JPH08319448A - Coating resin composition - Google Patents
Coating resin compositionInfo
- Publication number
- JPH08319448A JPH08319448A JP12857895A JP12857895A JPH08319448A JP H08319448 A JPH08319448 A JP H08319448A JP 12857895 A JP12857895 A JP 12857895A JP 12857895 A JP12857895 A JP 12857895A JP H08319448 A JPH08319448 A JP H08319448A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- group
- composition
- curing agent
- 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
- 239000011342 resin composition Substances 0.000 title claims description 12
- 238000000576 coating method Methods 0.000 title description 44
- 239000011248 coating agent Substances 0.000 title description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 229910000077 silane Inorganic materials 0.000 claims abstract description 13
- 229920003180 amino resin Polymers 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 55
- -1 silane compound Chemical class 0.000 claims description 50
- 239000012948 isocyanate Substances 0.000 claims description 25
- 125000000524 functional group Chemical group 0.000 claims description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 239000003973 paint Substances 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 abstract description 12
- 239000000178 monomer Substances 0.000 abstract description 9
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 abstract description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 3
- 229920005989 resin Polymers 0.000 description 32
- 239000011347 resin Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 19
- 239000010408 film Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000006087 Silane Coupling Agent Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- 239000008096 xylene Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 125000000962 organic group Chemical group 0.000 description 10
- 239000008199 coating composition Substances 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 239000013638 trimer Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 3
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 229940093858 ethyl acetoacetate Drugs 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- XMHDLKFMJMNOAX-UHFFFAOYSA-N 2-methyl-3-(2-methylprop-2-enoxy)prop-1-ene Chemical compound CC(=C)COCC(C)=C XMHDLKFMJMNOAX-UHFFFAOYSA-N 0.000 description 2
- FKTLISWEAOSVBS-UHFFFAOYSA-N 2-prop-1-en-2-yloxyprop-1-ene Chemical compound CC(=C)OC(C)=C FKTLISWEAOSVBS-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011211 glass fiber reinforced concrete Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 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
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-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
- FLFWDKGWSOCXQK-UHFFFAOYSA-N 1-ethenoxycyclohexan-1-ol Chemical compound C=COC1(O)CCCCC1 FLFWDKGWSOCXQK-UHFFFAOYSA-N 0.000 description 1
- HKQYAHHRYZOXLI-UHFFFAOYSA-N 1-phenyl-1-trimethylsilylurea Chemical compound C[Si](C)(C)N(C(N)=O)C1=CC=CC=C1 HKQYAHHRYZOXLI-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- RZYHXKLKJRGJGP-UHFFFAOYSA-N 2,2,2-trifluoro-n,n-bis(trimethylsilyl)acetamide Chemical compound C[Si](C)(C)N([Si](C)(C)C)C(=O)C(F)(F)F RZYHXKLKJRGJGP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- IZLFSDDOEKWVLD-UHFFFAOYSA-N 2-chloro-1,1,3,4,4,5,6,6,6-nonafluorohex-1-ene Chemical compound FC(C(F)(F)F)C(C(C(=C(F)F)Cl)F)(F)F IZLFSDDOEKWVLD-UHFFFAOYSA-N 0.000 description 1
- YOWQWFMSQCOSBA-UHFFFAOYSA-N 2-methoxypropene Chemical compound COC(C)=C YOWQWFMSQCOSBA-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- OJPSFJLSZZTSDF-UHFFFAOYSA-N 3-ethoxyprop-1-ene Chemical compound CCOCC=C OJPSFJLSZZTSDF-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- JSDZSLGMRRSAHD-UHFFFAOYSA-N 3-methylbutan-2-ylcyclopropane Chemical compound CC(C)C(C)C1CC1 JSDZSLGMRRSAHD-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001448862 Croton Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- YKFRUJSEPGHZFJ-UHFFFAOYSA-N N-trimethylsilylimidazole Chemical compound C[Si](C)(C)N1C=CN=C1 YKFRUJSEPGHZFJ-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 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
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- PAJFATIYVLZNFC-UHFFFAOYSA-N chloromethyl(dimethyl)silicon Chemical compound C[Si](C)CCl PAJFATIYVLZNFC-UHFFFAOYSA-N 0.000 description 1
- SZZZMXFBEKWPBU-UHFFFAOYSA-N chloromethyl-ethenyl-dimethylsilane Chemical compound ClC[Si](C)(C)C=C SZZZMXFBEKWPBU-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 239000003822 epoxy resin Substances 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
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NUFVQEIPPHHQCK-UHFFFAOYSA-N ethenyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)C=C NUFVQEIPPHHQCK-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- LWFWUJCJKPUZLV-UHFFFAOYSA-N n-trimethylsilylacetamide Chemical compound CC(=O)N[Si](C)(C)C LWFWUJCJKPUZLV-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- CDXZRBLOGJXGTN-UHFFFAOYSA-N prop-2-enoxycyclohexane Chemical compound C=CCOC1CCCCC1 CDXZRBLOGJXGTN-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-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
- 238000005406 washing Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塗料用樹脂組成物とこ
れにより塗装された屋外物品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition and an outdoor article coated with the resin composition.
【０００２】[0002]
【従来の技術】従来より、金属、無機、プラスチック、
木材、紙、皮革、繊維などの製品は、その表面の保護、
意匠性および機能性の付与などの目的で塗装などの表面
被覆が行われており、塗料の開発も様々になされてきて
いる。2. Description of the Related Art Conventionally, metals, inorganics, plastics,
Products such as wood, paper, leather and textiles have surface protection,
Surface coating such as painting is performed for the purpose of imparting designability and functionality, and various paints have been developed.
【０００３】最近、耐候性に優れた塗料としてフッ素樹
脂塗料が多く使われてきている。このフッ素樹脂塗料
は、以前から広く使用されてきた種々の合成樹脂塗料に
比べ格段の耐候性を示す。しかし、表面につく汚れに対
する防汚性については、他の合成樹脂塗料の場合と同程
度であり、そのため、高機能商品として使用するには、
その改善が望まれている。Recently, fluororesin paints have been widely used as paints having excellent weather resistance. This fluororesin paint exhibits marked weather resistance as compared with various synthetic resin paints that have been widely used for a long time. However, the antifouling property against stains on the surface is similar to that of other synthetic resin paints, and therefore, to use it as a high-performance product,
The improvement is desired.
【０００４】[0004]
【発明が解決しようとする課題】従来、塗装物品の表面
の汚れを解決しようとして、多フッ素化カーボン鎖と親
水基を有する重合体を添加した塗料用組成物が提案され
ている（例えば、特開平１−１９８６５３号公報参
照）。しかし、この提案の塗料用組成物は、雨水による
斑点上の汚れの発生を防止する効果は認められるが、屋
外物品例えば建築物の窓枠の下などの雨水が集まって流
れる部分に発生するすじ状の汚れ（以下、雨すじ汚れと
いう）を防止する点については充分なものではなかっ
た。In the past, coating compositions containing a polyfluorinated carbon chain and a polymer having a hydrophilic group have been proposed in an attempt to solve the stain on the surface of a coated article (for example, a special method). See Kaihei 1-18653). However, the coating composition of this proposal has an effect of preventing the generation of stains on spots due to rainwater, but streaks are generated in a portion where rainwater gathers and flows, such as an outdoor article, for example, under a window frame of a building. It was not sufficient to prevent such stains (hereinafter referred to as rain streak stains).
【０００５】また、ＷＯ９４／６８７０により、オルガ
ノシリケートおよび／またはその縮合物を配合した塗料
組成物が知られているが、雨すじ汚れを防止する点につ
いては必ずしも充分なものではなかった。Further, a coating composition containing an organosilicate and / or a condensate thereof is known from WO94 / 6870, but it is not always sufficient in terms of preventing rain streak stains.
【０００６】[0006]
【課題を解決するための手段】本発明は前述の課題を解
決しようとするものであり、数平均分子量が２，０００
〜９，０００、Ｔｇが４０℃以上および水酸基価が７８
〜２５０ｍｇＫＯＨ／ｇである官能基含有フッ素樹脂
（ａ）、官能基含有フッ素樹脂（ａ）を架橋し得る硬化
剤（ｂ）および明細書中で定義するシリカ分が４５％以
上の４官能加水分解性シラン化合物の多量体（ｃ）を含
み、（ａ）、（ｂ）および（ｃ）の割合が（ａ）１００
重量部に対して（ｂ）０．１〜１００重量部および
（ｃ）０．１〜１００重量部である塗料用樹脂組成物で
ある。The present invention is intended to solve the above-mentioned problems and has a number average molecular weight of 2,000.
~ 9,000, Tg of 40 ° C or higher and hydroxyl value of 78
˜250 mgKOH / g functional group-containing fluororesin (a), curing agent (b) capable of crosslinking functional group-containing fluororesin (a), and tetrafunctional hydrolysis having a silica content as defined in the specification of 45% or more. Containing a multimer (c) of a crystalline silane compound, wherein the ratio of (a), (b) and (c) is (a) 100.
The resin composition for coating is (b) 0.1 to 100 parts by weight and (c) 0.1 to 100 parts by weight with respect to parts by weight.
【０００７】本発明の組成物を特に屋外物品の雨すじ汚
れが発生しやすい箇所へ塗装することによりきわめて良
好に長期間雨すじ汚れの発生を防止できる。By coating the composition of the present invention on a portion of an outdoor article where rain streak stains are likely to occur, it is possible to prevent rain streak stains from occurring for a very long period of time.
【０００８】官能基含有フッ素樹脂（ａ）（以下単に樹
脂（ａ）という）としては、特に限定されることなく広
範囲のものが使用でき、塗料用フッ素樹脂として知られ
るフルオロオレフィンの１種以上の重合体またはフルオ
ロオレフィンと他の共重合可能な単量体を共重合して得
られる共重合体からなる樹脂が、溶剤に対する溶解性、
塗膜の耐候性、塗装作業性等の点から好ましい。その
他、フッ化ビニリデンの重合体や共重合体からなる塗料
用フッ素樹脂など種々の溶媒溶解性の塗料用フッ素樹脂
を使用することができる。The functional group-containing fluororesin (a) (hereinafter simply referred to as "resin (a)") is not particularly limited and a wide range can be used, and one or more fluoroolefins known as fluororesins for coating materials can be used. Resin comprising a copolymer obtained by copolymerizing a polymer or fluoroolefin and another copolymerizable monomer, solubility in a solvent,
It is preferable from the viewpoints of weather resistance of the coating film and workability of coating. In addition, various solvent-soluble fluororesins for paints such as fluororesins for paints made of vinylidene fluoride polymers or copolymers can be used.
【０００９】フルオロオレフィンとしては、例えばテト
ラフルオロエチレン、クロロトリフルオロエチレン、ト
リフルオロエチレン、フッ化ビニリデン、ヘキサフルオ
ロプロピレン、ペンタフルオロプロピレン等の炭素数２
あるいは３のフルオロオレフィンが挙げられる。特にテ
トラフルオロエチレンとクロロトリフルオロエチレンが
好ましい。フルオロオレフィン系共重合体としては、フ
ッ化ビニリデン／テトラフルオロエチレン／ヘキサフル
オロプロピレン共重合体のようなフルオロオレフィン２
種以上の共重合体であってもよい。しかし、フルオロオ
レフィンとフルオロオレフィン以外の共重合可能な単量
体を共重合して得られる共重合体がより好ましい。As the fluoroolefin, for example, tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene, pentafluoropropylene and the like having 2 carbon atoms.
Alternatively, a fluoroolefin of 3 may be mentioned. Particularly, tetrafluoroethylene and chlorotrifluoroethylene are preferable. Fluoroolefin-based copolymers include fluoroolefins such as vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymers.
It may be a copolymer of two or more species. However, a copolymer obtained by copolymerizing a fluoroolefin and a copolymerizable monomer other than the fluoroolefin is more preferable.
【００１０】このフルオロオレフィンと共重合可能な単
量体としては、ビニルエーテル、ビニルエステル、アリ
ルエーテル、アリルエステル、イソプロペニルエーテ
ル、イソプロペニルエステル、メタリルエーテル、メタ
リルエステル、α−オレフィン、アクリル酸エステル、
メタクリル酸エステル等の単量体がある。これらの単量
体は２種以上を併用できる。As the monomer copolymerizable with the fluoroolefin, vinyl ether, vinyl ester, allyl ether, allyl ester, isopropenyl ether, isopropenyl ester, methallyl ether, methallyl ester, α-olefin, acrylic ester,
There are monomers such as methacrylic acid esters. Two or more kinds of these monomers can be used in combination.
【００１１】ここでビニルエーテルとしては、例えばエ
チルビニルエーテル、ブチルビニルエーテル、シクロヘ
キシルビニルエーテル、（フルオロアルキル）ビニルエ
ーテル、パーフルオロ（アルキルビニルエーテル）等の
アルキルビニルエーテルが好ましい。ビニルエステルと
しては、例えば分岐状のアルキル基を有する「ベオバ−
１０」（シェル化学製商品名）、ピバリン酸ビニル、バ
ーサチック酸ビニル、酪酸ビニル、酢酸ビニル等の脂肪
酸ビニルエステルが好ましい。The vinyl ether is preferably an alkyl vinyl ether such as ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, (fluoroalkyl) vinyl ether or perfluoro (alkyl vinyl ether). As the vinyl ester, for example, "Veovar having a branched alkyl group
10 "(trade name of Shell Chemical Co.), vinyl pivalate, vinyl versatate, vinyl butyrate, vinyl acetate and other fatty acid vinyl esters are preferred.
【００１２】さらにアリルエーテルとしては、エチルア
リルエーテル、シクロヘキシルアリルエーテル等のアル
キルアリルエーテルが好ましく、アリルエステルとして
は、プロピオン酸アリル、酢酸アリル等の脂肪酸アリル
エステルが好ましい。イソプロペニルエーテルとして
は、メチルイソプロペニルエーテル等のアルキルイソプ
ロペニルエーテルが好ましい。イソプロペニルエステ
ル、メタリルエーテル、メタリルエステルとしては、各
種の脂肪酸イソプロペニルエステル、アルキルメタリル
エーテル、脂肪酸メタリルエステルが好ましい。α−オ
レフィンとしては、エチレン、プロピレン、イソブチレ
ンなどが好ましい。Further, the allyl ether is preferably an alkyl allyl ether such as ethyl allyl ether or cyclohexyl allyl ether, and the allyl ester is preferably a fatty acid allyl ester such as allyl propionate or allyl acetate. As the isopropenyl ether, alkyl isopropenyl ether such as methyl isopropenyl ether is preferable. As the isopropenyl ester, methallyl ether and methallyl ester, various fatty acid isopropenyl ester, alkyl methallyl ether and fatty acid methallyl ester are preferable. As the α-olefin, ethylene, propylene, isobutylene and the like are preferable.
【００１３】フルオロオレフィンの共重合割合があまり
に少ないと、耐候性塗料として充分に優れた耐候性が発
揮されない。また、フルオロオレフィンの共重合割合が
あまりに多くなると、溶剤への溶解性等が低下するため
好ましくない。したがって、樹脂（ａ）としては、フル
オロオレフィンが３０〜７０モル％の割合、特には４０
〜６０モル％の割合、で共重合した共重合体からなる樹
脂であることが好ましい。If the copolymerization ratio of the fluoroolefin is too low, the weather resistance of the weather resistant coating will not be sufficiently excellent. Further, if the copolymerization ratio of the fluoroolefin becomes too large, the solubility in a solvent will decrease, which is not preferable. Therefore, as the resin (a), the proportion of fluoroolefin is 30 to 70 mol%, particularly 40
The resin is preferably a resin composed of a copolymer copolymerized at a ratio of 60 mol%.
【００１４】フルオロオレフィンと共重合可能な単量体
のうちでは、特にビニルエーテル、ビニルエステル、ア
リルエーテル、アリルエステルがフルオロオレフィンと
の共重合性に優れる点から好ましい。さらに、炭素数１
〜１０の直鎖状、分岐状あるいは脂環状のアルキル基を
有するアルキルビニルエーテル、脂肪酸ビニルエステ
ル、アルキルアリルエーテル、脂肪酸アリルエステルが
好ましい。Of the monomers copolymerizable with the fluoroolefin, vinyl ether, vinyl ester, allyl ether, and allyl ester are particularly preferable because of their excellent copolymerizability with the fluoroolefin. Furthermore, carbon number 1
Alkyl vinyl ether, fatty acid vinyl ester, alkyl allyl ether and fatty acid allyl ester having a linear, branched or alicyclic alkyl group of 10 are preferable.
【００１５】樹脂（ａ）は、硬化剤（ｂ）と架橋反応し
得る官能基を有するためにより強靭な塗膜が得られる。
樹脂（ａ）には、イソシアネート系硬化剤やアミノプラ
スト系硬化剤などと反応し得る水酸基が必須である。こ
の水酸基に起因する樹脂（ａ）の水酸基価は重要であ
り、その値を７８〜２５０ｍｇＫＯＨ／ｇとすることに
より、好ましくは１００〜１５０ｍｇＫＯＨ／ｇとする
ことにより長期間雨すじ汚れの発生を防止できる。Since the resin (a) has a functional group capable of undergoing a crosslinking reaction with the curing agent (b), a stronger coating film can be obtained.
A hydroxyl group capable of reacting with an isocyanate curing agent, an aminoplast curing agent, or the like is essential in the resin (a). The hydroxyl value of the resin (a) due to this hydroxyl group is important, and by setting the value to 78 to 250 mgKOH / g, preferably 100 to 150 mgKOH / g, it is possible to prevent the generation of rain streak stains for a long period of time. it can.
【００１６】樹脂（ａ）には、アミノ基、酸アミド基、
カルボン酸基などの水酸基以外の活性水素含有基、また
はエポキシ基、ハロゲン、二重結合などの官能基を、水
酸基以外に有していてもよい。The resin (a) includes an amino group, an acid amide group,
It may have an active hydrogen-containing group other than a hydroxyl group such as a carboxylic acid group or a functional group such as an epoxy group, a halogen or a double bond, in addition to the hydroxyl group.
【００１７】このような官能基の導入方法としては、官
能基を有する単量体例えば、ヒドロキシブチルビニルエ
ーテル、ヒドロキシブチルアリルエーテル、エチレング
リコールモノアリルエーテル、シクロヘキサンジオール
モノビニルエーテル、アクリル酸、メタクリル酸、クロ
トン酸、ウンデセン酸、グリシジルビニルエーテル、グ
リシジルアリルエーテルなどを共重合せしめる方法があ
る。As a method of introducing such a functional group, a monomer having a functional group such as hydroxybutyl vinyl ether, hydroxybutyl allyl ether, ethylene glycol monoallyl ether, cyclohexanediol monovinyl ether, acrylic acid, methacrylic acid, croton. There is a method of copolymerizing an acid, undecenoic acid, glycidyl vinyl ether, glycidyl allyl ether and the like.
【００１８】また、共重合体を変性せしめることにより
官能基を導入する方法、例えば、水酸基またはエポキシ
基に、無水コハク酸のような多塩基酸無水物を反応せし
めてカルボン酸基を導入する方法、イソシアネートアル
キルメタアクリレートなどを反応せしめて二重結合を導
入する方法なども適用できる。Further, a method of introducing a functional group by modifying the copolymer, for example, a method of introducing a carboxylic acid group by reacting a hydroxyl group or an epoxy group with a polybasic acid anhydride such as succinic anhydride. Alternatively, a method of reacting an isocyanate alkyl methacrylate or the like to introduce a double bond can be applied.
【００１９】官能基を有する共重合単位は、共重合体中
の全共重合単位に対して５〜２０モル％であることが好
ましい。The content of the copolymerized units having a functional group is preferably 5 to 20 mol% based on all the copolymerized units in the copolymer.
【００２０】樹脂（ａ）の数平均分子量およびＴｇ（ガ
ラス転移温度）は重要であり、数平均分子量を２，００
０〜９，０００、好ましくは３，０００〜８，０００と
することにより、Ｔｇを４０℃以上とすることにより長
期間雨すじ汚れの発生を防止できる。The number average molecular weight and Tg (glass transition temperature) of the resin (a) are important, and the number average molecular weight is 2,000.
By setting the Tg to 0 to 9,000, preferably 3,000 to 8,000, it is possible to prevent the generation of rain streak stains for a long period of time by setting the Tg to 40 ° C. or higher.
【００２１】こうした樹脂（ａ）としては、例えば商品
名ルミフロン（旭硝子）、セフラルコート（セントラル
硝子）、ザフロン（東亜合成）、ゼッフル（ダイキン工
業）、フルオネート（大日本インキ工業）、フローレン
（日本合成ゴム）、カイナー（アトケム）などとして市
販されているものを使用できる。Examples of such resin (a) include Lumiflon (Asahi Glass), Cefraralcoat (Central Glass), Zaflon (Toa Gosei), Zeffle (Daikin Industries), Fluoronate (Dainippon Ink Kogyo), and Floren (Nippon Synthetic Rubber). ), Kainer (Atochem) and the like which are commercially available can be used.
【００２２】硬化剤（ｂ）としては、樹脂（ａ）の官能
基と反応して樹脂（ａ）を架橋し得るものであれば特に
限定されることなく使用できる。例えば水酸基を有する
樹脂（ａ）に使用する硬化剤としては、例えばアミノプ
ラスト系硬化剤、イソシアネート系硬化剤、多塩基酸系
硬化剤、多価アミン系硬化剤などを挙げられる。このな
かで、アミノプラスト系硬化剤、イソシアネート系硬化
剤が好ましい。The curing agent (b) is not particularly limited as long as it can react with the functional group of the resin (a) to crosslink the resin (a). Examples of the curing agent used for the resin (a) having a hydroxyl group include aminoplast-based curing agents, isocyanate-based curing agents, polybasic acid-based curing agents, polyvalent amine-based curing agents, and the like. Of these, aminoplast-based curing agents and isocyanate-based curing agents are preferable.
【００２３】この硬化剤（ｂ）が樹脂（ａ）と架橋する
ことによって優れた物性を有する硬化塗膜を形成される
とともに、４官能加水分解性シラン化合物の多量体
（ｃ）（以下単に多量体（ｃ）という）と樹脂（ａ）と
の反応が抑制され、多量体（ｃ）が塗膜表面に配向し
て、雨すじ汚れの発生を防止する効果が顕著になるもの
と考えられる。By cross-linking the curing agent (b) with the resin (a), a cured coating film having excellent physical properties is formed, and at the same time, a multimer (c) of a tetrafunctional hydrolyzable silane compound (hereinafter simply referred to as a large amount). It is considered that the reaction between the body (c) and the resin (a) is suppressed, the polymer (c) is oriented on the surface of the coating film, and the effect of preventing the generation of rain streaks becomes remarkable.
【００２４】アミノプラスト系硬化剤としては、メチロ
ールメラミン類、メチロールグアナミン類、メチロール
尿素類などが使用できる。メチロールメラミン類として
は、ブチル化メチロールメラミン、メチル化メチロール
メラミン等の低級アルコールによりエーテル化されたメ
チロールメラミン、エポキシ変性メチロールメラミン等
を使用できる。メチロール尿素類としては、メチル化メ
チロール尿素、エチル化メチロール尿素等のアルキル化
メチロール尿素なども使用できる。アミノプラスト系硬
化剤を使用する場合は通常酸性触媒を使用し架橋反応を
促進する。As the aminoplast type curing agent, methylol melamines, methylol guanamines, methylol ureas and the like can be used. As the methylolmelamines, methylolmelamine etherified with a lower alcohol such as butylated methylolmelamine and methylated methylolmelamine, and epoxy-modified methylolmelamine can be used. As the methylolureas, alkylated methylolureas such as methylated methylolurea and ethylated methylolurea can be used. When an aminoplast-based curing agent is used, an acidic catalyst is usually used to accelerate the crosslinking reaction.
【００２５】イソシアネート系硬化剤としては多価イソ
シアネート化合物やそのブロック化物がある。多価イソ
シアネート化合物は、２以上のイソシアネート基を有す
る化合物であり、またその変性体や多量体からなる２以
上のイソシアネート基を有する化合物であってもよい。As the isocyanate-based curing agent, there are polyvalent isocyanate compounds and blocked products thereof. The polyvalent isocyanate compound is a compound having two or more isocyanate groups, and may be a compound having two or more isocyanate groups which is a modified product or a multimer thereof.
【００２６】多価イソシアネート化合物としては、エチ
レンジイソシアネート、プロピレンジイソシアネート、
テトラメチレンジイソシアナート、ヘキサメチレンジイ
ソシアナート、ヘキサメチレントリイソシアナート、リ
ジンジイソシアネートなどの脂肪族多価イソシアネート
化合物、イソホロンジイソシアナート、ジシクロヘキシ
ルメタンジイソシアネート、ジイソシアネートメチルシ
クロヘキサンなどの脂環族多価イソシアネート化合物、
およびｍ−キシリレンジイソシアネート、ｐ−キシリレ
ンジイソシアネートなどの無黄変性芳香族多価イソシア
ネート化合物が使用される。As the polyvalent isocyanate compound, ethylene diisocyanate, propylene diisocyanate,
Aliphatic polyisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, hexamethylene triisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, alicyclic polyvalent isocyanate compounds such as diisocyanate methylcyclohexane ,
And non-yellowing aromatic polyvalent isocyanate compounds such as m-xylylene diisocyanate and p-xylylene diisocyanate are used.
【００２７】多価イソシアネート化合物の変性体や多量
体としては、例えばウレタン変性体、ウレア変性体、イ
ソシアヌレート変性体、ビューレット変性体、アロファ
ネート変性体、カルボジイミド変性体などと呼ばれてい
るものがある。特に３量体であるイソシアヌレート変性
体やトリメチロールプロパンなどの多価アルコールとの
反応生成物であるウレタン変性体などが好ましい。Examples of modified polymers and polymers of polyvalent isocyanate compounds include those called urethane modified products, urea modified products, isocyanurate modified products, burette modified products, allophanate modified products, and carbodiimide modified products. is there. Particularly preferred are isocyanurate modified products which are trimers and urethane modified products which are reaction products with polyhydric alcohols such as trimethylolpropane.
【００２８】好ましい多価イソシアネート化合物として
は、ヘキサメチレンジイソシアナート、イソホロンジイ
ソシアナートなどの無黄変性イソシアネート類や、これ
らのブロック化物、多量化物などが挙げられる。Examples of preferable polyvalent isocyanate compounds include non-yellowing isocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and their blocked and polymerized products.
【００２９】ブロック化されていない多価イソシアナー
ト化合物を用いた場合、常温で樹脂（ａ）を架橋できる
ため現場施工が容易であるとともに、補修塗装をする場
合に有利である。ブロック化されたイソシアネート基を
有するイソシアネート系硬化剤は他の硬化剤と同様通常
は加熱硬化型の塗料組成物となる。多価イソシアナート
化合物を使用した場合、ジブチル錫ジラウレートなどの
公知の触媒の添加によって架橋反応を促進することもで
きる。When a non-blocked polyvalent isocyanate compound is used, the resin (a) can be crosslinked at room temperature, which facilitates on-site construction and is advantageous for repair coating. An isocyanate-based curing agent having a blocked isocyanate group is usually a heat-curable coating composition like other curing agents. When a polyvalent isocyanate compound is used, the crosslinking reaction can be promoted by adding a known catalyst such as dibutyltin dilaurate.
【００３０】また、多塩基酸としては、長鎖脂肪族ジカ
ルボン酸類、芳香族多価カルボン酸類などが有用であ
り、その酸無水物も有用である。As the polybasic acid, long-chain aliphatic dicarboxylic acids, aromatic polyvalent carboxylic acids and the like are useful, and their acid anhydrides are also useful.
【００３１】４官能加水分解性シラン化合物は４個の加
水分解性基がケイ素原子に直接結合した化合物である。
多量体（ｃ）はこの化合物を縮合により多量化したもの
である。The tetrafunctional hydrolyzable silane compound is a compound in which four hydrolyzable groups are directly bonded to a silicon atom.
The polymer (c) is a compound obtained by condensation of this compound.
【００３２】加水分解性基としては、アルコキシ基、ア
ルコキシアルコキシ基、アシルオキシ基、アリールオキ
シ基、アミノキシ基、アミド基、ケトオキシム基、イソ
シアネート基、ハロゲン原子等が例示される。好ましく
はアルコキシ基、アルコキシアルコキシ基等の１価アル
コールの水酸基の水素原子を除いた基である。特にアル
コキシ基が好ましく、その炭素数は４個以下、特に１〜
２個が好ましい。Examples of the hydrolyzable group include an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an aryloxy group, an aminoxy group, an amide group, a ketoxime group, an isocyanate group and a halogen atom. Preferred is a group obtained by removing a hydrogen atom from a hydroxyl group of a monohydric alcohol such as an alkoxy group or an alkoxyalkoxy group. Particularly preferred is an alkoxy group, which has 4 or less carbon atoms, particularly 1 to
Two is preferable.
【００３３】多量体（ｃ）は、塗料用樹脂組成物中でゲ
ル状生成物を生成しない多量化度のものである。ここ
で、多量化度とは４官能加水分解性シラン化合物の縮合
分子数を意味する。多量体には直鎖状、分枝状、環状、
網目状構造を持つものがあり、通常は直鎖状構造を持つ
ものまたは直鎖状構造を持つものに分枝状、環状、網目
状構造を持つものが含まれている混合物であると考えら
れる。本発明で用いる多量体（ｃ）はこれらの構造を持
つものをそれぞれ単独で使用してもよくあるいはこれら
の構造を持つものの混合物として使用してもよい。The multimer (c) has a degree of multimerization that does not form a gel-like product in the coating resin composition. Here, the degree of multimerization means the number of condensed molecules of a tetrafunctional hydrolyzable silane compound. Linear, branched, cyclic,
Some have a network structure, usually considered to be a linear structure or a mixture of linear structures containing branched, cyclic, or network structures. . As the multimer (c) used in the present invention, those having these structures may be used alone or as a mixture of those having these structures.
【００３４】好ましい多量体（ｃ）としては、テトラア
ルコキシシランの多量体が挙げられる。これを直鎖状構
造を持つものとして示せば、一般式ＲＯ（Ｓｉ（ＯＲ）
2 Ｏ）n Ｒで表される。Examples of preferable polymer (c) include tetraalkoxysilane polymers. If this is shown as having a linear structure, the general formula RO (Si (OR)
2 O) n R.
【００３５】一般式中、ｎは多量体の多量化度を表わ
す。通常入手できる多量体はｎが異なる多量体の混合物
であり、その多量化度は平均したｎで表される。好まし
いｎは２〜１０であり、特に２〜８が好ましい。ｎが１
のものは目的の雨すじ汚れの発生を防止する効果が充分
ではなく、ｎが大きいものはその粘度が大きくなりす
ぎ、塗料用樹脂組成物の調合、塗装が難しくなるため好
ましくない。In the general formula, n represents the degree of multimerization. The normally available multimers are mixtures of multimers with different n, and the degree of multimerization is represented by n averaged. Preferable n is 2 to 10, and 2 to 8 is particularly preferable. n is 1
Those having a large n do not have sufficient effect of preventing the generation of stains on rain streaks, and those having a large n have an excessively large viscosity, which makes it difficult to prepare and coat a resin composition for coating, which is not preferable.
【００３６】一般式中、Ｒとしては、メチル基、エチル
基、プロピル基、ブチル基等の低級アルキル基が例示さ
れる。アルコキシ基の加水分解性、縮合性等の面から、
Ｒがメチル基であるテトラメトキシシランの多量体また
はＲがエチル基であるテトラエトキシシランの多量体が
好ましい。少量で効果を発現し、他の塗膜特性の低下を
おこすことなく雨すじ汚れ発生の防止効果を有する点か
らはメチル基が特に好ましい。複数のＲは１分子中で異
なっていてもよい。In the general formula, R is exemplified by lower alkyl groups such as methyl group, ethyl group, propyl group and butyl group. From the aspect of hydrolyzability and condensation of the alkoxy group,
A tetramethoxysilane multimer in which R is a methyl group or a tetraethoxysilane multimer in which R is an ethyl group is preferable. A methyl group is particularly preferable in that it exhibits an effect even in a small amount and has an effect of preventing the generation of rain streak stains without deteriorating other coating film characteristics. Plural Rs may be different in one molecule.
【００３７】多量体（ｃ）の市販品としては、三菱化成
社製のＭＫＣシリケートＭＳ５１、ＭＳ５６、ＭＳＥＰ
２、コルコート社製のメチルシリケート５１、エチルシ
リケート４８、松本交商のオルガチックスＳＩシリー
ズ、多摩化学製のエチルシリケート４５などが挙げられ
る。Commercially available products of the multimer (c) include MKC silicates MS51, MS56 and MSEP manufactured by Mitsubishi Kasei.
2. Methyl silicate 51, ethyl silicate 48 manufactured by Colcoat Co., Organix SI series manufactured by Matsumoto Trading, ethyl silicate 45 manufactured by Tama Chemical Co., Ltd., and the like.
【００３８】テトラアルコキシシランなどの４官能加水
分解性シラン化合物およびその多量体の多量化の程度を
「シリカ分」で表すこともある。「シリカ分」とは、そ
の化合物から生成するシリカ（ＳｉＯ2 ）の重量割合を
いい、その化合物を完全に加水分解し焼成して生成する
シリカの量を測定することにより得られる。また、「シ
リカ分」はその化合物１分子に対してその１分子から生
成するシリカの割合を示すものであり、式［シリカ分
（重量％）＝多量化度×（ＳｉＯ2 の分子量）×１００
／（その化合物の分子量）］で計算される値である。The degree of multimerization of a tetrafunctional hydrolyzable silane compound such as tetraalkoxysilane and its multimers may be represented by "silica content". The “silica content” means the weight ratio of silica (SiO 2 ) produced from the compound, and can be obtained by measuring the amount of silica produced by completely hydrolyzing the compound and calcining. Further, the "silica content" indicates the ratio of silica generated from one molecule of the compound to one molecule of the compound, and the formula [silica content (% by weight) = degree of multimerization × (molecular weight of SiO 2 ) × 100]
/ (Molecular weight of the compound)].
【００３９】テトラメトキシシランの多量体のシリカ分
を４５重量％以上とすることにより、長期にわたって雨
すじ汚れの発生を防止できる。By setting the silica content of the tetramethoxysilane polymer to 45% by weight or more, it is possible to prevent the generation of rain streak stains for a long period of time.
【００４０】本発明の組成物は、樹脂（ａ）、硬化剤
（ｂ）および多量体（ｃ）を溶解する溶媒（ｄ）ととも
に使用できる。例えば、エタノール、イソプロパノール
等のアルコール類、メチルエチルケトン、メチルイソブ
チルケトン等のケトン類、酢酸ブチル、酢酸エチル等の
エステル類、キシレン、トルエン等の芳香族系溶剤、さ
らには、脂肪族系溶剤、エーテル系溶剤、石油系溶剤等
が例示される。これらの溶媒は２種以上併用してもよ
い。本発明の組成物は、樹脂（ａ）、硬化剤（ｂ）およ
び多量体（ｃ）を有機溶媒または水性媒体に分散させた
ものでもよい。The composition of the present invention can be used together with the solvent (d) which dissolves the resin (a), the curing agent (b) and the multimer (c). For example, alcohols such as ethanol and isopropanol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as butyl acetate and ethyl acetate, aromatic solvents such as xylene and toluene, and aliphatic solvents and ethers. Examples include solvents and petroleum-based solvents. Two or more of these solvents may be used in combination. The composition of the present invention may be one in which the resin (a), the curing agent (b) and the multimer (c) are dispersed in an organic solvent or an aqueous medium.
【００４１】勿論、硬化剤（ｂ）が多価イソシアネート
化合物の場合には、アルコール類や水等の多価イソシア
ネート化合物と反応する溶媒の使用は避けなければなら
ない。多価イソシアネート化合物が本来の樹脂（ａ）に
対する架橋に充分用いられず樹脂（ａ）の架橋が不充分
となり硬化不良を起こすからである。Of course, when the curing agent (b) is a polyvalent isocyanate compound, the use of a solvent that reacts with the polyvalent isocyanate compound such as alcohols and water must be avoided. This is because the polyvalent isocyanate compound is not sufficiently used for the original cross-linking of the resin (a), and the cross-linking of the resin (a) is insufficient, resulting in poor curing.
【００４２】本発明の組成物中の樹脂（ａ）、硬化剤
（ｂ）、多量体（ｃ）の含有割合は樹脂（ａ）１００重
量部に対して硬化剤（ｂ）０．１〜１００重量部、多量
体（ｃ）０．１〜１００重量部の割合が好ましい。特に
好ましい割合は樹脂（ａ）１００重量部に対して硬化剤
（ｂ）１〜６０重量部、多量体（ｃ）１〜６０重量部の
割合である。The content ratio of the resin (a), the curing agent (b) and the multimer (c) in the composition of the present invention is 0.1 to 100 parts by weight of the curing agent (b) with respect to 100 parts by weight of the resin (a). The ratio of 0.1 to 100 parts by weight of the polymer (c) is preferable. A particularly preferable ratio is 1 to 60 parts by weight of the curing agent (b) and 1 to 60 parts by weight of the polymer (c) with respect to 100 parts by weight of the resin (a).
【００４３】樹脂（ａ）が水酸基含有フッ素樹脂の場
合、イソシアネート系硬化剤の含有割合は水酸基含有フ
ッ素樹脂の水酸基１モルに対しのイソシアネート基が
０．８モル以上になるように使用することが好ましい。
０．８モルよりも小さいと本発明の組成物の硬化が不充
分となり耐溶剤性などが低下することがあり好ましくな
い。特に、１．１モル以上になると雨すじ汚れ発生の防
止効果が増大して好ましい。上限は特に限定されない
が、未反応のイソシアネート基が塗膜中に残存し、耐候
性その他の性能に悪影響を起こすことがあるため好まし
い上限としては、２．０程度、さらに好ましくは１．２
〜１．６である。When the resin (a) is a hydroxyl group-containing fluororesin, the isocyanate curing agent should be used so that the isocyanate group content is 0.8 mol or more per 1 mol of the hydroxyl group-containing fluororesin. preferable.
If it is less than 0.8 mol, the composition of the present invention may be insufficiently cured and solvent resistance may be deteriorated. In particular, when the amount is 1.1 mol or more, the effect of preventing rain streak stains increases, which is preferable. The upper limit is not particularly limited, but unreacted isocyanate groups may remain in the coating film, which may adversely affect weather resistance and other performances. Therefore, the upper limit is preferably about 2.0, more preferably 1.2.
~ 1.6.
【００４４】多量体（ｃ）がテトラメトキシシランの多
量体やテトラエトキシシランの多量体の場合は、その含
有割合は樹脂（ａ）１００重量部に対してそれぞれ５〜
５０重量部の割合であることが好ましい。含有割合が少
な過ぎると目的の雨すじ汚れ発生の防止効果が低く、多
過ぎると塗膜の硬化不良を引きおこしやすく好ましくな
い。When the polymer (c) is a polymer of tetramethoxysilane or a polymer of tetraethoxysilane, the content ratio is 5 to 100 parts by weight of the resin (a).
The proportion is preferably 50 parts by weight. If the content is too small, the desired effect of preventing the generation of stains on rain streaks is low, and if the content is too large, it is not preferable because curing failure of the coating film is likely to occur.
【００４５】本発明の塗料用樹脂組成物により形成され
た塗膜により雨すじ汚れの発生が防止される作用は基本
的に塗膜表面が親水性かつ撥油性であることによると考
えられる。雨水中の油性汚れは疎水性表面上に雨水の流
れに沿って付着し、乾燥によりすじ状の汚れとして残
る。一方、親水性かつ撥油性の表面では油性汚れは拡が
らないために、その表面と油性汚れとの接触面積が狭く
なる。そのため、油性汚れのその表面に対する付着性が
低く、油性汚れは雨水の流れとともに流下しやすい。It is considered that the effect of preventing the generation of rain streak stains by the coating film formed from the coating resin composition of the present invention is basically due to the hydrophilicity and oil repellency of the coating film surface. The oily soil in rainwater adheres to the hydrophobic surface along the stream of rainwater and remains as streaky soil on drying. On the other hand, since the oily stain does not spread on the hydrophilic and oil-repellent surface, the contact area between the surface and the oily stain becomes narrow. Therefore, the adhesion of the oily stain to the surface is low, and the oily stain easily flows down with the flow of rainwater.
【００４６】表面の疎水性−親水性の程度は水中でのオ
クタン接触角を測定することにより測定できる。水中で
のオクタン接触角が大きいほど表面は親水性でありかつ
撥油性が高い。雨すじ汚れの発生を充分に防止するため
には水中でのオクタン接触角が１０２度以上であること
が好ましいことを本発明者は見いだした。前述の本発明
における塗料用樹脂組成物は、それにより形成される塗
膜の水中でのオクタン接触角を１０２度以上とすること
ができるものである。The degree of hydrophobicity-hydrophilicity of the surface can be measured by measuring the octane contact angle in water. The larger the octane contact angle in water, the more hydrophilic the surface and the higher the oil repellency. The present inventor has found that the octane contact angle in water is preferably 102 degrees or more in order to sufficiently prevent the generation of rain streaks. The coating resin composition of the present invention described above is one in which the coating film formed thereby can have an octane contact angle in water of 102 degrees or more.
【００４７】本発明者はまた水中でのオクタン接触角と
同様、表面の前進張力と雨すじ汚れの発生のしやすさと
の間にも相関性があることを見いだした。すなわち、表
面の前進張力が０ｄｙｎ／ｃｍよりも小さい場合には雨
すじ汚れが発生しやすく、これよりも大きい場合には雨
すじ汚れが発生し難いことを見いだした。The present inventor has also found that there is a correlation between the advancing tension of the surface and the susceptibility to the formation of rain streaks as well as the octane contact angle in water. That is, it was found that when the forward tension of the surface is smaller than 0 dyn / cm, rain streak stain is likely to occur, and when it is higher than this, rain streak stain is less likely to occur.
【００４８】この作用は必ずしも明確ではないが、表面
の前進張力が０ｄｙｎ／ｃｍよりも小さい場合には雨水
が流れ落ちる際に集まる傾向、すなわち、すじ状に流れ
るため、雨水の流れた跡にすじ状の汚れが発生し、表面
の前進張力が０ｄｙｎ／ｃｍよりも大きい場合には雨水
が流れ落ちる際に集まる傾向が少ないため雨すじ状の汚
れが発生しにくいものと考えられる。したがって、塗装
屋外物品表面の雨すじ汚れの発生を防止するためには、
表面処理剤より形成された薄膜の表面の前進張力が０ｄ
ｙｎ／ｃｍ以上であることが好ましい。このような前進
張力を有する薄膜は雨すじ汚れの発生防止効果がきわめ
て優れている。Although this action is not always clear, when the advancing tension of the surface is smaller than 0 dyn / cm, the rainwater tends to gather when it runs down, that is, because it flows like a streak, a streak appears at the trace of the rainwater. It is considered that when the surface tension is larger than 0 dyn / cm, rainwater-like stains are unlikely to occur because rainwater tends not to collect when the rainwater flows down. Therefore, in order to prevent the generation of rain streaks on the surface of painted outdoor articles,
The forward tension of the surface of the thin film formed by the surface treatment agent is 0d.
It is preferably yn / cm or more. A thin film having such a forward tension has an extremely excellent effect of preventing the generation of rain streaks.
【００４９】表面の前進張力とは、表面処理剤により形
成された薄膜を有する試料を蒸留水中に浸漬させるとき
の、水面に試料が接触した時点での単位周囲長さあたり
の張力をいう。試料を蒸留水より引き上げるときの、水
面から試料が離れる時点での単位周囲長さあたりの張力
である後退張力と区別される。The forward tension of the surface means the tension per unit peripheral length at the time when the sample comes into contact with the water surface when the sample having the thin film formed by the surface treatment agent is immersed in distilled water. When the sample is pulled up from distilled water, it is distinguished from the receding tension which is the tension per unit circumferential length at the time when the sample leaves the water surface.
【００５０】この前進張力は、動的接触角測定装置を用
いて測定できる。また、前進張力は直接測定することが
困難なため、試料を一定速度で２５℃の蒸留水に浸漬さ
せながら試料の重量変化の測定を重量変化量（ｄｙｎ）
が一定になるまで行い、この変化量の直線を試料が水面
に接触した時点まで外挿し、試料が水面に接触した時点
での重量変化量を求めこれを試料の単位周囲長さ（ｃ
ｍ）で割ることにより決定される値である。なお、本発
明者らは、前進張力として浸漬速度２０ｍｍ／ｍｉｎで
測定して得られる値を採用した。This advancing tension can be measured using a dynamic contact angle measuring device. Further, since it is difficult to directly measure the advancing tension, the weight change amount (dyn) of the weight change of the sample is measured while the sample is immersed in distilled water at 25 ° C. at a constant rate.
Until the sample comes into contact with the water surface, and the weight change amount at the time when the sample comes into contact with the water surface is determined to obtain the unit perimeter length (c
It is a value determined by dividing by m). In addition, the present inventors adopted the value obtained by measuring at the immersion speed of 20 mm / min as the forward tension.
【００５１】本発明の組成物は、樹脂（ａ）を含む溶液
からなる主剤組成物（Ａ）と硬化剤（ｂ）および多量体
（ｃ）を含む溶液からなる硬化剤組成物（Ｂ）とを予め
調製した後、主剤組成物（Ａ）と硬化剤組成物（Ｂ）と
を混合して本発明の塗料用樹脂組成物とすることが好ま
しい。この組成物は焼き付け処理を必要とせず現場施工
性に優れるものである。この場合の硬化剤（ｂ）は前述
のブロック化されていないイソシアネート系硬化剤等を
使用する。The composition of the present invention comprises a base composition (A) consisting of a solution containing a resin (a) and a curing agent composition (B) consisting of a solution containing a curing agent (b) and a multimer (c). It is preferable that the base resin composition (A) and the curing agent composition (B) are mixed with each other to prepare the resin composition for coating material of the present invention. This composition does not require a baking treatment and is excellent in on-site workability. As the curing agent (b) in this case, the above-mentioned non-blocked isocyanate curing agent or the like is used.
【００５２】硬化剤組成物（Ｂ）中の硬化剤（ｂ）およ
び多量体（ｃ）の配合量および主剤組成物（Ａ）中の樹
脂（ａ）の配合量は、主剤組成物（Ａ）と硬化剤組成物
（Ｂ）を混合したときに、前述の配合割合となるように
それぞれの組成物中に配合されることが好ましい。The compounding amounts of the curing agent (b) and the multimer (c) in the curing agent composition (B) and the compounding amount of the resin (a) in the main agent composition (A) are the same as the main agent composition (A). When the curing agent composition (B) is mixed with the curing agent composition (B), it is preferable to mix them in the respective compositions so as to have the above-mentioned mixing ratio.
【００５３】屋外物品表面に形成された本発明の組成物
の塗膜表面付近で多量体（ｃ）が加水分解を起こすと考
えられる。この加水分解を促進する触媒を使用してもよ
い。このような触媒として金属キレート、金属エステ
ル、金属アルコキシドなどの金属化合物触媒が用いら
れ、金属としてはアルミニウム、チタン、ケイ素、錫、
亜鉛などが挙げられる。具体的には、アルミニウムモノ
アセチルアセトネートビス（エチルアセトアセテー
ト）、アルミニウムトリス（アセチルアセトネート）な
どが挙げられる。使用量は多量体（ｃ）１００重量部に
対して０．１〜２０重量部、好ましくは１〜１０重量部
である。It is considered that the polymer (c) is hydrolyzed near the surface of the coating film of the composition of the present invention formed on the surface of the outdoor article. A catalyst that accelerates this hydrolysis may be used. As such a catalyst, a metal chelate, a metal ester, a metal compound catalyst such as a metal alkoxide is used, and as the metal, aluminum, titanium, silicon, tin,
Examples include zinc. Specific examples include aluminum monoacetylacetonate bis (ethylacetoacetate) and aluminum tris (acetylacetonate). The amount used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymer (c).
【００５４】本発明の組成物は、上記成分の他に硬化触
媒、顔料、紫外線吸収剤、光安定剤、レベリング剤、つ
や消し剤、界面活性剤、タレ防止剤または塗膜の付着性
向上のためのシランカップリング剤などが含まれていて
もよい。また雨すじ汚れ発生防止に支障ない範囲で、ア
クリル樹脂、ポリエステル樹脂、エポキシ樹脂、シリコ
ン樹脂等の他の塗料用樹脂を併用してもよい。In addition to the above components, the composition of the present invention is used for improving the adhesion of a curing catalyst, a pigment, an ultraviolet absorber, a light stabilizer, a leveling agent, a matting agent, a surfactant, an anti-sagging agent or a coating film. The silane coupling agent and the like may be included. Further, other paint resins such as acrylic resin, polyester resin, epoxy resin, and silicone resin may be used in combination within a range that does not hinder the generation of rain streaks.
【００５５】前記雨すじ汚れの発生を防止するための多
量体（ｃ）とともに、加水分解性基とそれ以外の有機基
とがケイ素原子に結合したシラン化合物であるシランカ
ップリング剤を塗膜の付着性向上のために併用すること
が好ましい。A silane coupling agent, which is a silane compound in which a hydrolyzable group and an organic group other than the hydrolyzable group are bonded to a silicon atom, is applied to the coating film together with the polymer (c) for preventing the generation of rain streaks. It is preferable to use them together for improving the adhesion.
【００５６】本発明においてシランカップリング剤とは
前記のような加水分解性基とそれ以外の有機基を有する
シラン化合物をいう。加水分解性基以外の有機基は末端
炭素原子でケイ素原子に結合している。この有機基は官
能基を有しない炭化水素基であってもよいが、少なくと
も１つの有機基は官能基を有することが好ましい。この
ケイ素原子に結合する加水分解性基としては特にアルコ
キシ基が好ましいが、さらにイソシアネート基も好まし
い。特に、２〜３個のアルコキシ基を有するシラン化合
物が好ましい。In the present invention, the silane coupling agent means a silane compound having the above-mentioned hydrolyzable group and other organic group. Organic groups other than hydrolyzable groups are bonded to silicon atoms at terminal carbon atoms. The organic group may be a hydrocarbon group having no functional group, but it is preferable that at least one organic group has a functional group. An alkoxy group is particularly preferable as the hydrolyzable group bonded to the silicon atom, and an isocyanate group is also preferable. Particularly, a silane compound having 2 to 3 alkoxy groups is preferable.
【００５７】上記シランカップリング剤において、加水
分解性基以外の有機基としては、官能基を有する有機基
を１つ有し、他の有機基がある場合にはそれは通常アル
キル基などの官能基を有しない有機基であることが通例
である。官能基を有する有機基における官能基として
は、例えばアミノ基、エポキシ基、メルカプト基、イソ
シアネート基などがある。特にアミノ基やエポキシ基を
有するシランカップリング剤が添加量が少なくても密着
性が改善されるため好ましい。シランカップリング剤の
配合量は多量体（ｃ）１００重量部に対して１〜５０重
量部が適当であり、好ましくは５〜３０重量部である。In the above silane coupling agent, the organic group other than the hydrolyzable group has one organic group having a functional group, and when there is another organic group, it is usually a functional group such as an alkyl group. It is usually an organic group having no. Examples of the functional group in the organic group having a functional group include an amino group, an epoxy group, a mercapto group, and an isocyanate group. Particularly, a silane coupling agent having an amino group or an epoxy group is preferable because the adhesion is improved even if the addition amount is small. The amount of the silane coupling agent is appropriately 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the polymer (c).
【００５８】シランカップリング剤は塗料用樹脂組成物
中に配合して用いる以外に、屋外物品表面に予めプライ
マーとして処理する方法でも使用できる。この場合、シ
ランカップリング剤を直接塗布してもよいし、アルコー
ル、水等の適当な溶剤に溶解して塗布してもよい。この
プライマー上に次いで表面処理剤が適用される。The silane coupling agent can be used not only by blending it with the coating resin composition but also by pretreating the surface of the outdoor article as a primer. In this case, the silane coupling agent may be applied directly, or may be dissolved in an appropriate solvent such as alcohol or water and applied. A surface treatment is then applied over this primer.
【００５９】シランカップリング剤以外に同様の効果を
発揮し得る他の化合物も使用できる。シランカップリン
グ剤やそれ以外の密着性向上剤としては、例えば以下の
ような化合物がある。Other than the silane coupling agent, other compounds capable of exhibiting the same effect can be used. Examples of the silane coupling agent and other adhesion improvers include the following compounds.
【００６０】メチルトリメトキシシラン、ジメチルビニ
ルメトキシシラン、３−グリシドキシプロピルトリメト
キシシラン、γ−アミノプロピルトリエトキシシラン、
ビニルトリエトキシシラン、γ−メルカプトプロピルト
リメトキシシラン、γ−メタクリロキシプロピルトリメ
トキシシラン、γ−イソシアネートプロピルトリメトキ
シシラン、メチルシリルトリイソシアネート、ビニルシ
リルトリイソシアネート、ジエトキシシリルジイソシア
ネート、ジメチルジクロロシラン、トリメチルクロロシ
ラン、クロロメチルジメチルシラン、メチルトリクロロ
シラン、クロロメチルジメチルビニルシラン、ヘキサメ
チルシラザン、環状シラザン、Ｎ，Ｎ−ビス（トリメチ
ルシリル）トリフルオロアセトアミド、Ｎ−トリメチル
シリルアセトアミド、Ｎ−トリメチルシリルフェニルウ
レア、ビストリメチルシリルウレア、ジメチルトリメチ
ルシリルアミン、トリメチルシリルイミダゾール、トリ
メチルシリルジメチルアミン、メチルトリアセトキシシ
ラン、１，３−ビス（γ−アミノプロピル）−１，１，
３，３−テトラメチルジシロキサン、３−グリシドキシ
プロピルトリメトキシシラン、３−グリシドキシプロピ
ルメチルジメトキシシラン、３−グリシドキシプロピル
メチルジエトキシシラン、２−（３，４−エポキシシク
ロヘキシル）エチルトリメトキシシラン、ＣＨ3 Ｓｉ
［ＯＮ＝Ｃ（ＣＨ3 ）（Ｃ2 Ｈ5 ）］3 。Methyltrimethoxysilane, dimethylvinylmethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
Vinyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, methylsilyltriisocyanate, vinylsilyltriisocyanate, diethoxysilyldiisocyanate, dimethyldichlorosilane, trimethyl Chlorosilane, chloromethyldimethylsilane, methyltrichlorosilane, chloromethyldimethylvinylsilane, hexamethylsilazane, cyclic silazane, N, N-bis (trimethylsilyl) trifluoroacetamide, N-trimethylsilylacetamide, N-trimethylsilylphenylurea, bistrimethylsilylurea, Dimethyl trimethyl silyl amine, trimethyl silyl imidazole, trimethyl silyl dimethyl Amine, methyl triacetoxy silane, 1,3-bis (.gamma.-aminopropyl) -1,1,
3,3-Tetramethyldisiloxane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, CH 3 Si
[ON = C (CH 3) (C 2 H 5)] 3.
【００６１】市販品としては、東芝シリコーン社製のＴ
ＳＬ８０００シリーズ、ＴＳＬ８１００シリーズ、ＴＳ
Ｌ８３００シリーズ、ＴＳＬ９３０６、ＴＳＬ８８シリ
ーズ、ＸＣ９５シリーズ、ＸＣ９９シリーズ、信越化学
工業社製のＫＢＭ１０００シリーズ、ＫＢＥ１０００シ
リーズ、ＫＢＣ１００シリーズ、ＫＢＭ４００，５０
０，６００，７００，８００，９００シリーズ、Ｘ−１
２シリーズ、ＫＢＰ５０３シリーズ、日本ユニカー社製
のＡＺシリース、Ａシリーズ、ユニオンカーバイドのシ
ランカップリング剤Ａシリーズなどが挙げられる。Commercially available products are T manufactured by Toshiba Silicone Co., Ltd.
SL8000 series, TSL8100 series, TS
L8300 series, TSL9306, TSL88 series, XC95 series, XC99 series, Shin-Etsu Chemical's KBM1000 series, KBE1000 series, KBC100 series, KBM400, 50
0,600,700,800,900 series, X-1
2 series, KBP503 series, AZ series of Nippon Unicar Co., A series, silane coupling agent A series of Union Carbide and the like.
【００６２】好ましいシランカップリング剤は、γ−ア
ミノプロピルトリエトキシシラン、γ−アミノプロピル
トリメトキシシラン、γ−アミノプロピルメチルジメト
キシシラン、Ｎ−（２−アミノエチル）−γ−アミノプ
ロピルトリエトキシシラン、Ｎ−（２−アミノエチル）
−γ−アミノプロピルトリメトキシシラン、Ｎ−（２−
アミノエチル）−γ−アミノプロピルメチルジメトキシ
シランなどのアミノ基含有シランカップリング剤、およ
び、３−グリシドキシプロピルトリメトキシシラン、３
−グリシドキシプロピルメチルジメトキシシラン、３−
グリシドキシプロピルメチルジエトキシシラン、２−
（３，４−エポキシシクロヘキシル）エチルトリメトキ
シシランなどのエポキシ基含有シランカップリング剤で
ある。Preferred silane coupling agents are γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -γ-aminopropyltriethoxysilane. , N- (2-aminoethyl)
-Γ-aminopropyltrimethoxysilane, N- (2-
Amino group-containing silane coupling agents such as aminoethyl) -γ-aminopropylmethyldimethoxysilane, and 3-glycidoxypropyltrimethoxysilane, 3
-Glycidoxypropylmethyldimethoxysilane, 3-
Glycidoxypropylmethyldiethoxysilane, 2-
An epoxy group-containing silane coupling agent such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
【００６３】雨すじ汚れが発生しやすい箇所を有する物
品の材質としては、例えば、コンクリート、ＡＬＣ（軽
量気泡コンクリート）、ＧＲＣ（ガラス繊維強化コンク
リート）、ＣＦＲＣ（カーボン繊維強化コンクリー
ト）、石、スレート、ガラス等の無機材、アクリル樹
脂、ポリカーボネート樹脂、塩化ビニル樹脂、ポリエチ
レン樹脂等の樹脂やゴムなどの有機材、アルミニウム、
銅、真鍮、チタン、鉄、ステンレス、亜鉛鋼板、鋼板等
の金属材、木材、さらにはＦＲＰ（ガラス繊維強化合成
樹脂）、ＣＦＲＰ（カーボン繊維強化合成樹脂）等の有
機無機複合材などがある。Examples of the material of the article having a portion where rain streaks are easily generated include concrete, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), CFRC (carbon fiber reinforced concrete), stone, slate, Inorganic materials such as glass, acrylic resins, polycarbonate resins, vinyl chloride resins, polyethylene resins and other organic materials such as rubber, aluminum,
Examples of the material include metal materials such as copper, brass, titanium, iron, stainless steel, zinc steel plate and steel plate, wood, and organic-inorganic composite materials such as FRP (glass fiber reinforced synthetic resin) and CFRP (carbon fiber reinforced synthetic resin).
【００６４】本発明の組成物はこれらの材質からなる基
材に直接塗装してもよく、またプライマー等の表面処理
をした後、または下塗り等をした後に塗装してもよい。
直接に塗装したときに密着性が不充分な基材には、サン
ディング等の表面処理、下塗り処理を施した後塗装する
ことが好ましい。The composition of the present invention may be applied directly to a substrate made of any of these materials, or may be applied after surface treatment with a primer or the like or after undercoating.
It is preferable to apply a surface treatment such as sanding or an undercoating treatment to a substrate which has insufficient adhesion when directly coated.
【００６５】本発明の組成物は例えば以下のような屋外
物品の、雨すじ汚れが発生しやすい箇所へ塗装される。
これによりきわめて長期間雨すじ汚れの発生を防止する
ことができる。屋外物品物として、例えば、自動車、電
車、ヘリコプター、船、自転車、雪上車、ロープウェ
イ、リフト、フォバークラフト、自動二輪車等の輸送用
機器、サッシュ、シャッター、貯水タンク、ドア、バル
コニー、建築用外板パネル、屋根材、階段、天窓、コン
クリート塀などの建築用部材、建築物外壁、ガードレー
ル、歩道橋、防音壁、標識、高速道路側壁、鉄道高架
橋、橋梁などの道路部材、タンク、パイプ、塔、煙突な
どのプラント設備、ビニールハウス、温室、サイロ、農
業用シートなどの農業用設備、電柱、送電鉄塔、パラボ
ラアンテナなどの通信用設備、電気配線ボックス、照明
器具、エアコン屋外器、洗濯機などの電気機器、および
そのカバー、モニュメント、墓石、舗装材、風防シー
ト、防水シート、建築用養生シートなどが挙げられる。The composition of the present invention is applied to, for example, the following outdoor articles where rain streak stains are likely to occur.
As a result, it is possible to prevent the generation of rain streaks for an extremely long period of time. As an outdoor article, for example, a car, a train, a helicopter, a ship, a bicycle, a snowmobile, a ropeway, a lift, a fovercraft, a transportation device such as a motorcycle, a sash, a shutter, a water tank, a door, a balcony, an exterior for construction. Construction materials such as board panels, roofing materials, stairs, skylights, concrete walls, building exterior walls, guardrails, pedestrian bridges, soundproof walls, signs, highway side walls, railway viaducts, road materials such as bridges, tanks, pipes, towers, Plant equipment such as chimneys, greenhouses, greenhouses, silos, agricultural equipment such as agricultural sheets, telephone poles, power transmission towers, communication equipment such as parabolic antennas, electrical wiring boxes, lighting equipment, air conditioners outdoor equipment, washing machines, etc. Electric appliances and their covers, monuments, tombstones, paving materials, windshields, tarpaulins, curing sheets for construction, etc. And the like.
【００６６】本発明の組成物は、通常の塗装方法、たと
えば、刷毛塗り、ローラー塗装、スプレー塗装、フロー
コーターによる塗装など特に塗装方法に限定なく塗装が
可能である。The composition of the present invention can be applied by any ordinary coating method such as brush coating, roller coating, spray coating and flow coater without any particular limitation.
【００６７】[0067]
【実施例】以下の例１〜６、８〜１０、１２〜１３およ
び２０〜２４は実施例、例７、１１および２５は比較
例、例１４〜１７は製造例、例１８〜１９は比較製造例
である。EXAMPLES Examples 1 to 6, 8 to 10, 12 to 13 and 20 to 24 below are Examples, Examples 7, 11 and 25 are Comparative Examples, Examples 14 to 17 are Production Examples, and Examples 18 to 19 are Comparative Examples. It is a manufacturing example.
【００６８】「例１」水酸基を有するフッ素樹脂（クロ
ロトリフルオロエチレン／シクロヘキシルビニルエーテ
ル／ヒドロキシブチルビニルエーテル＝５０／２５／２
５モル％の共重合体）のキシレン溶液（固形分６０重量
％、数平均分子量７，０００、Ｔｇ４５℃、水酸基価１
１６ｍｇＫＯＨ／ｇ）１００重量部に、メチルシリケー
ト５１［コルコート社製テトラメトキシシランの多量体
（平均多量化度約５、シリカ分５１重量％）］を添加
し、その量が２０重量部になったものをガラス板に塗装
し、２０℃で乾燥させた。"Example 1" Fluorine resin having a hydroxyl group (chlorotrifluoroethylene / cyclohexyl vinyl ether / hydroxybutyl vinyl ether = 50/25/2)
5 mol% copolymer) in xylene (solid content 60% by weight, number average molecular weight 7,000, Tg 45 ° C., hydroxyl value 1
To 16 parts KOH / g), 100 parts by weight of methyl silicate 51 [multimer of tetramethoxysilane (average degree of polymerization about 5, silica content 51% by weight) manufactured by Colcoat Co., Ltd.] was added, and the amount became 20 parts by weight. The thing was coated on a glass plate and dried at 20 ° C.
【００６９】上記の水酸基を有するフッ素樹脂１００重
量部に、硬化剤としてコロネートＨＸ（日本ポリウレタ
ン製イソシアネート系硬化剤：ヘキサメチレンジイソシ
アネート環状３量体））３６重量部、顔料として酸化チ
タン２５重量部、硬化触媒としてジブチル錫ジラウレー
ト（キシレンで１０００倍に希釈した溶液、以下ジブチ
ル錫ジラウレート溶液という）０．５重量部、メリルシ
リケート５１を２０重量部添加し、均一に混合しフッ素
樹脂塗料を得た。To 100 parts by weight of the above-mentioned fluorine resin having a hydroxyl group, 36 parts by weight of Coronate HX (isocyanate-based curing agent from Japan Polyurethane: hexamethylene diisocyanate cyclic trimer) as a curing agent, 25 parts by weight of titanium oxide as a pigment, As a curing catalyst, 0.5 part by weight of dibutyltin dilaurate (a solution diluted 1000 times with xylene, hereinafter referred to as a dibutyltin dilaurate solution) and 20 parts by weight of meryl silicate 51 were added and uniformly mixed to obtain a fluororesin coating material.
【００７０】得られた塗料を、１５ｃｍ×４０ｃｍのリ
ン酸亜鉛処理アルミニウム板に塗装し、室温で１週間乾
燥させて塗装物品を得た。アルミニウム板を半分に折り
曲げ、上部が水平面から３０度の角度になり下部が鉛直
になるように、塗装面を外にして屋外に暴露した。この
塗装物品は暴露５か月を経過しても雨すじ汚れの発生が
なかった。The obtained coating material was applied onto a 15 cm × 40 cm zinc phosphate-treated aluminum plate and dried at room temperature for 1 week to obtain a coated article. The aluminum plate was bent in half and exposed outdoors with the coated surface outside so that the upper part was at an angle of 30 degrees from the horizontal and the lower part was vertical. The coated article was free from rain streaks even after 5 months of exposure.
【００７１】「例２」次に、例１で使用した水酸基を有
するフッ素樹脂のキシレン溶液１００重量部に、硬化剤
としてコロネートＨＸ３６重量部、顔料として酸化チタ
ン２５重量部、硬化触媒としてジブチル錫ジラウレート
溶液０．５重量部、エチルシリケート４８［コルコート
社製テトラエトキシシランの多量体（平均多量化度約
８、シリカ分４８重量％）］を１０重量部添加し、均一
に混合しフッ素樹脂塗料を得た。Example 2 Next, 100 parts by weight of the xylene solution of the fluorine-containing fluororesin used in Example 1 was added with 36 parts by weight of Coronate HX as a curing agent, 25 parts by weight of titanium oxide as a pigment, and dibutyltin dilaurate as a curing catalyst. 0.5 parts by weight of the solution and 10 parts by weight of ethyl silicate 48 [multimer of tetraethoxysilane (average degree of polymerization about 8, silica content 48% by weight) manufactured by Colcoat Co., Ltd.] were added and mixed uniformly to give a fluororesin coating material. Obtained.
【００７２】得られた塗料を用いて例１と同様な塗装物
品を得、例１と同様に屋外暴露したところ、この塗装物
品は暴露３か月を経過しても雨すじ汚れの発生がなかっ
たが、暴露５か月を経過たところで雨すじ汚れがやや観
察された。A coated article similar to that of Example 1 was obtained using the obtained coating composition, and exposed outdoors as in Example 1. The coated article did not show rain streaks even after 3 months of exposure. However, after 5 months of exposure, some rain streak contamination was observed.
【００７３】「例３」次に、例１で使用した水酸基を有
するフッ素樹脂のキシレン溶液１００重量部に、硬化剤
としてコロネートＨＸ３６重量部、顔料として酸化チタ
ン２５重量部、硬化触媒としてジブチル錫ジラウレート
溶液０．５重量部、メチルシリケート５１を１２重量部
添加し、均一に混合しフッ素樹脂塗料を得た。Example 3 Next, 100 parts by weight of the xylene solution of the fluorine-containing fluororesin used in Example 1 was added with 36 parts by weight of Coronate HX as a curing agent, 25 parts by weight of titanium oxide as a pigment, and dibutyltin dilaurate as a curing catalyst. 0.5 parts by weight of the solution and 12 parts by weight of methyl silicate 51 were added and uniformly mixed to obtain a fluororesin coating material.
【００７４】得られた塗料を用いて例１と同様な塗装物
品を得、例１と同様に屋外暴露したところ、この塗装物
品は暴露５か月を経過しても雨すじ汚れの発生がなかっ
た。またこの塗装物品表面の前進張力は２．１５ｄｙｎ
／ｃｍであった。A coated article similar to that of Example 1 was obtained using the obtained coating composition, and exposed outdoors as in Example 1. The coated article did not show rain streaks even after 5 months of exposure. It was The forward tension of the surface of this coated article is 2.15 dyn.
Was / cm.
【００７５】「例４」例１で用いた水酸基を有するフッ
素樹脂のキシレン溶液１００重量部に、イソシアネート
系硬化剤としてコロネートＨＸ３６重量部、顔料として
酸化チタン２５重量部、硬化触媒としてジブチル錫ジラ
ウレート溶液０．５重量部、メチルシリケート５１の１
２重量部、アルミニウムモノアセチルアセトネートビス
（エチルアセトアセテート）０．１重量部を添加し、均
一に混合しフッ素樹脂塗料を得た。Example 4 100 parts by weight of the xylene solution of the fluorine-containing fluororesin used in Example 1, 36 parts by weight of Coronate HX as an isocyanate-based curing agent, 25 parts by weight of titanium oxide as a pigment, and a dibutyltin dilaurate solution as a curing catalyst were used. 0.5 parts by weight, 1 of methyl silicate 51
2 parts by weight and 0.1 parts by weight of aluminum monoacetylacetonate bis (ethylacetoacetate) were added and uniformly mixed to obtain a fluororesin coating material.
【００７６】得られた塗料を用いて例１と同様な塗装物
品を得、例１と同様に屋外暴露したところ、この塗装物
品は暴露５か月を経過しても雨すじ汚れの発生がなかっ
た。この塗装物品表面の前進張力は１３．２ｄｙｎ／ｃ
ｍであった。A coated article similar to that of Example 1 was obtained using the obtained coating composition, and exposed outdoors as in Example 1. The coated article did not show rain streaks even after 5 months of exposure. It was The forward tension of the surface of this coated article is 13.2 dyn / c.
It was m.
【００７７】またこの塗膜を室温で７日間乾燥させた
後、キシレンラビングテスト（キシレンをしみ込ませた
ガーゼを１ｋｇ／ｃｍ2 の負荷をかけながら塗膜表面を
こするテスト）を行った。２００回以後も塗膜に変化は
なかった。After the coating film was dried at room temperature for 7 days, a xylene rubbing test (a test of rubbing the surface of the coating film while applying a load of 1 kg / cm 2 of gauze impregnated with xylene) was performed. The coating film did not change after 200 times.
【００７８】「例５〜６、例７」表１に示す組成で塗料
を作成し、例１と同様の評価をした。暴露５か月経過後
の結果を表１に示す。また、例７の塗装物品表面の前進
張力は−４．３ｄｙｎ／ｃｍであった。"Examples 5-6, Example 7" Coating compositions having the compositions shown in Table 1 were prepared and evaluated in the same manner as in Example 1. The results after 5 months of exposure are shown in Table 1. The advancing tension on the surface of the coated article of Example 7 was -4.3 dyn / cm.
【００７９】「例８」メチルシリケート５１の代わりに
エチルシリケート４８を１０重量部添加する以外は例３
と同様の評価をしたところ、暴露５か月を経過しても雨
すじ汚れの発生がなかった。Example 8 Example 3 except that 10 parts by weight of ethyl silicate 48 was added instead of methyl silicate 51.
When the same evaluation as above was performed, no rain streak stain was generated even after 5 months of exposure.
【００８０】「例９〜１０」表２に示す組成で塗料を作
成し、例１と同様の評価をした。暴露５か月経過後の結
果を表２に示す。"Examples 9 to 10" Paints were prepared with the compositions shown in Table 2 and evaluated in the same manner as in Example 1. The results after 5 months of exposure are shown in Table 2.
【００８１】「例１１」例４においてメチルシリケート
５１の代わりにエチルシリケート２８（コルコート社製
テトラエトキシシラン単量体、シリカ分約２８．８重量
％）５０部を用いる以外は例４と同様の評価をしたとこ
ろ、暴露１か月を経過したところで雨すじ汚れが観察さ
れた。[Example 11] The same as Example 4 except that 50 parts of ethyl silicate 28 (tetraethoxysilane monomer manufactured by Colcoat Co., silica content about 28.8% by weight) was used in place of methyl silicate 51 in Example 4. As a result of evaluation, rain streaks were observed after one month of exposure.
【００８２】「例１２」例１で用いた水酸基を有するフ
ッ素樹脂のキシレン溶液１００重量部、酸化チタン２５
重量部、キシレン７５重量部、酢酸ブチル６０重量部、
ｎ−ブタノール８部、ブチロール化メラミン（三井東圧
化学社製ユーバン２０ＳＥ６０、固形分６０重量％）３
０重量部、硬化触媒（楠本化成社製ネイキュア５２２
５）０．５部およびエチルシリケート４８の５重量部か
らなる組成物をアルミニウム板に塗装し、１４０℃で３
０分間で乾燥硬化させた。"Example 12" 100 parts by weight of a xylene solution of the fluorine-containing fluororesin used in Example 1 and titanium oxide 25
Parts by weight, xylene 75 parts by weight, butyl acetate 60 parts by weight,
n-Butanol 8 parts, butyrolized melamine (Uban 20SE60 manufactured by Mitsui Toatsu Chemicals, Inc., solid content 60% by weight) 3
0 parts by weight, curing catalyst (Kusumoto Kasei Co., Ltd.
5) A composition consisting of 0.5 parts and 5 parts by weight of ethyl silicate 48 was coated on an aluminum plate and the mixture was mixed at 140 ° C. for 3 days.
It was dried and cured in 0 minutes.
【００８３】この試験体を例１と同様にして屋外に暴露
したところ、５か月を経過しても雨すじ汚れは観察され
なかった。When this test piece was exposed outdoors in the same manner as in Example 1, no rain streak stain was observed even after 5 months.
【００８４】「例１３」例１で用いた水酸基を有するフ
ッ素樹脂のキシレン溶液１００重量部、酸化チタン２５
重量部、キシレン７５重量部、酢酸ブチル６０重量部、
ブロックイソシアネート（日本ポリウレタン社製Ｃ−２
５０７、ヘキサメチレンジイソシアネート環状３量体の
メチルエチルケトオキシムブロック体、固形分８０重量
％）２０重量部、ジブチル錫ジラウリレート溶液０．５
重量部およびエチルシリケート４８の１０部からなる組
成物をアルミニウム板に塗装し、１６０℃で３０分間で
乾燥硬化させた。"Example 13" 100 parts by weight of a xylene solution of the fluororesin having a hydroxyl group used in Example 1 and 25 parts of titanium oxide.
Parts by weight, xylene 75 parts by weight, butyl acetate 60 parts by weight,
Blocked isocyanate (Nippon Polyurethane Co. C-2
507, methyl ethyl ketoxime block of hexamethylene diisocyanate cyclic trimer, solid content 80% by weight) 20 parts by weight, dibutyltin dilaurate solution 0.5
A composition consisting of 1 part by weight and 10 parts of ethyl silicate 48 was applied to an aluminum plate and dried and cured at 160 ° C. for 30 minutes.
【００８５】この試験体を例１と同様にして屋外に暴露
したところ、５か月を経過しても雨すじ汚れは観察され
なかった。When this test piece was exposed outdoors in the same manner as in Example 1, no rain streak stain was observed even after 5 months.
【００８６】「例１４」例１で用いた水酸基を有するフ
ッ素樹脂のキシレン溶液１００重量部に対し、顔料とし
て２５重量部の酸化チタンＣＲ−９５（石原産業製）、
末端エポキシ基含有シランカップリング剤として０．５
重量部の３−グリシドキシプロピルメチルジメトキシシ
ラン、紫外線吸収剤として２重量部のチヌビン１１３０
（チバガイギー製）、ヒンダードアミン系光安定剤とし
て０．１重量部のＣＧＬ１２３（チバガイギー製）、つ
や消し剤のファインシリカとして２重量部のエアロジル
Ｔ６００（日本エアロジル製）および加水分解による水
酸基の生成を促進する触媒として０．２重量部のアルミ
ニウムモノアセチルアセトネートビス（エチルアセトア
セテート）を混合し、２液型塗料用組成物の主剤組成物
を調製した。"Example 14" 25 parts by weight of titanium oxide CR-95 (manufactured by Ishihara Sangyo Co., Ltd.) as a pigment, based on 100 parts by weight of the xylene solution of the fluorine-containing fluororesin used in Example 1,
0.5 as a silane coupling agent containing terminal epoxy groups
3 parts by weight of 3-glycidoxypropylmethyldimethoxysilane, 2 parts by weight of Tinuvin 1130 as an ultraviolet absorber.
(Manufactured by Ciba Geigy), 0.1 part by weight of CGL123 (manufactured by Ciba Geigy) as a hindered amine-based light stabilizer, 2 parts by weight of Aerosil T600 (manufactured by Nippon Aerosil) as fine silica as a matting agent, and accelerates generation of hydroxyl groups by hydrolysis. As a catalyst, 0.2 part by weight of aluminum monoacetylacetonate bis (ethylacetoacetate) was mixed to prepare a main component composition of a two-pack type coating composition.
【００８７】また、ヘキサメチレンジイソシアネートの
３量体の１８重量部、メチルシリケート５１の２０重量
部、トルエン／酢酸ブチル（混合比＝４／３）の希釈溶
剤の３５重量部からなる硬化剤組成物を調製した。A curing agent composition comprising 18 parts by weight of hexamethylene diisocyanate trimer, 20 parts by weight of methyl silicate 51, and 35 parts by weight of a diluent solvent of toluene / butyl acetate (mixing ratio = 4/3). Was prepared.
【００８８】「例１５」例１４の硬化剤組成物において
メチルシリケート５１の２０重量部に代えてエチルシリ
ケート４０の５０重量部を用いた。Example 15 In the curing agent composition of Example 14, 50 parts by weight of ethyl silicate 40 was used instead of 20 parts by weight of methyl silicate 51.
【００８９】「例１６」例１４の硬化剤組成物において
ヘキサメチレンジイソシアネートの３量体の１８重量部
に代えてメチロールメラミン２０重量部を用いた。"Example 16" In the curing agent composition of Example 14, 20 parts by weight of methylolmelamine were used instead of 18 parts by weight of the trimer of hexamethylene diisocyanate.
【００９０】「例１７」例１４の硬化剤組成物において
ヘキサメチレンジイソシアネートの３量体の１８重量部
に代えてメチルエチルケトオキシムでブロックしたヘキ
サメチレンジイソシアネートの３量体の２５重量部を用
いた。"Example 17" In the curing agent composition of Example 14, 25 parts by weight of a trimer of hexamethylene diisocyanate blocked with methyl ethyl ketoxime was used instead of 18 parts by weight of a trimer of hexamethylene diisocyanate.
【００９１】「例１８」例１４においてメチルシリケー
ト５１を硬化剤組成物に加えるのではなく、主剤組成物
に加えた。Example 18 Methyl silicate 51 in Example 14 was added to the base composition rather than to the hardener composition.
【００９２】「例１９」例１５においてエチルシリケー
ト４０を硬化剤組成物に加えるのではなく、主剤組成物
に加えた。"Example 19" In Example 15, ethyl silicate 40 was added to the base composition rather than to the hardener composition.
【００９３】「貯蔵安定性」例１４〜１９で得られた組
成物の貯蔵安定性結果を以下の表３に示す。なお、表中
の貯蔵安定性は塗料の主剤組成物と硬化剤組成物をそれ
ぞれ１００ｇを５０℃で３０日間密閉容器に入れた後、
組成物を室温に戻し、組成物の濁り、固形化の有無を調
べた。"Storage Stability" The storage stability results of the compositions obtained in Examples 14 to 19 are shown in Table 3 below. In addition, the storage stability in the table is 100 g of each of the main component composition and the curing agent composition of the paint after putting them in a closed container at 50 ° C. for 30 days.
The composition was returned to room temperature and examined for turbidity and solidification.
【００９４】「例２０」例１４の主剤組成物と硬化剤組
成物をそれぞれ１００重量部と３５重量部混合して得ら
れた塗料を用いて例１と同様な塗装物品を得、例１と同
様に屋外暴露したところ、この塗装物品は暴露５か月を
経過しても雨すじ汚れの発生がなかった。"Example 20" A coated article similar to that of Example 1 was obtained by using a coating material obtained by mixing 100 parts by weight and 35 parts by weight of the main agent composition and the curing agent composition of Example 14, respectively. Similarly, when exposed outdoors, this coated article did not show rain streaks even after 5 months of exposure.
【００９５】「例２１」例１４の主剤組成物と例１５の
硬化剤組成物をそれぞれ１００重量部と３５重量部混合
して得られた塗料を用いて例１と同様な塗装物品を得、
例１と同様に屋外暴露したところ、この塗装物品は暴露
５か月を経過しても雨すじ汚れの発生がなかった。"Example 21" A coated article similar to that of Example 1 was obtained using a coating material obtained by mixing 100 parts by weight and 35 parts by weight of the main agent composition of Example 14 and the curing agent composition of Example 15, respectively.
When exposed outdoors in the same manner as in Example 1, this coated article did not show rain streaks even after 5 months of exposure.
【００９６】「例２２」例１４の主剤組成物と例１６の
硬化剤組成物をそれぞれ１００重量部と３５重量部混合
して得られた塗料を用いて例１と同様な塗装物品を得、
例１と同様に屋外暴露したところ、この塗装物品は暴露
５か月を経過しても雨すじ汚れの発生がなかった。"Example 22" A coated article similar to that of Example 1 was obtained using a coating material obtained by mixing 100 parts by weight and 35 parts by weight of the main agent composition of Example 14 and the curing agent composition of Example 16, respectively.
When exposed outdoors in the same manner as in Example 1, this coated article did not show rain streaks even after 5 months of exposure.
【００９７】「例２３」例１４の主剤組成物と例１７の
硬化剤組成物をそれぞれ１００重量部と３５重量部混合
して得られた塗料を用いて例１と同様な塗装物品を得、
例１と同様に屋外暴露したところ、この塗装物品は暴露
５か月を経過しても雨すじ汚れの発生がなかった。"Example 23" A coated article similar to that of Example 1 was obtained using a coating material obtained by mixing 100 parts by weight and 35 parts by weight of the main agent composition of Example 14 and the curing agent composition of Example 17, respectively.
When exposed outdoors in the same manner as in Example 1, this coated article did not show rain streaks even after 5 months of exposure.
【００９８】「例２４」例１で得られたフッ素樹脂塗料
中のフッ素樹脂１００重量部にｐ−トルエンスルホン酸
塩０．１重量部を加え、均一に混合した後アルミニウム
板に塗装し、室温で１週間乾燥硬化させた。この被覆物
品の表面の前進張力は１．２１ｄｙｎ／ｃｍであり、屋
外暴露品は暴露５か月を経過しても雨すじ汚れな発生は
なかった。[Example 24] To 100 parts by weight of the fluororesin in the fluororesin coating material obtained in Example 1, 0.1 parts by weight of p-toluenesulfonate was added and uniformly mixed, and then coated on an aluminum plate at room temperature. And dried and cured for 1 week. The advancing tension of the surface of this coated article was 1.21 dyn / cm, and the outdoor-exposed article did not show rain streaks even after 5 months of exposure.
【００９９】「例２５」例１のフッ素樹脂の代わりに
「クロロトリフルオロエチレン／ベオバ−１０（シェル
化学製分枝状アルキル基含有脂肪酸ビニルエステル）／
シクロヘキシルビニルエーテル／ヒドロキシブチルビニ
ルエーテル＝５０／２５／１５／１０モル％の共重合体
（数平均分子量１２，０００、Ｔｇ３５℃、水酸基価４
０ｍｇＫＯＨ／ｇ）」を用い、例１のメチルシリケート
５１の代わりにエチルシリケート４０［コルコート社製
テトラメトキシシランの多量体（平均多量化度約４、シ
リカ分４０重量％）］を用いる以外例１と同様に評価し
た。塗装物品は１か月経過後雨すじ汚れが発生した。"Example 25" Instead of the fluororesin of Example 1, "chlorotrifluoroethylene / Veova-10 (branched alkyl group-containing fatty acid vinyl ester manufactured by Shell Chemical Co., Ltd.) /
Copolymer of cyclohexyl vinyl ether / hydroxybutyl vinyl ether = 50/25/15/10 mol% (number average molecular weight 12,000, Tg 35 ° C., hydroxyl value 4
Example 1 except that ethyl silicate 40 [a tetramethoxysilane multimer manufactured by Colcoat Co., Ltd. (average multimerization degree: about 4, silica content 40% by weight)] is used in place of the methyl silicate 51 of Example 1] It evaluated similarly to. After one month, the coated articles were stained with rain streaks.
【０１００】[0100]
【表１】 [Table 1]
【０１０１】[0101]
【表２】 [Table 2]
【０１０２】[0102]
【表３】 [Table 3]
【０１０３】[0103]
【発明の効果】本発明の含フッ素塗料用組成物を塗装し
た物品は、雨すじ汚れの発生がないため、建築用外装
材、自動車外板等の屋外物品に使用すると、美観を維持
する効果に優れている。Since the article coated with the composition for a fluorine-containing coating of the present invention does not cause stains on rain lines, it has an effect of maintaining aesthetics when it is used as an outdoor article such as a building exterior material or an automobile outer panel. Is excellent.
Claims (5)
Ｔｇが４０℃以上および水酸基価が７８〜２５０ｍｇＫ
ＯＨ／ｇである官能基含有フッ素樹脂（ａ）、官能基含
有フッ素樹脂（ａ）を架橋し得る硬化剤（ｂ）および明
細書中で定義するシリカ分が４５％以上の４官能加水分
解性シラン化合物の多量体（ｃ）を含み、（ａ）、
（ｂ）および（ｃ）の割合が（ａ）１００重量部に対し
て（ｂ）０．１〜１００重量部および（ｃ）０．１〜１
００重量部である塗料用樹脂組成物。1. A number average molecular weight of 2,000 to 9,000,
Tg is 40 ° C or higher and hydroxyl value is 78 to 250 mgK
OH / g functional group-containing fluororesin (a), curing agent (b) capable of cross-linking functional group-containing fluororesin (a), and tetrafunctional hydrolyzability in which the silica content defined in the specification is 45% or more. A polymer (c) containing a silane compound,
The proportions of (b) and (c) are (b) 0.1 to 100 parts by weight and (c) 0.1 to 1 with respect to (a) 100 parts by weight.
The resin composition for paints, which is 00 parts by weight.
ルコキシシランである請求項１の組成物。2. The composition according to claim 1, wherein the tetrafunctional hydrolyzable silane compound is tetraalkoxysilane.
シランまたはテトラエトキシシランである請求項２の組
成物。3. The composition according to claim 2, wherein the tetraalkoxysilane is tetramethoxysilane or tetraethoxysilane.
フッ素樹脂であり、硬化剤（ｂ）がイソシアネート系硬
化剤またはアミノプラスト系硬化剤である請求項１、２
または３の組成物。4. The functional group-containing fluororesin (a) is a hydroxyl group-containing fluororesin, and the curing agent (b) is an isocyanate-based curing agent or an aminoplast-based curing agent.
Or the composition of 3.
塗装された屋外物品。5. An outdoor article coated with the composition according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12857895A JPH08319448A (en) | 1995-05-26 | 1995-05-26 | Coating resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12857895A JPH08319448A (en) | 1995-05-26 | 1995-05-26 | Coating resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08319448A true JPH08319448A (en) | 1996-12-03 |
Family
ID=14988222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12857895A Pending JPH08319448A (en) | 1995-05-26 | 1995-05-26 | Coating resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08319448A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998022547A1 (en) * | 1996-11-22 | 1998-05-28 | Sk Kaken Co., Ltd. | Non-staining coating composition |
| JPH10310740A (en) * | 1997-05-13 | 1998-11-24 | Toto Ltd | Planing coating composition and member having planing surface |
| JP2002060676A (en) * | 2000-08-11 | 2002-02-26 | Otsuka Chem Co Ltd | Coating composition |
| JP2010008035A (en) * | 2008-05-30 | 2010-01-14 | Daikin Ind Ltd | Heat exchanger |
| JP2016113535A (en) * | 2014-12-15 | 2016-06-23 | 旭硝子株式会社 | Coating composition and coated article |
| JP2016526073A (en) * | 2013-05-24 | 2016-09-01 | ベーイプシロンカー ヘミー ゲゼルシャフト ミット ベシュレンクター ハフトゥング | Hyperbranched polyalkoxysiloxane additive for dust repellent surface coating |
-
1995
- 1995-05-26 JP JP12857895A patent/JPH08319448A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998022547A1 (en) * | 1996-11-22 | 1998-05-28 | Sk Kaken Co., Ltd. | Non-staining coating composition |
| CN1105759C (en) * | 1996-11-22 | 2003-04-16 | Sk化研株式会社 | Non-staining coating composition |
| JPH10310740A (en) * | 1997-05-13 | 1998-11-24 | Toto Ltd | Planing coating composition and member having planing surface |
| JP2002060676A (en) * | 2000-08-11 | 2002-02-26 | Otsuka Chem Co Ltd | Coating composition |
| JP2010008035A (en) * | 2008-05-30 | 2010-01-14 | Daikin Ind Ltd | Heat exchanger |
| JP2016526073A (en) * | 2013-05-24 | 2016-09-01 | ベーイプシロンカー ヘミー ゲゼルシャフト ミット ベシュレンクター ハフトゥング | Hyperbranched polyalkoxysiloxane additive for dust repellent surface coating |
| JP2016113535A (en) * | 2014-12-15 | 2016-06-23 | 旭硝子株式会社 | Coating composition and coated article |
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