JP3717868B2 - Photocatalytic coating agent, photocatalytic composite material and production method thereof - Google Patents
Photocatalytic coating agent, photocatalytic composite material and production method thereof Download PDFInfo
- Publication number
- JP3717868B2 JP3717868B2 JP2002158949A JP2002158949A JP3717868B2 JP 3717868 B2 JP3717868 B2 JP 3717868B2 JP 2002158949 A JP2002158949 A JP 2002158949A JP 2002158949 A JP2002158949 A JP 2002158949A JP 3717868 B2 JP3717868 B2 JP 3717868B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- photocatalytic
- parts
- coating
- trade name
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 230000001699 photocatalysis Effects 0.000 title claims description 62
- 239000011248 coating agent Substances 0.000 title claims description 58
- 239000002131 composite material Substances 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000002245 particle Substances 0.000 claims description 87
- 239000000839 emulsion Substances 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 230000002209 hydrophobic effect Effects 0.000 claims description 45
- 238000000576 coating method Methods 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 18
- 239000000049 pigment Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000003973 paint Substances 0.000 description 31
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 22
- 238000004140 cleaning Methods 0.000 description 16
- 239000008199 coating composition Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000008119 colloidal silica Substances 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000011941 photocatalyst Substances 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000010422 painting Methods 0.000 description 7
- 239000002987 primer (paints) Substances 0.000 description 7
- 239000004606 Fillers/Extenders Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 4
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000000378 calcium silicate Substances 0.000 description 4
- 229910052918 calcium silicate Inorganic materials 0.000 description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 229910002089 NOx Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- YPHMISFOHDHNIV-FSZOTQKASA-N cycloheximide Chemical compound C1[C@@H](C)C[C@H](C)C(=O)[C@@H]1[C@H](O)CC1CC(=O)NC(=O)C1 YPHMISFOHDHNIV-FSZOTQKASA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 2
- DIZPPYBTFPZSGK-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-propylsilane Chemical compound CCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C DIZPPYBTFPZSGK-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- QBZIEGUIYWGBMY-FUZXWUMZSA-N (5Z)-5-hydroxyimino-6-oxonaphthalene-2-sulfonic acid iron Chemical compound [Fe].O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O.O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O.O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O QBZIEGUIYWGBMY-FUZXWUMZSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- JRGQKLFZSNYTDX-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOCC1CO1 JRGQKLFZSNYTDX-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- WALYBSCHCQWCPC-UHFFFAOYSA-N 3-[tris[(2-methylpropan-2-yl)oxy]silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C WALYBSCHCQWCPC-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- OXKAXHPVFLEQHV-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropan-1-amine Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCN OXKAXHPVFLEQHV-UHFFFAOYSA-N 0.000 description 1
- CHPNMYQJQQGAJS-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C(C)=C CHPNMYQJQQGAJS-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-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
- WZSFTHVIIGGDOI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3-[2-methyl-3-[(4,5,6,7-tetrachloro-3-oxoisoindol-1-yl)amino]anilino]isoindol-1-one Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(NC1=CC=CC(NC=3C4=C(C(=C(Cl)C(Cl)=C4Cl)Cl)C(=O)N=3)=C1C)=NC2=O WZSFTHVIIGGDOI-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- IYHIFXGFKVJNBB-UHFFFAOYSA-N 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonic acid Chemical compound C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S(O)(=O)=O IYHIFXGFKVJNBB-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- MZZSDCJQCLYLLL-UHFFFAOYSA-N Secalonsaeure A Natural products COC(=O)C12OC3C(CC1=C(O)CC(C)C2O)C(=CC=C3c4ccc(O)c5C(=O)C6=C(O)CC(C)C(O)C6(Oc45)C(=O)OC)O MZZSDCJQCLYLLL-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- IGLKFJCWZNXDIV-UHFFFAOYSA-N [1-amino-3-[tris[(2-methylpropan-2-yl)oxy]silyl]propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(N)CC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C IGLKFJCWZNXDIV-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- AOADSHDCARXSGL-ZMIIQOOPSA-M alkali blue 4B Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC2=CC=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C2=CC=CC=C2)=CC=C1N.[Na+] AOADSHDCARXSGL-ZMIIQOOPSA-M 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- UWMGVIKSCFGFDR-UHFFFAOYSA-N benzyl(dibromo)silane Chemical compound Br[SiH](Br)CC1=CC=CC=C1 UWMGVIKSCFGFDR-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- LILGYOCNANBWTO-UHFFFAOYSA-N decyl-tri(propan-2-yloxy)silane Chemical compound CCCCCCCCCC[Si](OC(C)C)(OC(C)C)OC(C)C LILGYOCNANBWTO-UHFFFAOYSA-N 0.000 description 1
- AGUMJWWZSTXCAM-UHFFFAOYSA-N decyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CCCCCCCCCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C AGUMJWWZSTXCAM-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- DBUGVTOEUNNUHR-UHFFFAOYSA-N dibromo(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Br)(Br)C1=CC=CC=C1 DBUGVTOEUNNUHR-UHFFFAOYSA-N 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- PROZFBRPPCAADD-UHFFFAOYSA-N ethenyl but-3-enoate Chemical compound C=CCC(=O)OC=C PROZFBRPPCAADD-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
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 1
- BQRPSOKLSZSNAR-UHFFFAOYSA-N ethenyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C=C BQRPSOKLSZSNAR-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- ZVQNVYMTWXEMSF-UHFFFAOYSA-N ethyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](CC)(OC(C)(C)C)OC(C)(C)C ZVQNVYMTWXEMSF-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 description 1
- 235000019233 fast yellow AB Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- DPTKSEHTOJHGOV-UHFFFAOYSA-N hexyl-tri(propan-2-yloxy)silane Chemical compound CCCCCC[Si](OC(C)C)(OC(C)C)OC(C)C DPTKSEHTOJHGOV-UHFFFAOYSA-N 0.000 description 1
- QECCXOBPOBIUMS-UHFFFAOYSA-N hexyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CCCCCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C QECCXOBPOBIUMS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- AHQDZKRRVNGIQL-UHFFFAOYSA-N methyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(OC(C)(C)C)OC(C)(C)C AHQDZKRRVNGIQL-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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 description 1
- VPLNCHFJAOKWBT-UHFFFAOYSA-N phenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C1=CC=CC=C1 VPLNCHFJAOKWBT-UHFFFAOYSA-N 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- MQVCTPXBBSKLFS-UHFFFAOYSA-N tri(propan-2-yloxy)-propylsilane Chemical compound CCC[Si](OC(C)C)(OC(C)C)OC(C)C MQVCTPXBBSKLFS-UHFFFAOYSA-N 0.000 description 1
- LYZDWEPTQWHDLZ-UHFFFAOYSA-N tribromo(decyl)silane Chemical compound CCCCCCCCCC[Si](Br)(Br)Br LYZDWEPTQWHDLZ-UHFFFAOYSA-N 0.000 description 1
- BZAROSBWJASVBU-UHFFFAOYSA-N tribromo(ethenyl)silane Chemical compound Br[Si](Br)(Br)C=C BZAROSBWJASVBU-UHFFFAOYSA-N 0.000 description 1
- KVENDAGPVNAYLY-UHFFFAOYSA-N tribromo(ethyl)silane Chemical compound CC[Si](Br)(Br)Br KVENDAGPVNAYLY-UHFFFAOYSA-N 0.000 description 1
- KBSUPJLTDMARAI-UHFFFAOYSA-N tribromo(methyl)silane Chemical compound C[Si](Br)(Br)Br KBSUPJLTDMARAI-UHFFFAOYSA-N 0.000 description 1
- HPTIEXHGTPSFDC-UHFFFAOYSA-N tribromo(phenyl)silane Chemical compound Br[Si](Br)(Br)C1=CC=CC=C1 HPTIEXHGTPSFDC-UHFFFAOYSA-N 0.000 description 1
- RWRKNKVDHIEKHS-UHFFFAOYSA-N tribromo(propyl)silane Chemical compound CCC[Si](Br)(Br)Br RWRKNKVDHIEKHS-UHFFFAOYSA-N 0.000 description 1
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 1
- HLWCOIUDOLYBGD-UHFFFAOYSA-N trichloro(decyl)silane Chemical compound CCCCCCCCCC[Si](Cl)(Cl)Cl HLWCOIUDOLYBGD-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- JIOBRIJHDZBWDE-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-(3,3,3-trifluoropropyl)silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CCC(F)(F)F JIOBRIJHDZBWDE-UHFFFAOYSA-N 0.000 description 1
- WUSDGIZCXCUHAI-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CCCOCC1CO1 WUSDGIZCXCUHAI-UHFFFAOYSA-N 0.000 description 1
- KGOOITCIBGXHJO-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-phenylsilane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C1=CC=CC=C1 KGOOITCIBGXHJO-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、光触媒性コーティング剤、及び光触媒性複合材並びにその製造方法に関する。
【０００２】
【従来の技術】
近年、光触媒材料が、建物外装に被覆することで、太陽光の照射により親水化して降雨によるセルフクリーニング機能を有する材料として注目されている。また、ＮＯｘ等の有害ガスを分解する環境上好ましい材料としても注目されている。
例えば、特開平１０−１９５３３３号には、水溶性珪酸塩、硬化剤及び光触媒粉末（二酸化チタンまたは酸化亜鉛）を含む塗料を、トンネルやガードレールに塗布し、加熱処理することで、ＮＯxを分解することができる塗膜が形成されることが開示されている。
また、特開平１０−２３７３５４号公報には、珪酸リチウムと二酸化チタンを含有する塗料を塗布し、加熱処理することで、自浄効果に優れた建材が得られることが開示されている。
【０００３】
作業環境、周辺への影響、臭いなどの観点から、最近では溶剤系塗料よりも水系塗料（水性塗料）を用いる傾向が高まりつつある。そのため、上記建物外装等の塗布するための光触媒の水性コート剤も提案されている。
特開平１０−１９５３６９号には光触媒とパーフルオロコポリマーをエマルジョンの状態で配合する塗料組成物が開示されている。
また、特開平１０−２７９８８６号には光触媒とフルオロ基が含有されているシリコーンエマルジョンのコーティング組成物が提案されている。
【０００４】
【発明が解決しようとする課題】
しかしながら、特開平１０−１９５３３３号や特開平１０−２３７３５４号の水性塗料は、プラスチックや塗装鋼板などの疎水性物質を表面に有する基材に対する濡れ性が悪いため、使用の対象がガラス、木材、金属などに限定されてしまう。
また、特開平１０−１９５３６９号や特開平１０−２７９８８６号の水性塗料は、プラスチックや塗装鋼板などの疎水性物質を表面に有する基材に対する濡れ性は改善されるものの屋外での使用を想定した場合、塗装直後の水との接触角が大きく、降雨によるセルフクリーニング機能を使用直後から享受することができなかった。
【０００５】
本発明は、上記事情に鑑みてなされたもので、その目的は、作業環境、周辺への影響、臭いなどの観点から問題がなく、プラスチックや塗装鋼板などの疎水性物質を表面に有する基材に塗布可能であり、疎水性物質を表面に有する基材に被膜を形成した場合に、基材と被膜との密着性が強固であり、かつ被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持される光触媒性コーティング剤、及びそれを疎水性物質を表面に有する基材に被覆した光触媒性複合材並びにその製造方法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明では、上記課題を解決すべく、（ａ）光触媒性酸化物粒子と、（ｂ）疎水性樹脂エマルジョンと、（ｃ）水とを少なくとも含んだ光触媒性コーティング剤であって、前記光触媒性酸化物粒子の平均粒径は、前記疎水性樹脂エマルジョン中に分散した粒子の平均粒径よりも小さいことを特徴とする光触媒性コーティング剤を提供する。
このような構成にすることで、作業環境、周辺への影響、臭いなどの観点での問題がなく、疎水性物質を表面に有する基材に被膜を形成した場合に、基材と被膜との密着性が強固であり、かつ被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持される光触媒性コーティング剤が提供可能となる。
【０００７】
上記光触媒性コーティング剤を、疎水性物質を表面に有する基材に塗布すると、粒径の小さな光触媒性酸化物粒子が上方に移動する。それによって、被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになる。また、同時に、粒径の大きな疎水性樹脂エマルジョン中に分散した粒子が下方に移動し、疎水性物質を表面に有する基材との密着性が増すのである。
【０００８】
本発明の好ましい態様においては、（ａ）光触媒性酸化物粒子と、（ｂ）疎水性樹脂エマルジョンと、（ｃ）水と、（ｄ）シリカ粒子と、を少なくとも含んだ光触媒性コーティング剤であって、前記光触媒性酸化物粒子及びシリカ粒子の平均粒径は、前記疎水性樹脂エマルジョン中に分散した粒子の平均粒径よりも小さいようにする。
シリカ粒子が加わることで、被膜表面の塗装直後における水との接触角がより小さくなり、降雨によるセルフクリーニング機能をより使用直後から享受しやすくなる。
【０００９】
上記光触媒性コーティング剤を、疎水性物質を表面に有する基材に塗布すると、粒径の小さな光触媒性酸化物粒子及びシリカ粒子が上方に移動する。それによって、被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになる。また、同時に、粒径の大きな疎水性樹脂エマルジョン中に分散した粒子が下方に移動し、疎水性物質を表面に有する基材との密着性が増すのである。
【００１０】
本発明の好ましい態様においては、光触媒性酸化物粒子の平均粒径は５〜５０ｎｍであり、前記疎水性樹脂エマルジョン中に分散した粒子の平均粒径は８０〜３００ｎｍであるようにする。
前記光触媒性酸化物粒子の平均粒径が５ｎｍ以上であれば、太陽光の照射による光触媒反応が充分に発揮されるようになり、長期に亘り親水性が維持されやすくなる。また、水との接触角が１０°以下の高度の親水状態が維持されやすくなる。
一方、前記光触媒性酸化物粒子の平均粒径が５０ｎｍ未満であり、かつ疎水性樹脂エマルジョン中に分散した粒子の平均粒径が８０ｎｍ以上であると、光触媒性酸化物粒子と疎水性樹脂エマルジョン中に分散した粒子との粒子径の大きさの差が充分に大きくなるために、粒径の小さな光触媒性酸化物粒子の上方への移動及び粒径の大きな疎水性樹脂エマルジョン中に分散した粒子の下方への移動が生じ易くなり、それによって、被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになると同時に、疎水性物質を表面に有する基材との密着性が増す。
また、疎水性樹脂エマルジョン中に分散した粒子の平均粒径が３００ｎｍ以上であると、エマルジョンとしての安定性が低下し、高粘度になるため塗料組成物として使用することが不可能となる。
【００１１】
本発明の好ましい態様においては、前記光触媒性酸化物粒子の平均粒径は５〜５０ｎｍであり、前記シリカ粒子の平均粒径は５〜１００ｎｍ、より好ましくは５〜５０ｎｍであり、前記疎水性樹脂エマルジョン中に分散した粒子の平均粒径は８０〜３００ｎｍ、より好ましくは１００〜３００ｎｍであるようにする。
シリカ粒子の平均粒径が５nmより小さい場合はシリカ同士の結合強度が大きくなるため、凝集しやすくなる。
光触媒性酸化物粒子の平均粒径は５０ｎｍ未満、前記シリカ粒子の平均粒径は１００ｎｍ未満、より好ましくは５０ｎｍ未満であり、かつ疎水性樹脂エマルジョン中に分散した粒子の平均粒径が８０ｎｍ以上、より好ましくは１００ｎｍ以上であると、光触媒性酸化物粒子及びシリカ粒子と疎水性樹脂エマルジョン中に分散した粒子との粒子径の大きさの差のために、粒径の小さな光触媒性酸化物粒子及びシリカ粒子の上方への移動及び粒径の大きな疎水性樹脂エマルジョン中に分散した粒子の下方への移動が生じ易くなり、それによって、被膜表面は塗装直後から水との接触角が非常に小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになると同時に、疎水性物質を表面に有する基材との密着性が増す。
【００１２】
本発明の好ましい態様においては、固形分中の配合割合が、前記光触媒性酸化物粒子が１〜２０重量％、より好ましくは１〜５重量％、前記疎水性樹脂エマルジョンが５〜９９重量％、より好ましくは１０〜９９重量％であり、前記水の配合割合が固形分１００重量部に対して１０〜５００重量部、より好ましくは１０〜１０９重量部であるようにする。
前記水の配合割合が１０〜５００重量部、より好ましくは１０〜１０９重量部であることで、膜厚１μｍ〜１ｍｍの塗料として適当な膜厚で塗膜が形成可能となる。
また、光触媒性酸化物粒子の配合割合が１重量％以上であることで、被膜表面は塗装直後から水との接触角が小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになる。
また、光触媒性酸化物粒子の配合割合が固形分中２０重量％未満、より好ましくは５重量％未満であることで、光触媒性酸化物の酸化還元力に基づく分解力による、疎水性樹脂エマルジョンの硬化により得られるバインダーへの影響がなく、屋外の使用において長期に亘り、セルフクリーニング機能が維持される。
また、疎水性樹脂エマルジョンの配合割合が５重量％以上、より好ましくは１０重量％以上であることで、疎水性物質を表面に有する基材との密着性が増す。
【００１３】
本発明の好ましい態様においては、固形分中の配合割合が、前記光触媒性酸化物粒子が１〜２０重量％、より好ましくは全固形分に対して１〜５重量％、前記シリカ粒子の配合割合が１〜９０重量％、前記疎水性樹脂エマルジョンの配合割合が５〜９８重量％、より好ましくは１０〜９８重量％、前記水の配合割合が固形分１００重量部に対して１０〜５００重量部、より好ましくは１０〜１０８重量部であるようにする。
シリカ粒子の配合割合が１重量％以上であることで、被膜表面は塗装直後から水との接触角がより小さく、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになる。
【００１４】
本発明の好ましい態様においては、（ａ）光触媒性酸化物粒子と、（ｂ）疎水性樹脂エマルジョンと、（ｃ）水と、を少なくとも含んだ光触媒性コーティング剤であって、前記光触媒性酸化物粒子は、全固形分に対して１〜５重量％であるようにする。
光触媒性酸化物粒子の配合割合が全固形分に対して５重量％未満であることで、光触媒性酸化物の酸化還元力に基づく分解力による、疎水性樹脂エマルジョンの硬化により得られるバインダーと光触媒性酸化物粒子のお互いの結合力及び基材との結合力への影響がなく、屋外の使用において長期に亘り、被膜の強度及び基材との密着性が維持される。
【００１５】
本発明の好ましい態様においては、（ａ）光触媒性酸化物粒子と、（ｂ）疎水性樹脂エマルジョンと、（ｃ）水と、（ｄ）シリカ粒子と、を少なくとも含んだ光触媒性コーティング剤であって、前記光触媒性酸化物粒子は、全固形分に対して１〜５重量％であるようにする。
光触媒性酸化物粒子の配合割合が全固形分に対して５重量部未満であることで、光触媒性酸化物の酸化還元力に基づく分解力による、疎水性樹脂エマルジョンの硬化により得られるバインダーと光触媒性酸化物粒子及びシリカ粒子のお互いの結合力及び基材との結合力への影響がなく、屋外の使用において長期に亘り、被膜の強度及び基材との密着性が維持される。
【００１６】
本発明の好ましい態様においては、前記疎水性樹脂エマルジョンは、フッ素樹脂エマルジョン、シリコーンエマルジョンのうちの１種以上であるようにする。フッ素樹脂エマルジョン及び／又はシリコーンエマルジョンであることで、耐候性が良好になる。
【００１７】
【発明の実施の形態】
以下に本発明の好ましい形態を説明する。
まず、以下に本発明で用いる語について説明する。
本発明において、「光触媒性酸化物粒子」には、例えば、酸化チタン、酸化亜鉛、酸化錫、酸化鉄、酸化ジルコニウム、酸化タングステン、酸化クロム、酸化モリブデン、酸化ルテニウム、酸化ゲルマニウム、酸化鉛、酸化カドミウム、酸化銅、酸化バナジウム、酸化ニオブ、酸化タンタル、酸化マンガン、酸化ロジウム、酸化ニッケル、酸化レニウム、チタン酸ストロンチウム等の粒子が利用できる。
なお、酸化チタンを光触媒として用いる場合は、結晶型がアナターゼ型、またはブルッカイト型のものを用いることが、光触媒活性がもっとも強く、しかも長期間発現するので好ましい。
【００１８】
「疎水性樹脂エマルジョン」としては、例えば、フッ素樹脂、シリコーン、アクリルシリコーン、酢酸ビニル、酢酸ビニルアクリル、アクリルウレタン、アクリル、エポキシ、塩化ビニル酢酸ビニル、塩化ビニリデン、ＳＢＲラテックス等のエマルジョンが利用できる。
フッ素樹脂エマルジョンとしては、例えばポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリフッ化ビニル、ポリクロロトリフルオロエチレン、テトラフルオロエチレン−ヘキサフルオロプロピレンコポリマー、エチレン−テトラフルオロエチレンコポリマー、エチレン−クロロトリフルオロエチレンコポリマー、テトラフルオロエチレン−パーフルオロアルキルビニルエーテルコポリマー、パーフルオロシクロポリマー、ビニルエーテル−フルオロオレフィンコポリマー、ビニルエステル−フルオロオレフィンコポリマー、テトラフルオロエチレン−ビニルエーテルコポリマー、クロロトリフルオロエチレン−ビニルエーテルコポリマー、テトラフルオロエチレンウレタン架橋体、テトラフルオロエチレンエポキシ架橋体、テトラフルオロエチレンアクリル架橋体、テトラフルオロエチレンメラミン架橋体等フルオロ基を含有するポリマーのエマルジョンが好適に利用できる。
また、シリコーンのエマルジョンとしては、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリクロシラン、メチルトリブロムシラン、メチルトリイソプロポキシシラン、メチルトリｔ−ブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリクロルシラン、エチルトリブロムシラン、エチルトリイソプロポキシシラン、エチルトリｔ−ブトキシシラン、ｎープロピルトリメトキシシラン、ｎープロピルトリエトキシシラン、ｎープロピルトリクロシラン、ｎープロピルトリブロムシラン、ｎープロピルトリイソプロポキシシラン、ｎープロピルトリｔ−ブトキシシラン、ｎーヘキシルトリメトキシシラン、ｎーヘキシルトリエトキシシラン、ｎーヘキシルトリクロシラン、ｎーヘキシルトリブロムシラン、ｎーヘキシルトリイソプロポキシシラン、ｎーヘキシルトリｔ−ブトキシシラン、ｎーデシルトリメトキシシラン、ｎーデシルトリエトキシシラン、ｎーデシルトリクロシラン、ｎーデシルトリブロムシラン、ｎーデシルトリイソプロポキシシラン、ｎーデシルトリｔ−ブトキシシラン、ｎーオクタトリメトキシシラン、ｎーオクタトリエトキシシラン、ｎーオクタトリクロシラン、ｎーオクタトリブロムシラン、ｎーオクタトリイソプロポキシシラン、ｎーオクタトリｔ−ブトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリクロシラン、フェニルトリブロムシラン、フェニルトリイソプロポキシシラン、フェニルトリｔ−ブトキシシラン、ジメチルジクロルシラン、ジメチルジブロムシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジクロルシラン、ジフェニルジブロムシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、フェニルメチルジクロルシラン、フェニルメチルジブロムシラン、フェニルメチルジメトキシシラン、フェニルメチルジエトキシシラン、ビニルトリクロルシラン、ビニルトリブロムシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリｔ−ブトキシシラン、トリフルオロプロピルトリクロルシラン、トリフルオロプロピルトリジブロムシラン、トリフルオロプロピルトリメトキシシラン、トリフルオロプロピルトリエトキシシラン、ビニルトリクロルシラン、トリフルオロプロピルトリイソプロポキシシラン、トリフルオロプロピルトリｔ−ブトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリイソプロポキシシラン、γ−グリシドキシプロピルトリｔ−ブトキシシラン、γ−メタアクリロキシプロピルメチルジメトキシシラン、γ−メタアクリロキシプロピルメチルジエトキシシラン、γ−メタアクリロキシプロピルトリメトキシシラン、γ−メタアクリロキシプロピルトリエトキシシラン、γ−メタアクリロキシプロピルトリイソプロポキシシラン、γ−メタアクリロキシプロピルトリｔ−ブトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリイソプロポキシシラン、γ−アミノメタアクリロキシプロピルトリｔ−ブトキシシラン、γ−メチルカプトプロピルメチルジメトキシシラン、γ−メチルカプトプロピルメチルジエトキシシラン、γ−メチルカプトプロピルトリメトキシシラン、γ−メチルカプトプロピルトリエトキシシラン、γ−メチルカプトプロピルトリイソプロポキシシラン、γ−メチルカプトプロピルトリｔ−ブトキシシラン、β−（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、β−（３，４−エポキシシクロヘキシル）エチルトリエトキシシランの加水分解、脱水縮重合物などのエマルジョンが好適に利用できる。
【００１９】
「シリカ粒子」の好ましい具体例としては、無定型シリカ粒子が好ましい。無定型シリカでは、コロイダルシリカの形態が挙げられる。コロイダルシリカには、水に分散させたもの、あるいは、アルコールなどの非水系の有機溶媒に分散したものがあり、両方とも使用可能ではあるが、本発明では構成要素のエマルジョンの安定性を若干低下させるので、水に分散させたものを使用することが好ましい。また、有機溶剤に分散したコロイダルシリカは、前記水分散コロイダルシリカ中の水溶媒を有機溶媒に置換することで容易に調整することが可能である。
【００２０】
光触媒性酸化物粒子及びシリカ粒子並びに疎水性樹脂エマルジョン中に分散した粒子の平均粒径は、レーザーを光源とした動的光散乱測定により測定した。測定装置は大塚電子株式会社製ＤＬＳ−６００を使用した。
【００２１】
本発明のコーティング剤は、例えば、水分散性の光触媒性酸化物粒子のゾルに、必要に応じてコロイダルシリカを添加した後に、疎水性樹脂エマルジョンをさらに添加し、必要に応じて水で希釈することにより得ることが可能である。
【００２２】
また、本発明のコーティング剤は、疎水性物質を表面に有する基材表面に被覆し、硬化せしめることで、降雨によるセルフクリーニング機能を使用直後から享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持される光触媒性複合材に改質できる。ここで、硬化は常温で行うのが、現場施工等には有利である。
【００２３】
「疎水性物質を表面に有する基材」は、例えば、プラスチック、有機物の繊維、有機物の布帛、塗装鋼板等の塗装体等が好適に利用できる。
【００２４】
本発明のコーティング剤には、さらに、Ag、Cu、Znのような金属を添加することが好ましい。このような金属が添加された表面層は、表面に付着した細菌や黴や藻を暗所でも死滅させることができ、よって防汚性をより向上させることができる。
【００２５】
本発明のコーティング剤には、さらに、Pt、Pd、Ru、Rh、Ir、Osのような白金族金属を添加することができる。このような金属が添加された表面層は、光触媒の酸化還元活性を増強でき、有機物汚れの分解性、有害気体や悪臭の分解性を向上させることができる。
【００２６】
本発明のコーティング剤には、さらに、疎水性樹脂エマルジョンの基材への造膜性を向上させるために造膜助剤を使用することが可能である。造膜助剤は、大部分の水分が気化した後も塗膜中に残存し、エマルション粒子どうしの融合を促進させる機能をもつものである。具体的には、沸点が１００℃以上の有機化合物が挙げられる。以下に具体例を示す。
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、エチレングリコールエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、等のエチレン系グリコールエーテル類。
プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、
ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、ポリプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールジアセテート、プロピレングリコールフェニルエーテル、等のプロピレン系グリコールエーテル類。
２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート、ｎ−ペンシルプロピオネ−ト（n-PENTYL PROPIONATE）、フタル酸ジブチル等のエステル類などが挙げられる。
そのうち、エステル類の一種である２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレートは、フッ素樹脂エマルジョンへの浸透能力が高いこと、最低造膜温度（MFT）の低下効果が高いことから、その使用は好ましい。逆にエチレン系グリコールエーテル類は人体への毒性が強いので、その使用は好ましくない。
【００２７】
本発明のコーティング剤には、さらに、着色料を添加することができる。着色料としては無機顔料、有機顔料、染料などから少なくとも１つを選ぶ。
無機顔料としては、酸化チタン、亜鉛華、ベンガラ、酸化クロム、コバルトブルー、鉄黒などの金属酸化物系、アルミナホワイト、黄色酸化鉄などの金属水酸化物系、紺青などのフェロシアン化合物系、黄鉛、ジンクロメート、モリブデンレッドなどのクロム酸鉛系、硫化亜鉛、朱、カドミウムイエロー、カドミウムレッドなどの硫化物、セレン化合物、バライト、沈降性硫酸バリウムなどの硫酸塩系、重質炭酸カルシウム、沈降性炭酸カルシウムなどの炭酸塩系、含水珪酸塩、クレイ、群青などの珪酸塩系、カーボンブラックなどの炭素系、アルミニウム粉、ブロンズ粉、亜鉛粉などの金属粉系、雲母・酸化チタン系などのパール顔料系などが挙げられる。
有機顔料としては、ナフトールグリーンＢなどのニトロソ系顔料、ナフトールＳなどのニトロ顔料系、リソールレッド、レーキレッドＣ、ファストエロー、ナフロールレッドなどのアゾ顔料系、アルカリブルーレッド、ローダミンキレート、キナクリドンレッド、ジオキサジンバイオレッド、イソインドリノンエローなどの縮合多環顔料系などが挙げられる。
染料としては、分散染料、塩基性染料、直接染料、酸性染料が挙げられる。
【００２８】
【実施例】
（塗料組成物の調製）
尚、本実施例、比較例の作成に用いた材料の固形分濃度、平均粒子径は表１の通り。
【００２９】
【表１】
【００３０】
実施例１
光触媒酸化物ゾル（日本パーカライジング株式会社製、商品名パルチタン５６１０）１０．２重量部、コロイダルシリカ（日本化学株式会社製、商品名シリカドール３０Ｂ）７９．６重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ３０００）１０．２重量部（以上固形分で表示）、造膜助剤（イーストマン・コダック社製、商品名テキサノール）２．１重量部を混合し、水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して４３３重量部であった。
【００３１】
実施例２
光触媒酸化物ゾル（テイカ株式会社製、商品名ＴＫＳ−２０３）２０．１重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）１０．２重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）６９．７重量部（以上固形分で表示）、造膜助剤（イーストマン・コダック社製、商品名テキサノール）１５．７重量部である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１５９重量部であった。
【００３２】
実施例３
光触媒酸化物ゾル（日本パーカライジング株式会社製、商品名パルチタン５６１０）３．２重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）２５．９重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）３．２重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)３８．９重量部、体質顔料（大塚化学株式会社製、商品名ティスモ−Ｎ）２８．８重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）０．７重量部である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１３２重量部であった。
【００３３】
実施例４
光触媒酸化物ゾル（石原産業株式会社製、商品名ＳＴＳ−２１）１．０重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ）３８．８重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）２３．１重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)２０．４重量部、体質顔料Ａ（大塚化学株式会社製、商品名ＨＴ−３００）４．７重量部、体質顔料Ｂ（日本タルク（株）製、ミクロエースＰ３）１２．０重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）７．８重量部である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１５２重量部であった。
【００３４】
実施例５
光触媒酸化物ゾル（石原産業株式会社製、商品名ＳＴＳ−２１）１．４重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ）５０．８重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）１５．０重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)２６．７重量部、体質顔料（大塚化学株式会社製、商品名ＨＴ−３００）６．１重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）３．３重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１７５重量部であった。
【００３５】
実施例６
光触媒酸化物ゾル（石原産業株式会社製、商品名ＳＴＳ−２１）１８．３重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）４４．３重量部、シリコーンエマルジョン（大日本インキ化学工業（株）製、商品名ボンコートＳＡ−５０８０）９．９重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)１５．２重量部、体質顔料（大塚化学株式会社製、商品名ＨＴ−３００）１２．３重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）２．４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して２９４重量部であった。
【００３６】
比較例１
フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）６７．８重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)２６．７重量部、体質顔料（大塚化学株式会社製、商品名ティスモ−Ｎ）５．５重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）１４．７重量部である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して８５重量部であった。
【００３７】
比較例２
光触媒酸化物ゾル（日本パーカライジング株式会社製、商品名パルチタン５６１０）１０重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）２３．９重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)１１．４重量部、体質顔料（大塚化学株式会社製、商品名ティスモ−Ｎ）５４．７重量部（以上固形分で表示）である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して２６９重量部であった。
【００３８】
比較例３
光触媒酸化物（日本パーカライジング株式会社製、商品名パルチタン５６１０）９．８重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）７９．３重量部、フッ素樹脂（旭硝子株式会社製、商品名ルミフロンＬＦ１００）１０．９重量部（以上固形分で表示）である塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して３２５重量部であった。塗布直前に硬化剤（日本ポリウレタン株式会社製、商品名コロネートＨＸ）を塗料組成物１００重量部に対して、０．４重量部添加した。
【００３９】
（基材への塗布方法）
１５０ｍｍ×６５ｍｍに裁断した石綿セメント珪酸カルシウム板（ＪＩＳ Ａ５４１８に準拠したもの）にエポキシ樹脂系プライマー（エスケー化研、商品名ＳＫサーフエポ）をスプレー塗装し、室温で２４時間乾燥させた。続いて、アクリルウレタン塗料（イサム塗料 商品名 ハイアート１０００）を、上記したプライマー塗装を行った石綿セメント珪酸カルシウム板上にスプレー塗装し、室温で２４時間乾燥させた。さらに続いて、前記で調製した実施例１、２、３及び比較例１、２、３の塗料組成物をプライマー塗装、アクリルウレタン塗装を行った石綿セメント珪酸カルシウム板上に刷毛塗りし、コーティング物を得た。
また、プライマー塗装を行った石綿セメント珪酸カルシウム板上にスズカファイン（株）製下地調整塗材（商品名「リメークプラ」）を刷毛塗し、室温で２４時間乾燥させたたものに、実施例４、５、６の塗料組成物の塗装を行ない、コーティング物を得た。
コーティングは試験片を垂直に立てた状態で行った。刷毛塗りした上記塗料組成物の重量は１５ｇ／ｍ2であった。最後に、上記コーティング物を室温で２４時間乾燥させて試験片１〜９を得た。
試験片１：実施例１の塗料を塗布
試験片２：実施例２の塗料を塗布
試験片３：実施例３の塗料を塗布
試験片４：実施例４の塗料を塗布
試験片５：実施例５の塗料を塗布
試験片６：実施例６の塗料を塗布
試験片７：比較例１の塗料を塗布
試験片８：比較例２の塗料を塗布
試験片９：比較例３の塗料を塗布
【００４０】
エリクセン評価、一酸化窒素分解性能評価用試験片の作成
１５０ｍｍ×６５ｍｍに裁断した亜鉛メッキ鋼板（ＪＩＳ Ａ５４００に準拠したもの）にエポキシ樹脂系プライマー（エスケー化研、商品名 ＳＫサーフエポ）をスプレー塗装し、室温で２４時間乾燥させた。続いて、前記で調製した実施例１、２、３、４、５、６及び比較例１、２、３の塗料組成物を、プライマー塗装を行った亜鉛メッキ鋼板上に刷毛塗りし、コーティング物を得た。
コーティングは試験片を垂直に立てた状態で行った。刷毛塗りした上記塗料組成物の重量は１５ｇ／ｍ2であった。最後に、上記コーティング物を室温で２４時間乾燥させて試験片１０〜１８を得た。
試験片１０：実施例１の塗料を塗布
試験片１１：実施例２の塗料を塗布
試験片１２：実施例３の塗料を塗布
試験片１３：実施例４の塗料を塗布
試験片１４：実施例５の塗料を塗布
試験片１５：実施例６の塗料を塗布
試験片１６：比較例１の塗料を塗布
試験片１７：比較例２の塗料を塗布
試験片１８：比較例３の塗料を塗布
【００４１】
次に、上記各試験片について、膜厚、クラックの有無、密着性、エリクセン評価、光沢、耐アルカリ性、耐沸騰水性、熱冷サイクル試験、親水性（初期接触角と紫外線照射時の接触角を測定）を評価し、その結果を（表２）に示す。また、自己洗浄性評価についてはその結果を（表３）に示す。一酸化窒素分解性能についてはその結果を（図１〜５）に示す。
【００４２】
【表２】
【００４３】
【表３】
【００４４】
評価方法は以下の通りである。
膜厚：走査型電子顕微鏡（日立製作所製Ｓ-4100）により試験片を断面方向から観察し、膜厚を測定した。
クラックの有無：光学顕微鏡（キーエンス製ＶＦ-7500）を用いて試験片表面を観察してクラックの有無を確認した。
密着性：ＪＩＳ Ｋ５４００ 碁盤目試験法により行った。即ち、作製した試験片の塗膜の上からカッターで２ｍｍ幅の碁盤目の切込みを入れる。大きさは１ｃｍ角にし、碁盤目の数を２５個とする。その後その碁盤目を完全に覆うようにセロハンテープを貼り付ける。その後、すばやく引き剥がして付着して残っている碁盤目の数を数える。
エリクセン評価：ＪＩＳ Ｂ７７２９に準拠したエリクセン試験機を用いて、金属板に塗布した試験片により裏面より鋼球を押し出し、試験片を変形させる。塗膜にクラック、割れ、剥がれ、を生じるまでの押し出し距離を調べる。
光沢：作製した試験片の光沢度を日本電色工業製ＶＧＳ-1Ｄを用いて測定した。
耐アルカリ性：水酸化カルシウム飽和水溶液に室温で７日間浸漬し、取り出した後蒸留水にて洗浄し、十分乾燥させた後、目視外観にて評価を行なう。
耐沸騰水性：９５℃以上の沸騰水中に２時間浸漬し、取り出した後蒸留水にて洗浄し、十分乾燥させた後、目視外観にて評価を行なう。
熱冷サイクル試験：５０℃の恒温槽に３時間、次いで、−２０℃の恒温槽に３時間、次いで２５℃の恒温水槽に１８時間を１サイクルとして１０サイクル繰り返す。取り出した後蒸留水にて洗浄し、十分乾燥させた後、目視外観にて評価を行なう。
親水性（初期接触角）：試験片表面の水との接触角を、協和界面科学製ＣＸ-150を用いて測定した。
親水性（紫外線照射時）：作製した試験片にＢＬＢランプから発生した0.5ｍＷ／ｃｍ2の紫外線を７日間または殺菌灯ランプから発生した3.0ｍＷ／ｃｍ2の紫外線を3日間照射し、その後水との接触角を、協和界面科学製ＣＸ-150を用いて測定した。
自己洗浄性（屋外暴露）：作製した試験片を南側に向け、鉛直に対して４５°傾斜させたものを屋外に設置する。暴露する前、暴露1ヶ月後、暴露2ヶ月後の目視による外観評価及び接触角を測定した。
一酸化窒素分解性能評価：評価装置の模式図を図６に示す。入口側の一酸化窒素の濃度を空気と調整して０．２５ｐｐｍとする。流量を毎分１リットルに調整する。試験片を設置してから、３０分間流量が安定するまで気体を流す。その後紫外線をＢＬＢ灯にて０．５ｍＷ／ｃｍ2の強度にて照射する。一酸化窒素と二酸化窒素の濃度を記録する。
【００４５】
【発明の効果】
以上に説明したように本発明によれば、光触媒を添加したことによる防汚、親水効果が発揮される。また、プラスチックなどの有機系基材表面に形成する塗膜の厚みを厚くしても、クラックが発生せず、しかも剥離強度に優れた塗膜となる水性塗料組成物が得られる。
【図面の簡単な説明】
【図１】 本発明の一実施例の一酸化窒素分解性能を示す図。
【図２】 本発明の他の実施例の一酸化窒素分解性能を示す図。
【図３】 本発明の他の実施例の一酸化窒素分解性能を示す図。
【図４】 比較例の一酸化窒素分解性能を示す図。
【図５】 比較例の一酸化窒素分解性能を示す図。
【図６】 一酸化窒素分解性能の評価装置の模式図[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photocatalytic coating agent, a photocatalytic composite material, and a method for producing the same.
[0002]
[Prior art]
In recent years, a photocatalyst material has attracted attention as a material having a self-cleaning function due to rainfall by being made hydrophilic by being irradiated with sunlight by covering the exterior of a building. Moreover, it attracts attention as an environmentally preferable material that decomposes harmful gases such as NOx.
For example, Japanese Patent Laid-Open No. 10-195333 discloses that NOx is decomposed by applying a paint containing a water-soluble silicate, a curing agent, and a photocatalyst powder (titanium dioxide or zinc oxide) to a tunnel or a guardrail and heat-treating it. It is disclosed that a coating can be formed.
Japanese Patent Application Laid-Open No. 10-237354 discloses that a building material having an excellent self-cleaning effect can be obtained by applying a paint containing lithium silicate and titanium dioxide and performing heat treatment.
[0003]
From the viewpoints of working environment, influence on surroundings, odor and the like, recently, the tendency to use water-based paint (water-based paint) rather than solvent-based paint is increasing. Therefore, an aqueous photocatalyst coating agent for applying the exterior of the building or the like has also been proposed.
Japanese Patent Application Laid-Open No. 10-195369 discloses a coating composition containing a photocatalyst and a perfluoro copolymer in an emulsion state.
JP-A-10-279886 proposes a coating composition of a silicone emulsion containing a photocatalyst and a fluoro group.
[0004]
[Problems to be solved by the invention]
However, since the water-based paints of JP-A-10-195333 and JP-A-10-237354 have poor wettability with respect to a substrate having a hydrophobic substance such as plastic or coated steel plate on the surface, the object of use is glass, wood, It is limited to metal.
In addition, the water-based paints of JP-A-10-195369 and JP-A-10-279886 are intended for outdoor use, although the wettability with respect to a substrate having a hydrophobic substance on the surface, such as plastic or coated steel plate, is improved. In this case, the contact angle with water immediately after painting was large and the self-cleaning function due to rain could not be enjoyed immediately after use.
[0005]
The present invention has been made in view of the above circumstances, and its purpose is no problem from the viewpoint of work environment, influence on the surroundings, odor, etc., and a substrate having a hydrophobic material such as plastic or painted steel sheet on the surface. When a coating is formed on a substrate having a hydrophobic substance on the surface, the adhesion between the substrate and the coating is strong, and the coating surface has a small contact angle with water immediately after coating. A photocatalytic coating agent that can enjoy a self-cleaning function due to rain immediately after use, and whose state is maintained for a long time by irradiation with sunlight, and a substrate having a hydrophobic substance on the surface thereof An object of the present invention is to provide a photocatalytic composite material coated on a material and a method for producing the same.
[0006]
[Means for Solving the Problems]
In the present invention, in order to solve the above problems, a photocatalytic coating agent comprising at least (a) photocatalytic oxide particles, (b) a hydrophobic resin emulsion, and (c) water, Provided is a photocatalytic coating agent characterized in that an average particle size of oxide particles is smaller than an average particle size of particles dispersed in the hydrophobic resin emulsion.
With such a configuration, there is no problem in terms of work environment, influence on the surroundings, smell, etc., and when a coating is formed on a substrate having a hydrophobic substance on the surface, The adhesion is strong, and the coating surface has a small contact angle with water immediately after painting, and it is possible to enjoy the self-cleaning function due to rain immediately after use, and the state can be maintained for a long time by irradiation with sunlight. It is possible to provide a photocatalytic coating agent that is maintained throughout.
[0007]
When the photocatalytic coating agent is applied to a substrate having a hydrophobic substance on the surface, photocatalytic oxide particles having a small particle size move upward. As a result, the coating surface has a small contact angle with water immediately after painting, it is possible to enjoy the self-cleaning function due to rain immediately after use, and the state is maintained for a long time by irradiation with sunlight. It becomes like this. At the same time, the particles dispersed in the hydrophobic resin emulsion having a large particle size move downward, and the adhesion to the substrate having the hydrophobic substance on the surface increases.
[0008]
In a preferred embodiment of the present invention, there is provided a photocatalytic coating agent comprising at least (a) photocatalytic oxide particles, (b) a hydrophobic resin emulsion, (c) water, and (d) silica particles. The average particle size of the photocatalytic oxide particles and silica particles is made smaller than the average particle size of the particles dispersed in the hydrophobic resin emulsion.
By adding silica particles, the contact angle with water immediately after coating of the coating surface becomes smaller, and it becomes easier to enjoy the self-cleaning function due to rain immediately after use.
[0009]
When the photocatalytic coating agent is applied to a substrate having a hydrophobic substance on the surface, the photocatalytic oxide particles and silica particles having a small particle size move upward. As a result, the coating surface has a small contact angle with water immediately after painting, it is possible to enjoy the self-cleaning function due to rain immediately after use, and the state is maintained for a long time by irradiation with sunlight. It becomes like this. At the same time, the particles dispersed in the hydrophobic resin emulsion having a large particle size move downward, and the adhesion to the substrate having the hydrophobic substance on the surface increases.
[0010]
In a preferred embodiment of the present invention, the average particle size of the photocatalytic oxide particles is 5 to 50 nm, and the average particle size of the particles dispersed in the hydrophobic resin emulsion is 80 to 300 nm.
When the average particle diameter of the photocatalytic oxide particles is 5 nm or more, the photocatalytic reaction due to irradiation with sunlight is sufficiently exhibited, and the hydrophilicity is easily maintained over a long period of time. Moreover, it becomes easy to maintain a highly hydrophilic state with a contact angle with water of 10 ° or less.
On the other hand, when the average particle diameter of the photocatalytic oxide particles is less than 50 nm and the average particle diameter of the particles dispersed in the hydrophobic resin emulsion is 80 nm or more, the photocatalytic oxide particles and the hydrophobic resin emulsion The difference in particle size from the dispersed particles is sufficiently large, so that the photocatalytic oxide particles having a small particle size are moved upward and the particles dispersed in the hydrophobic resin emulsion having a large particle size are dispersed. As a result, the surface of the coating has a small contact angle with water immediately after painting, and it is possible to enjoy the self-cleaning function due to rainfall immediately after use, and the state of the coating surface is sunlight. At the same time as being maintained for a long period of time by irradiation, adhesion with a substrate having a hydrophobic substance on the surface is increased.
Further, when the average particle size of the particles dispersed in the hydrophobic resin emulsion is 300 nm or more, the stability as an emulsion is lowered and the viscosity becomes high, so that it cannot be used as a coating composition.
[0011]
In a preferred embodiment of the present invention, the photocatalytic oxide particles have an average particle size of 5 to 50 nm, the silica particles have an average particle size of 5 to 100 nm, more preferably 5 to 50 nm, and the hydrophobic resin. The average particle size of the particles dispersed in the emulsion is 80 to 300 nm, more preferably 100 to 300 nm.
When the average particle diameter of the silica particles is smaller than 5 nm, the bonding strength between the silicas increases, so that the particles easily aggregate.
The average particle size of the photocatalytic oxide particles is less than 50 nm, the average particle size of the silica particles is less than 100 nm, more preferably less than 50 nm, and the average particle size of the particles dispersed in the hydrophobic resin emulsion is 80 nm or more, More preferably, when the particle diameter is 100 nm or more, the photocatalytic oxide particles having a small particle size and the photocatalytic oxide particles and silica particles and the particles dispersed in the hydrophobic resin emulsion have a small particle size. The upward movement of the silica particles and the downward movement of the particles dispersed in the hydrophobic resin emulsion having a large particle size are likely to occur, whereby the coating surface has a very small contact angle with water immediately after coating, It is possible to enjoy the self-cleaning function due to rain immediately after use, and the state will be maintained for a long time by the irradiation of sunlight. Made at the same time, it increases the adhesion to a substrate having a hydrophobic substance on the surface.
[0012]
In a preferred embodiment of the present invention, the blending ratio in the solid content is 1 to 20% by weight of the photocatalytic oxide particles, more preferably 1 to 5% by weight, and 5 to 99% by weight of the hydrophobic resin emulsion. More preferably, it is 10 to 99% by weight, and the mixing ratio of the water is 10 to 500 parts by weight, more preferably 10 to 109 parts by weight with respect to 100 parts by weight of the solid content.
When the mixing ratio of the water is 10 to 500 parts by weight, more preferably 10 to 109 parts by weight, a coating film can be formed with an appropriate film thickness as a paint having a film thickness of 1 μm to 1 mm.
Moreover, since the blending ratio of the photocatalytic oxide particles is 1% by weight or more, the coating surface has a small contact angle with water immediately after painting, and it is possible to enjoy a self-cleaning function due to rain immediately after use. And the state will be maintained over a long period of time by irradiation of sunlight.
Moreover, the blending ratio of the photocatalytic oxide particles is less than 20% by weight in the solid content, more preferably less than 5% by weight, so that the hydrophobic resin emulsion can be produced by the decomposition force based on the redox power of the photocatalytic oxide. There is no influence on the binder obtained by curing, and the self-cleaning function is maintained for a long time in outdoor use.
Moreover, adhesiveness with the base material which has a hydrophobic substance on the surface increases because the mixture ratio of hydrophobic resin emulsion is 5 weight% or more, More preferably, it is 10 weight% or more.
[0013]
In a preferred embodiment of the present invention, the blending ratio in the solid content is 1 to 20 wt% of the photocatalytic oxide particles, more preferably 1 to 5 wt% based on the total solid content, and the blending ratio of the silica particles. Is 1 to 90% by weight, the blending ratio of the hydrophobic resin emulsion is 5 to 98% by weight, more preferably 10 to 98% by weight, and the blending ratio of water is 10 to 500 parts by weight with respect to 100 parts by weight of the solid content. More preferably, the amount is 10 to 108 parts by weight.
When the blending ratio of silica particles is 1% by weight or more, the coating surface has a smaller contact angle with water immediately after painting, and it is possible to enjoy a self-cleaning function due to rain immediately after use, and in this state Is maintained over a long period of time by the irradiation of sunlight.
[0014]
In a preferred embodiment of the present invention, a photocatalytic coating agent comprising at least (a) photocatalytic oxide particles, (b) a hydrophobic resin emulsion, and (c) water, wherein the photocatalytic oxide The particles should be 1-5% by weight relative to the total solids.
The binder and photocatalyst obtained by curing the hydrophobic resin emulsion by the decomposition force based on the oxidation-reduction power of the photocatalytic oxide because the blending ratio of the photocatalytic oxide particles is less than 5% by weight with respect to the total solid content. The bonding strength of the conductive oxide particles and the bonding strength with the substrate are not affected, and the strength of the coating and the adhesion with the substrate are maintained over a long period of outdoor use.
[0015]
In a preferred embodiment of the present invention, there is provided a photocatalytic coating agent comprising at least (a) photocatalytic oxide particles, (b) a hydrophobic resin emulsion, (c) water, and (d) silica particles. The photocatalytic oxide particles should be 1 to 5% by weight based on the total solid content.
The binder and photocatalyst obtained by curing the hydrophobic resin emulsion by the decomposition force based on the oxidation-reduction power of the photocatalytic oxide because the blending ratio of the photocatalytic oxide particles is less than 5 parts by weight with respect to the total solid content. There is no influence on the bonding force between the conductive oxide particles and the silica particles and the bonding force with the base material, and the strength of the coating and the adhesion with the base material are maintained for a long time in outdoor use.
[0016]
In a preferred embodiment of the present invention, the hydrophobic resin emulsion is one or more of a fluororesin emulsion and a silicone emulsion. A weather resistance becomes favorable because it is a fluororesin emulsion and / or a silicone emulsion.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described.
First, terms used in the present invention will be described below.
In the present invention, “photocatalytic oxide particles” include, for example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, and oxidation. Particles such as cadmium, copper oxide, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, rhodium oxide, nickel oxide, rhenium oxide, and strontium titanate can be used.
When titanium oxide is used as a photocatalyst, it is preferable to use an anatase type or brookite type crystal because it has the strongest photocatalytic activity and develops over a long period of time.
[0018]
As the “hydrophobic resin emulsion”, for example, emulsions of fluororesin, silicone, acrylic silicone, vinyl acetate, vinyl acetate acrylic, acrylic urethane, acrylic, epoxy, vinyl vinyl acetate, vinylidene chloride, SBR latex and the like can be used.
Examples of the fluororesin emulsion include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, perfluorocyclopolymer, vinyl ether-fluoroolefin copolymer, vinyl ester-fluoroolefin copolymer, tetrafluoroethylene-vinyl ether copolymer, chlorotrifluoroethylene-vinyl ether copolymer, cross-linked tetrafluoroethylene urethane, Tetrafluoroethylene epoxy crosslinked product, tetra Le Oro ethylene acrylic crosslinked emulsion polymers containing tetrafluoroethylene melamine crosslinked body and the like fluoro group can be suitably used.
Silicone emulsions include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltribromosilane, methyltriisopropoxysilane, methyltrit-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyl Trichlorosilane, ethyltribromosilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltrichlorosilane, n-propyltribromosilane, n-propyl Triisopropoxysilane, n-propyltri-t-butoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltrichlorosilane, n-hexyltri Romsilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltrichlorosilane, n-decyltribromosilane, n-decyltriisopropoxy Silane, n-decyltri-t-butoxysilane, n-octatrimethoxysilane, n-octatriethoxysilane, n-octatrichlorosilane, n-octatribromosilane, n-octatriisopropoxysilane, n-octatrit-butoxysilane , Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltribromosilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane, dimethyldichlorosilane, dimethyldibromide Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldi Ethoxysilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltridibromosilane, trifluoropropyl Trimethoxysilane, trifluoropropyltriethoxysilane, vinyltrichlorosilane, trifluoropropyltriisopropyl Lopoxysilane, trifluoropropyltri-t-butoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Silane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacrylic Roxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltri-t-butoxysilane, γ-aminopropylmethyldi Toxisilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminomethacryloxypropyltri-t-butoxysilane, γ -Methylcaptopropylmethyldimethoxysilane, γ-methylcaptopropylmethyldiethoxysilane, γ-methylcaptopropyltrimethoxysilane, γ-methylcaptopropyltriethoxysilane, γ-methylcaptopropyltriisopropoxysilane, γ-methylcapto Hydrolysis of propyltri-t-butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, dehydration condensation polymer, etc. Rujon can be suitably used.
[0019]
As a preferred specific example of “silica particles”, amorphous silica particles are preferred. Amorphous silica includes colloidal silica. There are colloidal silica dispersed in water or dispersed in a non-aqueous organic solvent such as alcohol. Both can be used, but in the present invention, the stability of the constituent emulsion is slightly reduced. Therefore, it is preferable to use one dispersed in water. The colloidal silica dispersed in the organic solvent can be easily adjusted by replacing the aqueous solvent in the water-dispersed colloidal silica with an organic solvent.
[0020]
The average particle size of the photocatalytic oxide particles, silica particles, and particles dispersed in the hydrophobic resin emulsion was measured by dynamic light scattering measurement using a laser as a light source. As a measuring device, DLS-600 manufactured by Otsuka Electronics Co., Ltd. was used.
[0021]
In the coating agent of the present invention, for example, a colloidal silica is added to a sol of water-dispersible photocatalytic oxide particles as necessary, and then a hydrophobic resin emulsion is further added, and diluted with water as necessary. Can be obtained.
[0022]
In addition, the coating agent of the present invention can enjoy a self-cleaning function due to rainfall immediately after use by coating the base material surface having a hydrophobic substance on the surface and allowing it to harden. It can be modified to a photocatalytic composite material that is maintained over a long period of time by light irradiation. Here, curing at room temperature is advantageous for on-site construction.
[0023]
As the “base material having a hydrophobic substance on the surface”, for example, a plastic, an organic fiber, an organic fabric, a coated body such as a coated steel plate, or the like can be suitably used.
[0024]
It is preferable to add a metal such as Ag, Cu, or Zn to the coating agent of the present invention. The surface layer to which such a metal is added can kill bacteria, moths and algae attached to the surface even in the dark, and thus can further improve the antifouling property.
[0025]
Furthermore, platinum group metals such as Pt, Pd, Ru, Rh, Ir, and Os can be added to the coating agent of the present invention. The surface layer to which such a metal is added can enhance the redox activity of the photocatalyst, and can improve the degradability of organic contaminants and the decomposability of harmful gases and odors.
[0026]
In the coating agent of the present invention, a film-forming auxiliary can be used to improve the film-forming property of the hydrophobic resin emulsion on the substrate. The film-forming aid remains in the coating film even after most of the water has evaporated, and has a function of promoting the fusion of the emulsion particles. Specifically, an organic compound having a boiling point of 100 ° C. or higher can be given. Specific examples are shown below.
Ethylene glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol ethyl ether acetate, and diethylene glycol monobutyl ether acetate.
Propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether,
Propylene glycol ethers such as dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, polypropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, etc. Kind.
Examples include esters such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, n-PENTYL PROPIONATE, and dibutyl phthalate.
Among them, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, which is a kind of ester, has a high ability to penetrate into the fluororesin emulsion and has a lowering effect on the minimum film-forming temperature (MFT). Its use is preferred because it is expensive. Conversely, ethylene glycol ethers are highly toxic to the human body and are not preferred for use.
[0027]
A colorant can be further added to the coating agent of the present invention. As the colorant, at least one is selected from inorganic pigments, organic pigments, dyes and the like.
Inorganic pigments include metal oxides such as titanium oxide, zinc white, bengara, chromium oxide, cobalt blue and iron black, metal hydroxides such as alumina white and yellow iron oxide, ferrocyan compounds such as bitumen, Lead chromate such as chrome lead, zinc chromate, molybdenum red, sulfides such as zinc sulfide, vermilion, cadmium yellow, cadmium red, sulfates such as selenium compounds, barite, precipitated barium sulfate, heavy calcium carbonate, Carbonates such as precipitated calcium carbonate, silicates such as hydrous silicate, clay and ultramarine, carbons such as carbon black, metal powders such as aluminum powder, bronze powder and zinc powder, mica and titanium oxide systems Pearl pigment system.
Organic pigments include nitroso pigments such as naphthol green B, nitro pigments such as naphthol S, azo pigments such as risol red, lake red C, fast yellow and naflor red, alkali blue red, rhodamine chelate, quinacridone red And condensed polycyclic pigments such as dioxazine bio red and isoindolinone yellow.
Examples of the dye include disperse dyes, basic dyes, direct dyes, and acid dyes.
[0028]
【Example】
(Preparation of coating composition)
In addition, the solid content concentration and the average particle diameter of the materials used in the preparation of the present examples and comparative examples are as shown in Table 1.
[0029]
[Table 1]
[0030]
Example 1
10.2 parts by weight of photocatalytic oxide sol (Nippon Parkerizing Co., Ltd., trade name Pal Titanium 5610), colloidal silica (Nihon Chemical Co., Ltd., trade name Silica Doll 30B), 79.6 parts by weight, fluororesin emulsion (Asahi Glass Co., Ltd.) Manufactured by trade name, Lumiflon FE3000, 10.2 parts by weight (shown as solid content above) and 2.1 parts by weight of a film-forming aid (trade name Texanol, manufactured by Eastman Kodak Co., Ltd.) It was adjusted. The water content at this time was 433 parts by weight with respect to a total of 100 parts by weight of the solid content.
[0031]
Example 2
20.1 parts by weight of photocatalytic oxide sol (trade name, TKS-203, manufactured by Teika Co., Ltd.), 10.2 parts by weight of colloidal silica (trade name, Snowtex 50, manufactured by Nissan Chemical Co., Ltd.), fluororesin emulsion (Asahi Glass Co., Ltd.) A water-based coating composition comprising 69.7 parts by weight (made by trade name Lumiflon FE4300) (shown as solid content above) and 15.7 parts by weight of a film-forming aid (trade name Texanol, manufactured by Eastman Kodak Company) was prepared. . The water content at this time was 159 parts by weight with respect to a total of 100 parts by weight of the solid content.
[0032]
Example 3
Photocatalyst oxide sol (Nippon Parkerizing Co., Ltd., trade name Pal Titanium 5610) 3.2 parts by weight, colloidal silica (Nissan Chemical Co., Ltd., trade name Snowtex 50) 25.9 parts by weight, fluororesin emulsion (Asahi Glass Co., Ltd.) Manufactured, trade name Lumiflon FE4300) 3.2 parts by weight, coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name MF Color MF5160) 38.9 parts by weight, extender pigment (made by Otsuka Chemical Co., Ltd., trade name Tismo-N) ) 28.8 parts by weight (shown as solid content above) and 0.7 parts by weight of a film-forming aid (manufactured by Chisso Corporation, trade name CS-12) were prepared. The water content at this time was 132 parts by weight with respect to a total of 100 parts by weight of the solid content.
[0033]
Example 4
Photocatalyst oxide sol (Ishihara Sangyo Co., Ltd., trade name STS-21) 1.0 part by weight, colloidal silica (Nissan Chemical Co., Ltd., trade name Snowtex ZL) 38.8 parts by weight, fluororesin emulsion (Asahi Glass Co., Ltd.) Company-made, trade name Lumiflon FE4300) 23.1 parts by weight, color pigment (Daiichi Seika Kogyo Co., Ltd., trade name MF Color MF5160) 20.4 parts by weight, extender pigment A (manufactured by Otsuka Chemical Co., Ltd., trade name HT) -300) 4.7 parts by weight, extender pigment B (manufactured by Nippon Talc Co., Ltd., Microace P3) 12.0 parts by weight (shown as solid content above), film-forming aid (manufactured by Chisso Corporation, trade name CS -12) A water-based coating composition that was 7.8 parts by weight was prepared. The water content at this time was 152 parts by weight with respect to a total of 100 parts by weight of the solid content.
[0034]
Example 5
1.4 parts by weight of photocatalytic oxide sol (trade name STS-21, manufactured by Ishihara Sangyo Co., Ltd.), 50.8 parts by weight of colloidal silica (trade name Snowtex ZL, manufactured by Nissan Chemical Co., Ltd.), fluororesin emulsion (Asahi Glass Co., Ltd.) 15.0 parts by weight made by company, trade name Lumiflon FE4300), 26.7 parts by weight pigment (made by Dainichi Seika Kogyo Co., Ltd., trade name MF Color MF5160), extender pigment (trade name HT- by Otsuka Chemical Co., Ltd.) 300) 6.1 parts by weight (displayed as solid content above) and 3.3 parts by weight of a film-forming aid (trade name CS-12, manufactured by Chisso Corporation) were prepared. The water content at this time was 175 parts by weight with respect to a total of 100 parts by weight of the solid content.
[0035]
Example 6
18.3 parts by weight of photocatalytic oxide sol (Ishihara Sangyo Co., Ltd., trade name STS-21), colloidal silica (Nissan Chemical Co., Ltd., trade name Snowtex 50), 44.3 parts by weight, silicone emulsion (Dainippon Ink) 9.9 parts by weight of Chemical Industry Co., Ltd., trade name Boncoat SA-5080), 15.2 parts by weight of colored pigment (Daiichi Seika Kogyo Co., Ltd., trade name MF Color MF5160), extender pigment (Otsuka Chemical Co., Ltd.) A coating composition of 12.3 parts by weight (manufactured by trade name HT-300) (shown as solid content above) and 2.4 parts by weight of a film-forming aid (trade name CS-12, manufactured by Chisso Corporation) was prepared. The water content at this time was 294 parts by weight with respect to a total of 100 parts by weight of the solid content.
[0036]
Comparative Example 1
Fluorine resin emulsion (Asahi Glass Co., Ltd., trade name Lumiflon FE4300) 67.8 parts by weight Color pigment (Daiichi Seika Kogyo Co., Ltd., trade name MF Color MF5160) 26.7 parts by weight, extender (Otsuka Chemical Co., Ltd.) The water-based coating composition is 5.5 parts by weight (made by trade name Tismo-N) (indicated by solid content) and 14.7 parts by weight of a film-forming aid (trade name CS-12, manufactured by Chisso Corporation). did. The water content at this time was 85 parts by weight with respect to a total of 100 parts by weight of the solid content.
[0037]
Comparative Example 2
10 parts by weight of photocatalytic oxide sol (Nippon Parkerizing Co., Ltd., trade name Pal Titanium 5610), 23.9 parts by weight of colloidal silica (Nissan Chemical Co., Ltd., trade name Snowtex 50), Coloring pigment (Daiichi Seika Kogyo Co., Ltd.) The water-based paint composition was 11.4 parts by weight manufactured by trade name MF color MF5160) and 54.7 parts by weight (made by Otsuka Chemical Co., Ltd., trade name Tismo-N) (shown as solid content above). . The water content at this time was 269 parts by weight with respect to a total of 100 parts by weight of the solid content.
[0038]
Comparative Example 3
9.8 parts by weight of a photocatalytic oxide (Nippon Parkerizing Co., Ltd., trade name Pal Titanium 5610), colloidal silica (Nissan Chemical Co., Ltd., trade name Snowtex 50), 79.3 parts by weight, fluororesin (Asahi Glass Co., Ltd., A coating composition having a trade name of Lumiflon LF100) of 10.9 parts by weight (shown as solid content above) was prepared. The water content at this time was 325 parts by weight with respect to a total of 100 parts by weight of the solid content. Immediately before coating, 0.4 part by weight of a curing agent (trade name Coronate HX, manufactured by Nippon Polyurethane Co., Ltd.) was added to 100 parts by weight of the coating composition.
[0039]
(Applying method to substrate)
An asbestos-cement calcium silicate board cut according to 150 mm × 65 mm (in accordance with JIS A5418) was spray-coated with an epoxy resin primer (SK Kaken, trade name: SK Surf Epo) and dried at room temperature for 24 hours. Subsequently, acrylic urethane paint (Isamu paint, trade name: High Art 1000) was spray-coated on the asbestos-cement calcium silicate plate subjected to the primer coating described above, and dried at room temperature for 24 hours. Subsequently, the coating compositions of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 prepared above were brush-coated on asbestos cement calcium silicate plates subjected to primer coating and acrylic urethane coating, and then coated. Got.
In addition, Example 4 was obtained by brush-coating a primer preparation coating material (trade name “Remake Plastic”) manufactured by Suzuka Fine Co., Ltd. on a primer coated asbestos cement calcium silicate plate and drying at room temperature for 24 hours. The coating compositions 5 and 6 were applied to obtain a coating.
The coating was performed with the test piece upright. The weight of the paint composition brushed on was 15 g / m @ 2. Finally, the coating was dried at room temperature for 24 hours to obtain test pieces 1-9.
Test piece 1: Application of the paint of Example 1
Test piece 2: Application of paint of Example 2
Specimen 3: Applying paint of Example 3
Test piece 4: Application of the paint of Example 4
Test piece 5: Application of the paint of Example 5
Test piece 6: Applying the paint of Example 6
Test piece 7: Application of the paint of Comparative Example 1
Test piece 8: Application of the paint of Comparative Example 2
Test piece 9: coated with the paint of Comparative Example 3
[0040]
Preparation of test pieces for Erichsen evaluation and nitric oxide decomposition performance evaluation
An epoxy resin-based primer (SK Kaken, trade name: SK Surf Epoxy) was spray-coated on a galvanized steel sheet (compliant with JIS A5400) cut to 150 mm × 65 mm, and dried at room temperature for 24 hours. Subsequently, the coating compositions of Examples 1, 2, 3, 4, 5, 6 and Comparative Examples 1, 2, and 3 prepared above were brush-coated onto the primer-coated galvanized steel sheet and coated Got.
The coating was performed with the test piece upright. The weight of the paint composition brushed on was 15 g / m @ 2. Finally, the coating material was dried at room temperature for 24 hours to obtain test pieces 10 to 18.
Test piece 10: Application of the paint of Example 1
Test piece 11: Application of the paint of Example 2
Test piece 12: Application of the paint of Example 3
Test piece 13: Application of the paint of Example 4
Test piece 14: Application of the paint of Example 5
Test piece 15: Application of the paint of Example 6
Test piece 16: Application of the paint of Comparative Example 1
Test piece 17: Application of the paint of Comparative Example 2
Test piece 18: Application of the paint of Comparative Example 3
[0041]
Next, for each of the above test pieces, the film thickness, presence or absence of cracks, adhesion, Erichsen evaluation, gloss, alkali resistance, boiling water resistance, thermal cooling cycle test, hydrophilicity (the initial contact angle and the contact angle at the time of ultraviolet irradiation) Measurement) was evaluated, and the results are shown in Table 2. The results of self-cleaning evaluation are shown in Table 3. The results of the nitric oxide decomposition performance are shown in FIGS.
[0042]
[Table 2]
[0043]
[Table 3]
[0044]
The evaluation method is as follows.
Film thickness: The specimen was observed from the cross-sectional direction with a scanning electron microscope (S-4100, manufactured by Hitachi, Ltd.), and the film thickness was measured.
Presence or absence of cracks: The presence or absence of cracks was confirmed by observing the surface of the test piece using an optical microscope (VF-7500 made by Keyence).
Adhesiveness: JIS K5400 A cross-cut test method was used. That is, a 2-mm wide grid cut is made with a cutter from the top of the coating film of the prepared test piece. The size is 1 cm square and the number of grids is 25. Then, apply cellophane tape so that the grid is completely covered. After that, quickly peel off and count the number of grids that remain attached.
Erichsen evaluation: Using an Erichsen tester in accordance with JIS B7729, a steel ball is extruded from the back surface by a test piece applied to a metal plate, and the test piece is deformed. Extrude distance until cracks, cracks, and peeling occur in the coating is examined.
Gloss: The glossiness of the prepared test piece was measured using VGS-1D manufactured by Nippon Denshoku Industries Co., Ltd.
Alkali resistance: Soaked in a saturated aqueous solution of calcium hydroxide at room temperature for 7 days, taken out, washed with distilled water, sufficiently dried, and then evaluated by visual appearance.
Boiling water resistance: immersed in boiling water of 95 ° C. or higher for 2 hours, taken out, washed with distilled water, sufficiently dried, and then evaluated by visual appearance.
Thermal cooling cycle test: 10 cycles of 3 hours in a constant temperature bath at 50 ° C., 3 hours in a constant temperature bath at −20 ° C., then 18 hours in a constant temperature water bath at 25 ° C. After taking out, it wash | cleans with distilled water, and after making it fully dry, it evaluates by visual appearance.
Hydrophilicity (initial contact angle): The contact angle of the test piece surface with water was measured using CX-150 manufactured by Kyowa Interface Science.
Hydrophilicity (at the time of UV irradiation): The prepared test piece was irradiated with 0.5 mW / cm2 UV light generated from a BLB lamp for 7 days or 3.0 mW / cm2 UV light generated from a germicidal lamp lamp for 3 days, and then with water. The contact angle was measured using CX-150 manufactured by Kyowa Interface Science.
Self-cleaning property (exposure outdoors): The prepared test piece is directed to the south side, and is inclined outdoors by 45 ° with respect to the vertical. Visual appearance evaluation and contact angle were measured before exposure, 1 month after exposure, and 2 months after exposure.
Nitric oxide decomposition performance evaluation: A schematic diagram of the evaluation apparatus is shown in FIG. The concentration of nitric oxide on the inlet side is adjusted to 0.25 ppm with air. Adjust the flow rate to 1 liter per minute. After installing the test piece, let the gas flow until the flow rate is stable for 30 minutes. Then UV light is 0.5mW / cm with BLB lamp. 2 Irradiate with the intensity of. Record the concentration of nitric oxide and nitrogen dioxide.
[0045]
【The invention's effect】
As described above, according to the present invention, the antifouling and hydrophilic effects due to the addition of the photocatalyst are exhibited. Moreover, even if the thickness of the coating film formed on the surface of an organic base material such as plastic is increased, a water-based coating composition that does not generate cracks and becomes a coating film having excellent peel strength can be obtained.
[Brief description of the drawings]
FIG. 1 is a diagram showing the nitric oxide decomposition performance of an example of the present invention.
FIG. 2 is a graph showing the nitric oxide decomposition performance in another example of the present invention.
FIG. 3 is a graph showing the nitric oxide decomposition performance in another example of the present invention.
FIG. 4 is a graph showing the nitric oxide decomposition performance of a comparative example.
FIG. 5 is a graph showing the nitric oxide decomposition performance of a comparative example.
FIG. 6 is a schematic diagram of an apparatus for evaluating nitric oxide decomposition performance.
Claims (6)
前記（a）成分及び（d）成分の平均粒径は、前記（b）成分中に分散した粒子の平均粒径よりも小さく、
前記（ a ）成分の全固形分中の割合が１〜５重量％で且つ前記（ｄ）成分の配合割合が１０〜９０重量％であり、
基材に塗布すると、光触媒性酸化物粒子及びシリカ粒子が上方に移動し、膜厚１μｍ〜１ｍｍの塗膜が形成されることを特徴とする光触媒性コーティング剤。A photocatalytic coating agent comprising at least (a) photocatalytic oxide particles, (b) a hydrophobic resin emulsion, (c) water, (d) silica particles, and ( e ) a color pigment ,
The average particle size of the component (a) and the component (d) is smaller than the average particle size of the particles dispersed in the component (b),
The proportion of the component ( a ) in the total solid content is 1 to 5% by weight, and the proportion of the component (d) is 10 to 90% by weight,
When applied to a substrate, the photocatalytic oxide particles and silica particles move upward to form a coating film having a thickness of 1 μm to 1 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002158949A JP3717868B2 (en) | 2001-08-30 | 2002-05-31 | Photocatalytic coating agent, photocatalytic composite material and production method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001261886 | 2001-08-30 | ||
| JP2002157656 | 2002-05-30 | ||
| JP2002158949A JP3717868B2 (en) | 2001-08-30 | 2002-05-31 | Photocatalytic coating agent, photocatalytic composite material and production method thereof |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004130037A Division JP2004269898A (en) | 2001-08-30 | 2004-04-26 | Photocatalytic coating agent and photocatalytic composite material, and preparation process for this agent |
| JP2005005333A Division JP2005179686A (en) | 2001-08-30 | 2005-01-12 | Photocatalytic coating agent, photocatalytic composite material and method for producing the same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2004051644A JP2004051644A (en) | 2004-02-19 |
| JP2004051644A5 JP2004051644A5 (en) | 2005-04-28 |
| JP3717868B2 true JP3717868B2 (en) | 2005-11-16 |
Family
ID=31950396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002158949A Expired - Fee Related JP3717868B2 (en) | 2001-08-30 | 2002-05-31 | Photocatalytic coating agent, photocatalytic composite material and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3717868B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004269898A (en) * | 2001-08-30 | 2004-09-30 | Toto Ltd | Photocatalytic coating agent and photocatalytic composite material, and preparation process for this agent |
| JP2009280829A (en) * | 2001-08-30 | 2009-12-03 | Toto Ltd | Photocatalytic coating material, photocatalytic composite material, and method of manufacturing the same |
| CN104861861A (en) * | 2014-02-24 | 2015-08-26 | Toto株式会社 | Coating composition and coated body |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004018338A1 (en) * | 2004-04-15 | 2005-11-10 | Sto Ag | coating material |
| KR100876529B1 (en) * | 2004-09-15 | 2008-12-31 | 주식회사 엘지화학 | Film or building exterior material using self-cleaning coating composition and method for producing same |
| JP2006328196A (en) * | 2005-05-25 | 2006-12-07 | Daikin Ind Ltd | Structure of stain-resistant coated film |
| JP2007262150A (en) * | 2006-03-27 | 2007-10-11 | Ohbayashi Corp | Photocatalyst coating agent and photocatalyst carrier |
| JP5957175B2 (en) * | 2008-03-04 | 2016-07-27 | 株式会社東芝 | Antibacterial membrane and antibacterial member |
| JP5391890B2 (en) * | 2009-07-14 | 2014-01-15 | Ｔｏｔｏ株式会社 | Photocatalyst-coated body and photocatalyst coating liquid |
| JP5391892B2 (en) * | 2009-07-16 | 2014-01-15 | Ｔｏｔｏ株式会社 | Photocatalyst-coated body and photocatalyst coating liquid |
| JP5391902B2 (en) * | 2009-07-30 | 2014-01-15 | Ｔｏｔｏ株式会社 | Photocatalyst-coated body and photocatalyst coating liquid |
| JP2012250134A (en) | 2009-09-30 | 2012-12-20 | Toto Ltd | Photocatalyst-coated object, and photocatalyst coating liquid therefor |
| JP2012250133A (en) | 2009-09-30 | 2012-12-20 | Toto Ltd | Photocatalyst-coated object, and photocatalyst coating liquid therefor |
| WO2012060398A1 (en) | 2010-11-02 | 2012-05-10 | Toto株式会社 | Photocatalyst-coated object and photocatalyst coating liquid for same |
| KR101868192B1 (en) * | 2011-06-07 | 2018-06-15 | 주식회사 다이셀 | Photocatalytic coating film and method for producing same |
| JP2017042683A (en) * | 2014-03-03 | 2017-03-02 | 株式会社鯤コーポレーション | Photocatalyst coating liquid, and photocatalyst film using the same |
| JP6381483B2 (en) * | 2014-10-29 | 2018-08-29 | 三菱電機株式会社 | Coating composition, antifouling member, air conditioner and ventilation fan |
| JP6953107B2 (en) * | 2015-08-31 | 2021-10-27 | 日本光触媒センター株式会社 | Enclosure |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09234375A (en) * | 1996-03-01 | 1997-09-09 | Mitsubishi Paper Mills Ltd | Photo-reactive harmful matter removing material |
| DE19613645A1 (en) * | 1996-04-04 | 1997-10-09 | Inst Neue Mat Gemein Gmbh | Graded-structure optical components and method of making the same |
| JPH10363A (en) * | 1996-06-13 | 1998-01-06 | Dainippon Toryo Co Ltd | Formation of coating film having photochemical activity |
| JP3991172B2 (en) * | 1997-02-06 | 2007-10-17 | 信越化学工業株式会社 | Coating composition, hydrophilic film, and coated article having hydrophilic film |
| JPH11140433A (en) * | 1997-11-10 | 1999-05-25 | Toto Ltd | Photocatalytic aqueous composition and formation of photocatalytic aqueous coat |
| JPH11166132A (en) * | 1997-12-05 | 1999-06-22 | Toto Ltd | Photocatalytic hydrophilic composition |
| TW473400B (en) * | 1998-11-20 | 2002-01-21 | Asahi Chemical Ind | Modified photocatalyst sol |
| JP2001064583A (en) * | 1999-08-31 | 2001-03-13 | Toto Ltd | Photocatalyst coating composition, photocatalytic coating film, article covered therewith, and method for forming the coating film |
| JP2002273233A (en) * | 2000-12-04 | 2002-09-24 | Asahi Kasei Corp | Modified photocatalyst and photocatalytic composition using the same |
-
2002
- 2002-05-31 JP JP2002158949A patent/JP3717868B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004269898A (en) * | 2001-08-30 | 2004-09-30 | Toto Ltd | Photocatalytic coating agent and photocatalytic composite material, and preparation process for this agent |
| JP2009280829A (en) * | 2001-08-30 | 2009-12-03 | Toto Ltd | Photocatalytic coating material, photocatalytic composite material, and method of manufacturing the same |
| CN104861861A (en) * | 2014-02-24 | 2015-08-26 | Toto株式会社 | Coating composition and coated body |
| CN104861861B (en) * | 2014-02-24 | 2017-09-15 | Toto株式会社 | Coating composition and coated-body |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004051644A (en) | 2004-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3717868B2 (en) | Photocatalytic coating agent, photocatalytic composite material and production method thereof | |
| EP1512728B1 (en) | Photocatalytic coating material, photocatalytic composite material and process for producing the same, self-cleaning water-based coating compositions, and self-cleaning member | |
| JP5589267B2 (en) | Self-cleaning coating composition | |
| US8512855B2 (en) | Self-cleaning member and coating composition | |
| JP3985164B2 (en) | Functional coating material, functional composite material and method for producing the same | |
| KR20040095156A (en) | A self-decontaminating or self-cleaning coating for protection against hazardous bio-pathogens and toxic chemical agents | |
| JP4812902B1 (en) | Antifouling paint composition and method for forming antifouling coating film | |
| JP2004143452A (en) | Self-cleaning aqueous coating composition and self- cleaning member | |
| JP6046436B2 (en) | Method for forming antifouling coating film and antifouling paint | |
| JP2005179686A (en) | Photocatalytic coating agent, photocatalytic composite material and method for producing the same | |
| JP3584935B1 (en) | Base coating composition for photocatalytic coating film, photocatalytic coated product, and method for producing photocatalytic coated product | |
| JP2003342526A (en) | Self-cleaning aqueous coating composition and self- cleaning member | |
| JP5065236B2 (en) | Antifouling coating liquid, antifouling coating layer forming method, and ceramic building material having antifouling coating layer | |
| JP2004269898A (en) | Photocatalytic coating agent and photocatalytic composite material, and preparation process for this agent | |
| JP2009280829A (en) | Photocatalytic coating material, photocatalytic composite material, and method of manufacturing the same | |
| JP2010222427A (en) | Aqueous coating agent | |
| JP2005120212A (en) | Functional coating material, functional composite material and method for producing the same | |
| JP2010138358A5 (en) | ||
| JP2010222427A5 (en) | ||
| JP6116045B2 (en) | Painted building materials | |
| JP2007145977A (en) | Aqueous coating liquid and functional coating film | |
| JP6953107B2 (en) | Enclosure | |
| JP2004051643A (en) | Self-cleaning water-borne coating composition and self-cleaning member | |
| JP2004323739A (en) | Method for controlling contact angle of photocatalyst coating film with water and photocatalyst coating film | |
| JP2001089711A (en) | Primer composition for fixing photocatalytic thin film to plastic substrate, and photocatalytic member |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040415 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040415 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20040415 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20040415 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040616 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040615 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040903 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20040913 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20041012 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20041221 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050106 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20050830 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050831 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3717868 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313114 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| S631 | Written request for registration of reclamation of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313631 |
|
| S201 | Request for registration of exclusive licence |
Free format text: JAPANESE INTERMEDIATE CODE: R314201 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313114 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080909 Year of fee payment: 3 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090909 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100909 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100909 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110909 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120909 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120909 Year of fee payment: 7 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130909 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |