WO2010150906A1 - 光触媒塗装体および光触媒コーティング液 - Google Patents
光触媒塗装体および光触媒コーティング液 Download PDFInfo
- Publication number
- WO2010150906A1 WO2010150906A1 PCT/JP2010/060958 JP2010060958W WO2010150906A1 WO 2010150906 A1 WO2010150906 A1 WO 2010150906A1 JP 2010060958 W JP2010060958 W JP 2010060958W WO 2010150906 A1 WO2010150906 A1 WO 2010150906A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photocatalyst
- photocatalytic
- particles
- coated body
- metal oxide
- Prior art date
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 201
- 239000011248 coating agent Substances 0.000 title claims abstract description 96
- 238000000576 coating method Methods 0.000 title claims abstract description 92
- 239000007788 liquid Substances 0.000 title claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 142
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 230000001699 photocatalysis Effects 0.000 claims abstract description 77
- 239000000839 emulsion Substances 0.000 claims abstract description 52
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 43
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 28
- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 28
- 229920001296 polysiloxane Polymers 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 22
- 239000000049 pigment Substances 0.000 claims description 14
- 229910000077 silane Inorganic materials 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 81
- -1 silane compound Chemical class 0.000 description 66
- 239000000463 material Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910052809 inorganic oxide Inorganic materials 0.000 description 10
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- 239000013032 Hydrocarbon resin Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
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- 238000013461 design Methods 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
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- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
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- 229940121375 antifungal agent Drugs 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
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- 229910052918 calcium silicate Inorganic materials 0.000 description 5
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
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- 239000012855 volatile organic compound Substances 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
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- 150000001412 amines Chemical class 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- 239000005361 soda-lime glass Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
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- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 3
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- 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
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
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- 229940031957 lauric acid diethanolamide Drugs 0.000 description 1
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- 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
- LLZATBMLXDAAOR-UHFFFAOYSA-N n-benzyl-n-methyltetradecan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCCCCCC[NH+](C)CC1=CC=CC=C1 LLZATBMLXDAAOR-UHFFFAOYSA-N 0.000 description 1
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- XQAABEDPVQWFPN-UHFFFAOYSA-N octyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCCCCCCC)=CC(N2N=C3C=CC=CC3=N2)=C1O XQAABEDPVQWFPN-UHFFFAOYSA-N 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- CAVXVRQDZKMZDB-UHFFFAOYSA-M sodium;2-[dodecanoyl(methyl)amino]ethanesulfonate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CCS([O-])(=O)=O CAVXVRQDZKMZDB-UHFFFAOYSA-M 0.000 description 1
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- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
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- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- VDWRUZRMNKZIAJ-UHFFFAOYSA-N tetradecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCN VDWRUZRMNKZIAJ-UHFFFAOYSA-N 0.000 description 1
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- PCADGSDEFOMDNL-UHFFFAOYSA-N tri(propan-2-yloxy)-(3,3,3-trifluoropropyl)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCC(F)(F)F PCADGSDEFOMDNL-UHFFFAOYSA-N 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
- 150000003918 triazines Chemical class 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
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229940094989 trimethylsilane Drugs 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
- 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 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
- A61L9/18—Radiation
- A61L9/20—Ultra-violet radiation
- A61L9/205—Ultra-violet radiation using a photocatalyst or photosensitiser
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Definitions
- the present invention is capable of decomposing harmful gases, self-cleaning by rain and water washing, easy to wash, VOC (volatile organic compounds (volatile organic compounds)) relates to a photocatalyst-coated body having photocatalytic functions such as degradability, antibacterial properties, antifungal properties, and antiviral properties. Furthermore, the present invention forms a coating layer on members constituting the exterior, interior, etc., thereby decomposing harmful gases, self-cleaning by rain / washing, ease of washing, VOC degrading, antibacterial, antifungal. The present invention relates to a photocatalyst coating solution capable of imparting a photocatalytic function such as antiviral properties.
- photocatalysts such as titanium oxide have been used for building structures, structures, vehicles, members constituting them, and composite materials.
- a base material surface is supported with a photocatalyst to give the base material a function of decomposing harmful substances such as NOx and SOx using light energy.
- the layer surface that has become hydrophilic upon light irradiation has a so-called self-cleaning function in which attached dirt is washed away by rain.
- the base material is given a function of decomposing toxic substances such as VOC using light energy, an antibacterial function, and an antifungal function. It has been done to give antiviral function.
- Patent Document 1 proposes the use of a coating agent using a photocatalyst and silica having a particle size smaller than that of a hydrophobic resin emulsion.
- this aqueous dispersion of the coating agent is applied to the substrate, the photocatalyst particles and silica particles move toward the surface of the photocatalyst layer and solidify before drying.
- more photocatalyst particles are present on the surface of the photocatalyst layer, and the photocatalytic function is enhanced.
- JP 2004-97630 A Patent Document 2
- a photocatalyst layer containing photocatalyst particles is provided on a sunshade base material, and the photocatalyst particles have a high concentration in the surface direction of the layer.
- a specific method for this is to use photocatalyst particles modified with a hydrophobic silane compound or hydrosilane to lower the surface energy as photocatalyst particles, and phenyl having a relatively large surface energy as a binder for binding the photocatalyst particles to each other.
- the surface energy of the photocatalyst particles is made smaller than the surface energy of the binder.
- a coating agent in which the photocatalyst particles and the binder are dispersed in a mixed solvent of toluene-isopropanol-butyl cellosolve in which they are easily dispersed is used.
- the organic solvent dispersion of the coating agent is applied to the substrate, the photocatalyst particles move toward the surface of the photocatalyst layer and solidify until the substrate is dried. As a result, more photocatalyst particles are present on the surface of the photocatalyst layer, and the photocatalytic function is enhanced.
- Patent Document 3 proposes a coating agent containing a tetrafluoroethylene-hexafluoropropylene copolymer emulsion as a binder.
- the binder is unevenly distributed in the direction of the interface with the base material, and the photocatalyst is relatively unevenly distributed on the surface of the photocatalyst layer.
- the photocatalyst particles are present at a high concentration on the surface of the photocatalyst layer and are present at a relatively low concentration on the interface side of the photocatalyst layer with the base material, the influence of the photocatalyst on the base material is reduced. It is advantageous.
- the base material itself has design properties, the base material is hardly decomposed and deteriorated by the photocatalyst.
- the photocatalyst layer needs to have a certain thickness. Even in this case, the fact that the photocatalyst is small on the interface side with the base material can reduce the influence thereof even though a relatively large amount of the photocatalyst is supported on the base material, It can be said that it is preferable.
- the present inventors have recently developed a photocatalyst layer formed of a coating liquid containing photocatalytic metal oxide particles and a resin emulsion on silica particles coated or modified with a substance having a hydrophobic group. It has been found that the photocatalyst function is remarkably improved as compared with the photocatalyst layer formed using the particles as they are. Such improvement of the photocatalytic function is due to the fact that the concentration of the metal element of the photocatalytic metal oxide particles in the photocatalytic layer shows a concentration gradient that gradually increases from the center of the layer toward the outermost layer. The present invention is based on such knowledge.
- an object of the present invention is to provide a photocatalyst-coated body excellent in photocatalytic function and a photocatalyst coating liquid used for the formation thereof.
- the photocatalyst coating body by this invention is a photocatalyst coating body provided with the photocatalyst layer on the base-material surface, Comprising:
- the said photocatalyst layer is a photocatalytic metal oxide particle, a silica particle, the dried material of a resin emulsion,
- the silica particles are coated or modified with a substance having a hydrophobic group.
- the photocatalytic coating liquid according to the present invention includes photocatalytic metal oxide particles, silica particles, a resin emulsion, and a solvent, and the silica particles are coated or modified with a substance having a hydrophobic group. Yes.
- the photocatalyst-coated body according to the present invention has an excellent photocatalytic function. Furthermore, according to a preferred embodiment of the present invention, when the photocatalyst layer is transparent, the substrate design can be utilized when the photocatalyst layer is transparent, and the photocatalyst layer contains a color pigment. When it exists, it is excellent in base-material concealing property and a design can be provided with a photocatalyst layer.
- the photocatalyst-coated body according to the present invention is a photocatalyst-coated body having a photocatalyst layer on a substrate surface, and the photocatalyst layer includes photocatalytic metal oxide particles, silica particles, and a dried resin emulsion. And the silica particles are coated or modified with a substance having a hydrophobic group.
- the photocatalytic activity can be significantly increased by using silica particles coated or modified with a substance having a hydrophobic group as compared with the case where silica particles are added as they are.
- the external appearance change of a coating body is suppressed over a long period of time.
- the photocatalyst layer as used in the field of this invention means the part formed by applying the coating liquid containing a photocatalyst particle to the base-material surface.
- the photocatalyst particles exist in the portion, any form may be used. That is, it may be completely film-shaped or partially film-shaped. Moreover, it may exist discretely in the shape of islands on the substrate surface.
- the concentration of the metal element of the photocatalytic metal oxide particles in the outermost layer of the photocatalyst layer is higher than that in the center of the layer.
- the concentration gradient of the metal element of the photocatalytic metal oxide particles in the photocatalyst layer increases from the vicinity of the interface with the substrate to the outermost layer. It is considered that the strength of the photocatalytic function as a coated body is mainly governed by the amount of the photocatalytic metal oxide present in the outermost layer.
- the photocatalytic function of the coated body according to the present invention in which the photocatalytic oxide particles are unevenly distributed in the outermost layer of the photocatalytic layer is high.
- the coated body according to the present invention in which the photocatalytic metal oxide particles are present at a high concentration on the surface of the photocatalyst layer and is present at a relatively low concentration on the interface side with the base material of the photocatalyst layer is a base material of the photocatalyst. This is advantageous because the influence on the is small.
- the base material when the base material itself has design properties, the base material is hardly decomposed and deteriorated by the photocatalyst.
- the coated body according to the present invention having a small amount of photocatalyst on the interface side with the base material reduces the influence of the photocatalyst on the base material even though a relatively large amount of the photocatalyst is supported on the base material. This is advantageous in that
- the substance having a hydrophobic group is a silane having a hydrophobic group and / or a silicone having a hydrophobic group. Since these substances have a siloxane bond in common with the silica particles, the silica surface can be easily coated and modified with these substances by a coupling treatment or the like.
- the film thickness of the photocatalyst layer is more than 3 ⁇ m and less than 3 mm.
- the concealment property of the ultraviolet ray by the photocatalyst layer is enhanced, and the influence of the ultraviolet ray on the substrate can be reduced.
- the photocatalyst layer contains a color pigment
- the substrate can be sufficiently concealed, and a design can be imparted to the substrate by the photocatalyst layer.
- the coating film formation in an appropriate curing time is attained.
- the photocatalytic layer is transparent.
- the design which a base material has can be utilized as it is because a photocatalyst layer is transparent.
- the degree of “transparency” it is more preferable to ensure the linear transmittance of the photocatalyst layer at a wavelength of 550 nm of 50% or more, preferably 70% or more, more preferably 80% or more.
- the dry matter content of the resin emulsion is 50% or more, preferably 70% or more, based on the total mass of the solid content of the resin emulsion, photocatalytic metal oxide particles, and silica particles. Most preferably, it is 85% or more. By setting it as such a content, it becomes easy to ensure the transparency of a photocatalyst layer.
- the photocatalyst layer can further contain a color pigment. Since the photocatalyst layer is colored with a color pigment, the concealability of the substrate can be obtained, and a design can be imparted to the substrate by the photocatalyst layer.
- the resin emulsion is a silicone emulsion and / or a fluororesin emulsion.
- the average particle size of the resin emulsion is larger than the average particle size of the photocatalytic metal oxide particles and the silica particles. This is preferable because the ratio of the photocatalytic metal oxide particles moving toward the surface of the photocatalyst layer is considered to increase.
- the photocatalytic metal oxide particles include titanium oxide such as anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, tin oxide, zinc oxide, strontium titanate, tungsten oxide, Particles of metal oxides such as cerium oxide, particles in which these particles are combined, and these particles are combined or doped with copper, platinum, iron, palladium, silver, gold, cuprous oxide, cupric oxide, etc. Particles obtained by coating or modifying the surface of these particles with silane, silicone or hydrolyzable metal salt can be suitably used.
- the photocatalytic metal oxide particles preferably have an average particle size of 10 nm or more and less than 100 nm, more preferably 10 nm or more and 60 nm or less.
- the average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope.
- a true sphere is the best, but it may be substantially circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2). Within this range, weather resistance and harmful gas decomposability are efficiently exhibited, and transparency, coating strength, and the like are improved.
- the photocatalytic metal oxide particles preferably have an average crystallite diameter of 3 nm or more and less than 30 nm, more preferably 5 nm or more and 20 nm or less.
- the average particle diameter is calculated by the Scherrer equation from the integral width of the three strong lines of the X-ray profile obtained by the powder X-ray diffraction method.
- the content of the photocatalytic metal oxide particles is a dry mass (solid content mass) with respect to the total mass of the resin emulsion, the photocatalytic metal oxide particles, and the silica particles. It is more than 0.1% by mass and less than 15% by mass, more preferably more than 0.5% by mass and less than 5% by mass.
- the silica particles preferably have an average particle size of more than 5 nm and 100 nm or less, more preferably more than 10 nm and 50 nm or less.
- the average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope.
- a true sphere is the best, but it may be substantially circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2).
- Use of such silica particles is advantageous because the photocatalytic degradation activity can be improved while improving the coating film strength.
- a substance having a hydrophobic group for coating or modifying silica particles for example, a substance having a functional group and a hydrophobic group for binding to the silica particles can be suitably used.
- the amount of the substance used for the coating or modification treatment is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass with respect to the amount of silica.
- hydrolyzable silane having a hydrophobic group examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and isopropyltrimethoxy.
- Silane isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane , 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,
- hydrolyzable silicone having a hydrophobic group used in the present invention a (partial) hydrolyzed / condensed product of the above silane can be suitably used.
- resin emulsion used in the present invention for example, emulsions such as fluororesin, silicone, acrylic silicone, vinyl acetate, vinyl acetate acrylic, acrylic urethane, acrylic, epoxy, vinyl chloride vinyl acetate, vinylidene chloride, and SBR latex can be used.
- emulsions such as fluororesin, silicone, acrylic silicone, vinyl acetate, vinyl acetate acrylic, acrylic urethane, acrylic, epoxy, vinyl chloride vinyl acetate, vinylidene chloride, and SBR latex can be used.
- fluororesin emulsion examples 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, Tet Fluoro ethylene acrylic crosslinked emulsion polymers containing tetrafluoro
- Silicone emulsions include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltribromosilane, methyltriisopropoxysilane, methyltri-t-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-hexy
- an inorganic pigment is preferable because it can easily suppress a change in appearance over a long period of time.
- 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 series 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.
- the photocatalyst layer may contain inorganic oxide particles other than the hydrophilic silica particles.
- the inorganic oxide particles are not particularly limited as long as they are inorganic oxide particles capable of forming a layer together with the photocatalyst particles, and various inorganic oxide particles can be used.
- examples of such inorganic oxide particles include alumina, zirconia, ceria, yttria, tin oxide, iron oxide, manganese oxide, nickel oxide, cobalt oxide, hafnia and other single oxide particles; and barium titanate, Examples thereof include composite oxide particles such as calcium silicate, aluminum borate, and potassium titanate.
- At least one selected from the group consisting of vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, copper, silver, platinum and gold is used to develop higher photocatalytic ability.
- the coated body may contain a metal compound and / or a metal compound comprising the metal. These compounds may be mixed in a coating liquid described later and exist in the photocatalyst layer, or these compounds can be present in the photocatalyst layer by supporting them on the photocatalyst particles.
- the photocatalyst layer of the coated body according to the present invention may contain an organic antifungal agent.
- organic antifungal agent include organic nitrogen sulfur compounds, pyrithion compounds, organic iodine compounds, triazine compounds, isothiazoline compounds. , Imidazole compounds, pyridine compounds, nitrile compounds, thiocarbamate compounds, thiazole compounds, organic iodine compounds, and disulfide compounds are used alone or as a mixture. Since many antifungal agents generally have an effect of preventing algae, addition of the antifungal agent can be expected to suppress both mold and algae.
- the photocatalyst layer of the coated body according to the present invention may contain an ultraviolet absorber.
- the content of the ultraviolet absorber is not limited as long as the weather resistance can be improved without inhibiting the photocatalytic activity and / or the expression of hydrophilicity, for example, 0.001 to 10% by mass, preferably 0, in the photocatalyst. 0.01 to 5% by mass.
- UV absorbers in the present invention benzophenone-based, benzotriazole-based, and triazine-based UV absorbers can be given as preferable examples.
- triazine-based ultraviolet absorbers are preferable because they are chemically stable.
- hydroxyphenyltriazine or a derivative thereof can be suitably used as the triazine-based ultraviolet absorber.
- benzophenone-based UV absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4.
- benzotriazole-based ultraviolet absorber examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-tert-butylphenyl) benzo Triazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy- 3,5-di-tert-octylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ ′-dimethylbenzyl) phenyl] benzotriazole), methyl-3- [3 -Tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol Condensate with Cole (Molecular weight 300) (product name: TINUVIN-1130, manufactured by Ciba-G
- TINUVIN-384-2 product name, manufactured by Ciba-Geigy Corporation of Japan
- TINUVIN-99-2 product name, manufactured by Ciba-Geigy Corporation of Japan
- TINUVIN-109 product name, manufactured by Ciba-Geigy Corporation of Japan
- TINUVIN-328 product name, manufactured by Ciba Geigy Japan
- TINUVIN-928 product name, Ciba Nippon Made Iggy Co., Ltd.
- the photocatalyst layer may further contain a light stabilizer such as a hindered amine and / or a hindered phenol.
- a light stabilizer such as a hindered amine and / or a hindered phenol.
- the photocatalyst layer of the present invention is preferable because it exhibits excellent weather resistance and light resistance due to a synergistic effect with the ultraviolet absorber.
- a hydroxyphenyl triazine compound may be blended as an ultraviolet absorber and a hindered amine compound as a light stabilizer.
- the content of the light stabilizer in the photocatalyst layer is not limited as long as the weather resistance can be improved without inhibiting the expression of photocatalytic activity and / or hydrophilicity. It is preferable to contain 001 to 10% by mass, preferably 0.01 to 5% by mass.
- hindered amine light stabilizer examples include bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, 1- [2- [3- (3 5-Di-tert-butyl-4-hydroxyphenyl) propynyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] -2,2,6 6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-seba Mixture (manufactured by Ciba Geigy Japan, product name
- hindered phenol light stabilizers include bis (3,5-tert-butyl) -4-hydroxytoluene, TINUVIN-144 (product name, manufactured by Ciba Geigy Japan, Inc.) and the like. it can.
- Photocatalyst coating liquid According to another aspect of the present invention, there is provided a photocatalyst coating liquid which is preferable for the formation of the above-described coated body according to the present invention.
- the coating liquid comprises photocatalytic metal oxide particles, silica particles, and a resin. It comprises an emulsion and a solvent, and the silica particles are coated or modified with a substance having a hydrophobic group.
- the photocatalytic metal oxide particles, the silica particles, and the resin emulsion contained in the coating liquid according to the present invention are substantially the same except that they are in a state of constituting the liquid composition and the components constituting the above-mentioned coated body. It may be the same. Moreover, what was mentioned as a preferable aspect about these components may be similarly added as a preferable thing in the coating liquid by this invention.
- the composition of the coating solution may be any material that realizes the above-described composition after drying. Therefore, although the following explanation has been partly explained, the following explanation will be given regardless of duplication for the sake of clarity.
- the solid content of the resin emulsion is 50% or more, preferably 70% or more, most preferably based on the total mass of the solid content of the resin emulsion, photocatalytic metal oxide particles and silica particles. Preferably, it should be 85% or more.
- the coating liquid according to the present invention can further contain a color pigment.
- the resin emulsion is a silicone emulsion and / or a fluororesin emulsion.
- the average particle size of the resin emulsion in the coating liquid is larger than the average particle size of the photocatalytic metal oxide particles and the silica particles. Therefore, it is considered that the rate at which the photocatalytic metal oxide particles move toward the surface of the photocatalyst layer is increased.
- the photocatalytic metal oxide particles include titanium oxide such as anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, tin oxide, zinc oxide, strontium titanate, tungsten oxide, Particles of metal oxides such as cerium oxide, particles in which these particles are combined, and these particles are combined or doped with copper, platinum, iron, palladium, silver, gold, cuprous oxide, cupric oxide, etc. Particles obtained by coating and modifying the surfaces of these particles with silane, silicone or hydrolyzable metal salt can be suitably used.
- the photocatalytic metal oxide particles preferably have an average particle size of 10 nm or more and less than 100 nm, more preferably 10 nm or more and 60 nm or less.
- the average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope.
- a true sphere is the best, but it may be a substantially circular or elliptical shape, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2). Within this range, weather resistance and harmful gas decomposability are efficiently exhibited, and transparency, coating strength, and the like are improved.
- the photocatalytic metal oxide particles preferably have an average crystallite diameter of 3 nm or more and less than 30 nm, more preferably 5 nm or more and 20 nm or less.
- the average particle diameter is calculated by the Scherrer equation from the integral width of the three strong lines of the X-ray profile obtained by the powder X-ray diffraction method.
- the content of the photocatalytic metal oxide particles in the coating liquid is a dry mass (solid content mass), and is a total of the resin emulsion, the photocatalytic metal oxide particles, and the silica particles. More than 0.1% by mass and less than 15% by mass, and more preferably more than 0.5% by mass and less than 5% by mass.
- the silica particles preferably have an average particle size of more than 5 nm and 100 nm or less, more preferably more than 10 nm and 50 nm or less.
- the average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope.
- a true sphere is the best, but it may be substantially circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2).
- a substance having a hydrophobic group for coating or modifying silica particles for example, a substance having a functional group and a hydrophobic group for binding to the silica particles can be suitably used.
- the amount of the substance used for the coating or modification treatment is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass with respect to the amount of silica.
- resin emulsion used in the present invention for example, emulsions such as fluororesin, silicone, acrylic silicone, vinyl acetate, vinyl acetate acrylic, acrylic urethane, acrylic, epoxy, vinyl chloride vinyl acetate, vinylidene chloride, and SBR latex can be used.
- emulsions such as fluororesin, silicone, acrylic silicone, vinyl acetate, vinyl acetate acrylic, acrylic urethane, acrylic, epoxy, vinyl chloride vinyl acetate, vinylidene chloride, and SBR latex can be used.
- an inorganic pigment is preferable as the color pigment because it is easy to suppress changes in appearance over a long period of time.
- 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 series 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.
- the coating liquid according to the present invention may contain inorganic oxide particles other than hydrophilic silica particles.
- the inorganic oxide particles are not particularly limited as long as they are inorganic oxide particles capable of forming a layer together with the photocatalyst particles, and various inorganic oxide particles can be used.
- examples of such inorganic oxide particles include alumina, zirconia, ceria, yttria, tin oxide, iron oxide, manganese oxide, nickel oxide, cobalt oxide, hafnia and other single oxide particles; and barium titanate, Examples thereof include composite oxide particles such as calcium silicate, aluminum borate, and potassium titanate.
- the coating liquid according to the present invention is made of vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, copper, silver, platinum and gold in order to develop higher photocatalytic ability. It may contain at least one metal selected from the group consisting of and / or a metal compound comprising the metal.
- the solvent used in the photocatalyst coating liquid according to the present invention is not particularly limited, but water, alcohols such as methanol, ethanol, propanol, and butanol, mixed solvents of water and alcohol, and the like can be particularly preferably used.
- water it is preferable to use water as a solvent because it can effectively prevent the odor and environmental pollution caused by the volatilization and evaporation of organic substances during coating film formation.
- the solid content concentration of the photocatalyst coating liquid is not particularly limited, but it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and most preferably 10 to 50% by mass because it is easy to apply.
- the components in the photocatalyst coating solution are analyzed by separating the coating solution into particle components and filtrate by ultrafiltration, and analyzing each by infrared spectroscopic analysis, gel permeation chromatography, fluorescent X-ray spectroscopic analysis, etc. It can be evaluated by analyzing the spectrum.
- the photocatalyst coating liquid can contain a film forming aid having a boiling point of 100 ° C. or higher, which is soluble in water or can be uniformly dispersed in water.
- This film-forming aid remains in the film even after most of the water has evaporated, and it can promote fusion by dissolving the resin emulsion interface and lower the film-forming temperature.
- alcohols such as 1-butanol, isobutyl alcohol, 2-pentanol, 3-pentanol, isopentyl alcohol, methyl lactate, ethyl lactate, 3-methyl-3-methoxybutanol, 1,2-propane
- Polyols such as diol, 1,3-butanediol 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, glycerin, trimethylolpropane
- Ethylene glycol derivatives such as 2-butoxyethanol, 2-phenoxyethanol, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, diethylene glycol monobutyl ether acetate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methoxy-2 Propylene glycol derivatives such as methyl ethyl
- esters examples thereof include esters.
- alkylene glycol derivatives such as 2-ethoxyethyl acetate, 2-butoxyethyl acetate, diethylene glycol monobutyl ether acetate, 1-ethoxy-2-methylethyl acetate, dipropylene glycol monomethyl ether acetate and the like are preferable.
- the amount of the film forming aid added to the coating liquid according to the present invention is preferably 0 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the silicone resin.
- the coating liquid according to the present invention may contain a surfactant as an optional component.
- the surfactant is added in an amount of less than 10 parts by weight, more preferably about 0.1 to 2 parts by weight with respect to 1 part by weight of the photocatalyst particles.
- surfactants examples include sulfonic acid polyoxyethylene alkylphenyl ether ammonium salt, sulfonic acid polyoxyethylene alkylphenyl ether sodium salt, fatty acid sodium soap, fatty acid potassium soap, dioctyl sulfosuccinic acid Sodium, alkyl sulfate, alkyl ether sulfate, alkyl sulfate soda salt, alkyl ether sulfate soda salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether sulfate soda salt, alkyl sulfate TEA salt, polyoxyethylene alkyl ether sulfate TEA salt, 2-ethylhexyl alkyl sulfate sodium salt, acylmethyl taurate sodium , Sodium lauroylmethyl taurate, sodium dodecylbenzenesulfonate, disodium la
- the photocatalyst coating body of this invention can be manufactured by apply
- a method for coating the photocatalyst layer generally used methods such as brush coating, roller, spray, roll coater, flow coater, dip coating, flow coating, and screen printing can be used. After applying the coating liquid to the substrate, it may be dried at room temperature, or may be heat-dried as necessary.
- the base material used in the present invention may be various materials regardless of inorganic materials, organic materials, and multilayer materials, and the shape thereof is not limited.
- Preferred examples of the substrate from the viewpoint of materials include metals, ceramics, glasses, plastics, rubber, stones, cement, concrete, fibers, fabrics, wood, paper, combinations thereof, laminates thereof, Examples thereof include those having at least one layer of coating on the surface.
- base materials from the viewpoint of applications include building materials, building exteriors and interiors, window frames, window glass, structural members, exteriors and coatings of vehicles, exteriors of machinery and articles, dust covers and coatings, traffic signs, Various display devices, advertising towers, sound insulation walls for roads, sound insulation walls for railways, bridges, guard rail exteriors and paintings, tunnel interiors and paintings, insulators, solar battery covers, solar water heater heat collection covers, plastic houses, vehicle lighting Covers, outdoor lighting fixtures, tables, bathroom materials, kitchen panels, sinks, ranges, ventilation fans, air conditioning, filters, toilets, bathtubs, and films, sheets, seals and the like for attachment to the surface of the article.
- Example 1 Silica particle surface coating treatment
- Hydrophobized silica particles were prepared by reacting 5 parts by weight of trialkoxysilane with 100 parts by weight of silica particles (average particle size 50 nm).
- (Production of photocatalyst coating) 90 parts by mass of 1.3 parts by mass of anatase-type titanium oxide particles (average crystallite diameter: 10 nm), 8.7 parts by mass of the above-mentioned hydrophobized silica particles, and a silicone emulsion having a methylphenylsilyl group as a solid content
- a photocatalytic aqueous coating liquid having a solid content concentration of 25% by mass was prepared and dried on a transparent 2 mm thick soda lime glass substrate at 150 ° C.
- the cross section of the photocatalyst layer of the obtained photocatalyst-coated body is measured by energy dispersive X-ray spectroscopy (EDX) at a spot size of 1 ⁇ m ⁇ 0.5 ⁇ m near the surface, near the center, and near the interface with the substrate.
- EDX energy dispersive X-ray spectroscopy
- Example 2 Hydrophobized silica particles were prepared by reacting 5 parts by weight of trialkoxysilane with 100 parts by weight of silica particles (average particle size 50 nm).
- a photocatalyst aqueous coating solution having a partial concentration of 25% by mass was prepared and dried on a transparent 2 mm thick soda lime glass substrate at 150 ° C.
- Comparative Example 1 Anatase-type titanium oxide particles (average crystallite size 10 nm) 1.3 parts by mass, silica particles (average particle size 50 nm) 8.7 parts by mass, solid content concentration of 90 parts by mass of methylphenyl silicone emulsion as solid content 25 mass % Photocatalyst aqueous coating solution was prepared and dried on a transparent 2 mm thick soda lime glass substrate at 150 ° C. for 5 minutes to obtain a photocatalyst-coated body. When the photocatalyst layer of the obtained photocatalyst-coated body was observed in cross section, the film thickness was about 7 ⁇ m.
- the transmittance of light having a wavelength of 550 nm of the photocatalyst layer was 83%.
- This photocatalyst-coated body was subjected to photocatalytic decomposition activity in accordance with the test method of JIS R 1703-2 “Testing method for self-cleaning performance of photocatalytic material—Part 2: Wet decomposition performance”.
- the MB activity index showed a low value of 1.1.
- FIG. Silica particle surface coating treatment
- Hydrophobized silica particles were prepared by reacting 5 parts by weight of trialkoxysilane with 100 parts by weight of silica particles (average particle size 50 nm).
- (Preparation of photocatalyst coating) 1.3 parts by mass of anatase-type titanium oxide particles (average crystallite diameter: 10 nm), 8.7 parts by mass of the above-mentioned hydrophobized silica particles, 45 parts by mass of methylphenylsilicone emulsion as a solid content, and 45 parts by mass of an inorganic pigment
- a photocatalyst aqueous coating solution having a solid content concentration of 40% by mass was prepared to obtain a photocatalyst paint.
- Asbestos-cement calcium silicate board cut to 150mm x 65mm JIS Epoxy resin-based primer was spray-coated on A5418) and dried at room temperature for 24 hours. Subsequently, an acrylic urethane paint was spray-coated on the asbestos-cement calcium silicate plate subjected to the above-described primer coating, and dried at room temperature for 24 hours. Subsequently, the photocatalyst paint was brush-coated on an asbestos cement calcium silicate board coated with acrylic urethane to obtain a coating. (Evaluation of coated photocatalyst) When the photocatalyst layer of the obtained photocatalyst-coated body was observed in cross section, the film thickness was about 40 ⁇ m.
- the photocatalyst-coated body was subjected to photocatalytic decomposition activity according to the test method of JIS R 1703-2 “Testing method for self-cleaning performance of photocatalytic material—Part 2: Wet decomposition performance”. As a result, the MB activity index was as good as 6.0.
- the weather resistance test was done as follows. The photocatalyst-coated body was put into a sunshine weatherometer (S-300C, manufactured by Suga Test Instruments) defined in JIS B7753. After 100 hours had passed, the test piece was taken out and the appearance change before and after the addition was observed. As a result, no change was observed in the appearance.
- Example 4 (Surface coating treatment of anatase-type titanium oxide particles) Hydrophobized titanium oxide particles were prepared by reacting 5 parts by weight of trialkoxysilane with 100 parts by weight of anatase-type titanium oxide particles (average crystallite diameter: 10 nm). (Silica particle surface coating treatment) Hydrophobized silica particles were prepared by reacting 5 parts by weight of trialkoxysilane with 100 parts by weight of silica particles (average particle size 50 nm).
- the transmittance of light having a wavelength of 550 nm of the photocatalyst layer was 84%.
- the photocatalyst-coated body was subjected to photocatalytic decomposition activity according to the test method of JIS R 1703-2 “Testing method for self-cleaning performance of photocatalytic material—Part 2: Wet decomposition performance”.
- the MB activity index was as good as 9.3.
- the weather resistance test was done as follows.
- the photocatalyst-coated body was put into a sunshine weatherometer (S-300C, manufactured by Suga Test Instruments) defined in JIS B7753. After 100 hours had elapsed, the test piece was taken out and the appearance change before and after the addition was observed. As a result, no change was observed in the appearance.
- the photocatalyst-coated body was put into a sunshine weatherometer (S-300C, manufactured by Suga Test Instruments) defined in JIS B7753. After 100 hours had elapsed, the test piece was taken out and the appearance change before and after the addition was observed. As a result, no change was observed in the appearance.
Abstract
Description
organic compounds))分解性、抗菌性、防カビ性、抗ウイルス性等の光触媒機能を有する光触媒塗装体に関する。さらに、本発明は、外装、内装等を構成する部材にコーティング層を形成することにより、有害ガス分解性、降雨・水洗によるセルフクリーニング性、水洗容易性、VOC分解性、抗菌性、防カビ性、抗ウイルス性等の光触媒機能を付与可能な光触媒コーティング液に関する。
本発明による光触媒塗装体は、基材表面に光触媒層を備えた光触媒塗装体であって、前記光触媒層は、光触媒性金属酸化物粒子と、シリカ粒子と、樹脂エマルジョンの乾燥物とを含んでなり、前記シリカ粒子が疎水性基を有する物質により被覆又は変性処理されている。疎水性基を有する物質により被覆又は変性処理されたシリカ粒子を用いることにより、意外なことにシリカ粒子をそのまま添加した場合よりも顕著に光触媒活性を増加させることができる。また長期に亘り塗装体の外観変化が抑制される。
〕ベンゾトリアゾール、2,2-メチレンビス〔4-(1,1,3,3-テトラメチルブチル)-6-(2H-ベンゾトリアゾール-2-イル)フェノール〕、2-(2H-ベンゾトリアゾール-2-イル)-4,6-ビス(1-メチル-1-フェニルエチル)フェノール(日本チバガイギー(株)製、製品名:TINUVIN-900)、及び2-(2’-ヒドロキシ-5’-メタクリロキシエチルフェニル)-2H-ベンゾトリアゾール(大塚化学(株)製、製品名:RUVA-93)、2-(2’-ヒドロキシ-5’-メタクリロキシエチル-3-tert-ブチルフェニル)-2H-ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メタクリリルオキシプロピル-3-tert-ブチルフェニル)-5-クロロ-2H-ベンゾトリアゾール、3-メタクリロイル-2-ヒドロキシプロピル-3-〔3’-(2”-ベンゾトリアゾリル)-4-ヒドロキシ-5-tert-ブチル〕フェニルプロピオネート(日本チバガイギー(株)製、製品名:CGL-104)等の重合性のベンゾトリアゾール系紫外線吸収剤やそれらの(共)重合物の他、TINUVIN-384-2(製品名、日本チバガイギー(株)製)、TINUVIN-99-2(製品名、日本チバガイギー(株)製)、TINUVIN-109(製品名、日本チバガイギー(株)製)、TINUVIN-328(製品名、日本チバガイギー(株)製)、TINUVIN-928(製品名、日本チバガイギー(株)製)などが挙げられる。
本発明の別の態様によれば、上述の本発明による塗装体の形成に好ましい、光触媒コーティング液が提供され、このコーティング液は、光触媒性金属酸化物粒子と、シリカ粒子と、樹脂エマルジョンと、溶媒とを含んでなり、前記シリカ粒子は、疎水性基を有する物質により被覆又は変性処理されてなるものである。
また、コーティング液の組成は、乾燥後に上述した組成を実現するものであればよい。従って、以下の説明は、一部既に説明されたものであるが、以下にその明確性のために重複を問わず説明する。
本発明の光触媒塗装体は、上記光触媒コーティング液を、基材上に塗布することにより製造することができる。光触媒層の塗装方法は、前記液剤を刷毛塗り、ローラー、スプレー、ロールコーター、フローコーター、ディップコート、流し塗り、スクリーン印刷等、一般に広く行われている方法を利用できる。コーティング液の基材への塗布後は、常温乾燥させればよく、あるいは必要に応じて加熱乾燥してもよい。
本発明に用いる基材は、無機材料、有機材料、複層材料を問わず種々の材料であってよく、その形状も限定されない。材料の観点からみた基材の好ましい例としては、金属、セラミック、ガラス、プラスチック、ゴム、石、セメント、コンクリ-ト、繊維、布帛、木、紙、それらの組合せ、それらの積層体、それらの表面に少なくとも一層の被膜を有するものが挙げられる。用途の観点からみた基材の好ましい例としては、建材、建物外装および内装、窓枠、窓ガラス、構造部材、乗物の外装及び塗装、機械装置や物品の外装、防塵カバー及び塗装、交通標識、各種表示装置、広告塔、道路用遮音壁、鉄道用遮音壁、橋梁、ガードレ-ルの外装及び塗装、トンネル内装及び塗装、碍子、太陽電池カバー、太陽熱温水器集熱カバー、ビニールハウス、車両用照明灯のカバー、屋外用照明器具、台、浴室材、キッチンパネル、流し台、レンジ、換気扇、空調、フィルター、便器、浴槽及び上記物品表面に貼着させるためのフィルム、シート、シール等が挙げられる。
(シリカ粒子の表面被覆処理)
シリカ粒子(平均粒径50nm)100重量部に対してトリアルコキシシラン5重量部を反応させて、疎水化処理されたシリカ粒子を作製した。
(光触媒塗装体の作製)
アナターゼ型酸化チタン粒子(平均結晶子径10nm)1.3質量部、上記疎水化処理されたシリカ粒子8.7質量部、およびメチルフェニルシリル基を有するシリコーンエマルジョンを固形分として90質量部配合した固形分濃度25質量%の光触媒水性コーティング液を調製し、透明な2mm厚のソーダライムガラス基材上に150℃×5分乾燥して、光触媒塗装体を得た。
(光触媒塗装体の評価)
得られた光触媒塗装体の光触媒層を断面観察したところ、膜厚は約7μmであった。
また、光触媒層の550nmの波長の光の透過率は82%であった。
この光触媒塗装体について、光触媒分解活性を、JISR1703-2「光触媒材料のセルフクリーニング性能試験方法-第2部:湿式分解性能」の試験法に従い行った。その結果、MB活性指数は6.5と良好な結果を示した。
(シリカ粒子の表面被覆処理)
シリカ粒子(平均粒径50nm)100重量部に対してトリアルコキシシラン5重量部を反応させて、疎水化処理されたシリカ粒子を作製した。
(光触媒塗装体の作製)
アナターゼ型酸化チタン粒子(平均結晶子径10nm)1.3質量部、上記疎水化処理されたシリカ粒子8.7質量部、およびジメチルシリル基を有するシリコーンエマルジョンを固形分として90質量部配合した固形分濃度25質量%の光触媒水性コーティング液を調製し、透明な2mm厚のソーダライムガラス基材上に150℃×5分乾燥して、光触媒塗装体を得た。
(光触媒塗装体の評価)
得られた光触媒塗装体の光触媒層を断面観察したところ、膜厚は約7μmであった。
また、光触媒層の550nmの波長の光の透過率は84%であった。
この光触媒塗装体について、光触媒分解活性を、JISR1703-2「光触媒材料のセルフクリーニング性能試験方法-第2部:湿式分解性能」の試験法で行った。その結果、MB活性指数は6.4と良好な結果を示した。
アナターゼ型酸化チタン粒子(平均結晶子径10nm)1.3質量部、シリカ粒子(平均粒径50nm)8.7質量部、メチルフェニルシリコーンエマルジョンを固形分として90質量部配合した固形分濃度25質量%の光触媒水性コーティング液を調製し、透明な2mm厚のソーダライムガラス基材上に150℃×5分乾燥して、光触媒塗装体を得た。
得られた光触媒塗装体の光触媒層を断面観察したところ、膜厚は約7μmであった。
また、光触媒層の550nmの波長の光の透過率は83%であった。
この光触媒塗装体について、光触媒分解活性を、JISR1703-2「光触媒材料のセルフクリーニング性能試験方法-第2部:湿式分解性能」の試験法に従い行った。その結果、MB活性指数は1.1と低い値を示した。
(シリカ粒子の表面被覆処理)
シリカ粒子(平均粒径50nm)100重量部に対してトリアルコキシシラン5重量部を反応させて、疎水化処理されたシリカ粒子を作製した。
(光触媒塗装体の作製)
アナターゼ型酸化チタン粒子(平均結晶子径10nm)1.3質量部、上記疎水化処理されたシリカ粒子8.7質量部、およびメチルフェニルシリコーンエマルジョンを固形分として45質量部、無機顔料45質量部を配合した固形分濃度40質量%の光触媒水性コーティング液を調製し光触媒塗料を得た。
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、上記光触媒塗料を、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。
(光触媒塗装体の評価)
得られた光触媒塗装体の光触媒層を断面観察したところ、膜厚は約40μmであった。
この光触媒塗装体について、光触媒分解活性を、JISR1703-2「光触媒材料のセルフクリーニング性能試験方法-第2部:湿式分解性能」の試験法に従って行った。その結果、MB活性指数は6.0と良好な結果を示した。
得られた光触媒塗装体について、以下の通り耐候性試験を行った。光触媒塗装体をJIS B7753に規定されるサンシャインウエザオメーター(スガ試験機製、S-300C)に投入した。100hr経過後に試験片を取り出し、投入前後の外観変化を観察した。その結果、外観に変化は認められなかった。
(アナターゼ型酸化チタン粒子の表面被覆処理)
アナターゼ型酸化チタン粒子(平均結晶子径10nm)100重量部に対してトリアルコキシシラン5重量部を反応させて、疎水化処理された酸化チタン粒子を作製した。
(シリカ粒子の表面被覆処理)
シリカ粒子(平均粒径50nm)100重量部に対してトリアルコキシシラン5重量部を反応させて、疎水化処理されたシリカ粒子を作製した。
(光触媒塗装体の作製)
上記疎水化処理された酸化チタン粒子1.3質量部、上記疎水化処理されたシリカ粒子8.7質量部、およびメチルフェニルシリル基を有するシリコーンエマルジョンを固形分として90質量部配合した固形分濃度25質量%の光触媒水性コーティング液を調製し、透明な2mm厚のソーダライムガラス基材上に150℃×5分乾燥して、光触媒塗装体を得た。
(光触媒塗装体の評価)
得られた光触媒塗装体の光触媒層を断面観察したところ、膜厚は約7μmであった。
また、光触媒層の550nmの波長の光の透過率は84%であった。
この光触媒塗装体について、光触媒分解活性を、JISR1703-2「光触媒材料のセルフクリーニング性能試験方法-第2部:湿式分解性能」の試験法に従って行った。その結果、MB活性指数は9.3と良好な結果を示した。
(シリカ粒子の表面被覆処理)
シリカ粒子(平均粒径50nm)100重量部に対してトリアルコキシシラン5重量部を反応させて、疎水化処理されたシリカ粒子を作製した。
(光触媒塗装体の作製)
アナターゼ型酸化チタン粒子(平均結晶子径10nm)1.3質量部、上記疎水化処理されたシリカ粒子8.7質量部、およびメチルフェニルシリル基を有するシリコーンエマルジョンを固形分として90質量部配合した固形分濃度25質量%の光触媒水性コーティング液を調製し、スレート板上にアクリル系着色塗装した基材上に80℃×30分乾燥して、光触媒塗装体を得た。
こうして得られた50×100mmの大きさの光触媒塗装体について、以下の通り耐候性試験を行った。光触媒塗装体をJIS B7753に規定されるサンシャインウエザオメーター(スガ試験機製、S-300C)に投入した。100hr経過後に試験片を取り出し、投入前後の外観変化を観察した。その結果、外観に変化は認められなかった。
(アナターゼ型酸化チタン粒子の表面被覆処理)
アナターゼ型酸化チタン粒子(平均結晶子径10nm)100重量部に対してトリアルコキシシラン5重量部を反応させて、疎水化処理された酸化チタン粒子を作製した。
(シリカ粒子の表面被覆処理)
シリカ粒子(平均粒径50nm)100重量部に対してトリアルコキシシラン5重量部を反応させて、疎水化処理されたシリカ粒子を作製した。
(光触媒塗装体の作製)
上記疎水化処理された酸化チタン粒子1.3質量部、上記疎水化処理されたシリカ粒子8.7質量部、およびメチルフェニルシリル基を有するシリコーンエマルジョンを固形分として90質量部配合した固形分濃度25質量%の光触媒水性コーティング液を調製し、透明なスレート板上にアクリル系着色塗装した基材上に150℃×5分乾燥して、光触媒塗装体を得た。
こうして得られた50×100mmの大きさの光触媒塗装体について、以下の通り耐候性試験を行った。光触媒塗装体をJIS B7753に規定されるサンシャインウエザオメーター(スガ試験機製、S-300C)に投入した。100hr経過後に試験片を取り出し、投入前後の外観変化を観察した。その結果、外観に変化は認められなかった。
Claims (17)
- 基材表面に光触媒層を備えた光触媒塗装体であって、
前記光触媒層が、光触媒性金属酸化物粒子と、シリカ粒子と、樹脂エマルジョンの乾燥物とを含んでなり、
前記シリカ粒子は疎水性基を有する物質により被覆又は変性処理されており、
前記光触媒層の最表層における光触媒性金属酸化物粒子の金属元素の濃度が、当該層の中央におけるそれよりも高いことを特徴とする光触媒塗装体。 - 前記光触媒層中の光触媒性金属酸化物粒子の金属元素の濃度が、当該層の基材との界面付近から最表層に向って徐々に高くなる濃度傾斜を示す、請求項1に記載の光触媒塗装体。
- 前記疎水性基を有する物質が、疎水性基を有するシラン及び/又は疎水性基を有するシリコーンである、請求項1又は2に記載の光触媒塗装体。
- 前記光触媒性金属酸化物が、光触媒性酸化チタンである、請求項1~3のいずれか一項に記載の光触媒塗装体。
- 前記光触媒層の膜厚が3μmを超え3mm未満であることを特徴とする請求項1~4のいずれか一項に記載の光触媒塗装体。
- 前記光触媒層が透明である、請求項1~5のいずれか一項に記載の光触媒塗装体。
- 前記樹脂エマルジョンの乾燥物の含量が、前記樹脂エマルジョンの乾燥物、前記光触媒性金属酸化物粒子および前記シリカ粒子の合計質量に対して50%以上である、請求項1~6のいずれか一項に記載の光触媒塗装体。
- 前記光触媒層が、更に着色顔料を含んでなる、請求項1~5および7のいずれか一項に記載の光触媒塗装体。
- 前記樹脂エマルジョンが、シリコーンエマルジョン及び/又はフッ素樹脂エマルジョンである、請求項1~8のいずれか一項に記載の光触媒塗装体。
- 前記樹脂エマルジョンの平均粒径が、前記光触媒性金属酸化物粒子および前記シリカ粒子の平均粒径よりも大である、請求項1~9のいずれか一項に記載の光触媒塗装体。
- 光触媒性金属酸化物粒子と、
シリカ粒子と、
樹脂エマルジョンと、
溶媒とを含んでなり、
前記シリカ粒子が、疎水性基を有する物質により被覆または変性処理されなるものであることを特徴とする、光触媒コーティング液。 - 前記疎水性基を有する物質が、疎水性基を有するシラン及び/又は疎水性基を有するシリコーンである、請求項11に記載の光触媒コーティング液。
- 前記光触媒性金属酸化物が、光触媒性酸化チタンである、請求項11又は12に記載の光触媒コーティング液。
- 前記光触媒層が更に着色顔料を含んでなる、請求項11~13のいずれか一項に記載の光触媒コーティング液。
- 前記樹脂エマルジョンの固形分の含量が、前記樹脂エマルジョン、前記光触媒性金属酸化物粒子および前記シリカ粒子の固形分の合計質量に対して50%以上である、請求項11~14のいずれか一項に記載の光触媒コーティング液。
- 前記樹脂エマルジョンが、シリコーンエマルジョン及び/又はフッ素樹脂エマルジョンである、請求項11~15のいずれか一項に記載の光触媒コーティング液。
- 前記樹脂エマルジョンの平均粒径が、前記光触媒性金属酸化物粒子および前記シリカ粒子の平均粒径よりも大である、請求項11~16のいずれか一項に記載の光触媒コーティング液。
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Cited By (6)
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JP2011025234A (ja) * | 2009-06-26 | 2011-02-10 | Toto Ltd | 光触媒塗装体および光触媒コーティング液 |
JP2011050846A (ja) * | 2009-09-01 | 2011-03-17 | Toto Ltd | 光触媒塗装体、および光触媒コーティング液 |
JP2012246344A (ja) * | 2011-05-25 | 2012-12-13 | Fujikura Kasei Co Ltd | 水系塗料組成物 |
JP2013184100A (ja) * | 2012-03-07 | 2013-09-19 | Showa Denko Kk | 可視光応答型光触媒組成物及びその製造方法 |
KR101506344B1 (ko) | 2014-12-03 | 2015-03-26 | 영남강철 주식회사 | 친환경 목재보드 및 그 제조방법 |
EP2910613A1 (en) * | 2014-02-24 | 2015-08-26 | Toto Ltd. | Coating composition and coated body |
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JP5478700B1 (ja) * | 2012-11-28 | 2014-04-23 | 株式会社ハマキャスト | 外壁塗装方法 |
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CN105536882A (zh) | 2016-05-04 |
KR20120011884A (ko) | 2012-02-08 |
JPWO2010150906A1 (ja) | 2012-12-10 |
JP5614709B2 (ja) | 2014-10-29 |
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