. It is expressed as
This is what I did.
〔色差（ΔＥ））
ＪＩＳ−２８７２２の試験規格に準拠する光学条件によ
り、促進耐候試験又は紫外線照射試験の前後で測定し、
ハンターの色差式により、色差（ΔＥ）を求めた。[Color difference (ΔE)] Measured before and after accelerated weathering test or ultraviolet irradiation test under optical conditions in accordance with JIS-28722 test standard,
Color difference (ΔE) was determined using Hunter's color difference formula.
上記試験方法ｆｉｌ〜（３）に従って行なった試験結果
を表に示した。The test results conducted according to the above test method fil-(3) are shown in the table.
本発明のフッ素樹脂塗料から成る塗膜は、型子地模様の
風あいを具現し、その塗膜性能は現行塗料の低光沢品（
比較例２）の塗膜性能を遥かに上廻り、全艶品（比較例
１）の塗膜性能をも凌ぐものであることを示している。The coating film made of the fluororesin paint of the present invention embodies the texture of the stencil pattern, and its coating performance is superior to that of current paints with low gloss.
This shows that the coating performance far exceeds that of Comparative Example 2), and even that of the full-gloss product (Comparative Example 1).
本発明のフッ素樹脂塗料は、耐候性、耐蝕性、耐薬品性
及び可撓性等を損なわずに、梨子地ｇ４様に代表される
意匠性のある塗膜を形成することが出来る。これにより
、建築材のみならず、家具等に用いる金属化粧板の美観
を高め、家具等の意匠性を高め、その実用価値を増加さ
せることができる。The fluororesin paint of the present invention can form a decorative coating typified by Nashiji G4 without impairing weather resistance, corrosion resistance, chemical resistance, flexibility, etc. Thereby, it is possible to enhance the beauty of metal decorative boards used not only as building materials but also for furniture, etc., enhance the design of furniture, etc., and increase its practical value.
平成１年５月１６日May 16, 1999
Claims (5)
径が５〜３００μｍの範囲にある請求項１記載の硬化性
フッ素樹脂塗料。(2) The curable fluororesin paint according to claim 1, wherein the silica fine powder surface-treated with silicone oil has a particle size in the range of 5 to 300 μm.
マー、水酸基を有する共重合性ビニルモノマー及び他の
共重合可能なビニルモノマーから成る重合性ビニルモノ
マーを共重合させて得た共重合体である請求項１又は２
記載の硬化性フッ素樹脂塗料。(3) A claim that the fluororesin having a hydroxyl group is a copolymer obtained by copolymerizing a polymerizable vinyl monomer consisting of a fluorine-containing vinyl monomer, a copolymerizable vinyl monomer having a hydroxyl group, and another copolymerizable vinyl monomer. Item 1 or 2
Curable fluororesin paint as described.
が水酸基を有するフッ素樹脂の水酸基価が固形分換算で
３０〜７０ｍｇＫＯＨ／ｇの範囲となる量である請求項
１ないし３いずれかに記載の硬化性フッ素樹脂塗料。(4) The amount of the copolymerizable vinyl monomer having a hydroxyl group used is such that the hydroxyl value of the fluororesin having a hydroxyl group is in the range of 30 to 70 mgKOH/g in terms of solid content. Curable fluororesin paint.
ブロックポリイソシアネート、多塩基酸、多塩基酸無水
物、ポリエポキシ化合物、エポキシ基又はイソシアネー
ト基を含有するシランカップリング剤から成る群から選
ばれる少なくとも１つであることを特徴とする請求項１
ないし４いずれかに記載の硬化性フッ素樹脂塗料。(5) The curing agent is aminoplast, polyisocyanate,
Claim 1 characterized in that it is at least one selected from the group consisting of blocked polyisocyanates, polybasic acids, polybasic acid anhydrides, polyepoxy compounds, and silane coupling agents containing epoxy groups or isocyanate groups.
The curable fluororesin coating according to any one of 4 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12041689A JPH02300253A (en) | 1989-05-16 | 1989-05-16 | Curable fluorinated resin coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12041689A JPH02300253A (en) | 1989-05-16 | 1989-05-16 | Curable fluorinated resin coating material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02300253A true JPH02300253A (en) | 1990-12-12 |
Family
ID=14785679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12041689A Pending JPH02300253A (en) | 1989-05-16 | 1989-05-16 | Curable fluorinated resin coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02300253A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0805186A1 (en) * | 1995-10-13 | 1997-11-05 | Nof Corporation | Thermosetting composition, method of finish coating, and coated articles |
| US7175901B1 (en) * | 1999-01-14 | 2007-02-13 | Reflec Plc | Retroreflective inks |
| JP2007526366A (en) * | 2004-02-23 | 2007-09-13 | ライプニッツ−インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク | Abrasion and alkali resistant coatings or molded bodies having a low energy surface |
| JP2012214676A (en) * | 2011-03-31 | 2012-11-08 | Nisshin Steel Co Ltd | Coated metal plate and method of manufacturing the same |
-
1989
- 1989-05-16 JP JP12041689A patent/JPH02300253A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0805186A1 (en) * | 1995-10-13 | 1997-11-05 | Nof Corporation | Thermosetting composition, method of finish coating, and coated articles |
| EP0805186A4 (en) * | 1995-10-13 | 1998-12-09 | Nof Corp | Thermosetting composition, method of finish coating, and coated articles |
| US7175901B1 (en) * | 1999-01-14 | 2007-02-13 | Reflec Plc | Retroreflective inks |
| JP2007526366A (en) * | 2004-02-23 | 2007-09-13 | ライプニッツ−インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク | Abrasion and alkali resistant coatings or molded bodies having a low energy surface |
| US9371411B2 (en) | 2004-02-23 | 2016-06-21 | Leibniz-Institut Fuer Neue Materialien Gemeinnuetzige Gmbh | Abrasion-resistant and alkali-resistant coatings or moulded bodies having a low-energy surface |
| JP2012214676A (en) * | 2011-03-31 | 2012-11-08 | Nisshin Steel Co Ltd | Coated metal plate and method of manufacturing the same |
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