JP6467502B2 - Photocatalyst-containing coating liquid and photocatalyst carrying structure - Google Patents
Photocatalyst-containing coating liquid and photocatalyst carrying structure Download PDFInfo
- Publication number
- JP6467502B2 JP6467502B2 JP2017517604A JP2017517604A JP6467502B2 JP 6467502 B2 JP6467502 B2 JP 6467502B2 JP 2017517604 A JP2017517604 A JP 2017517604A JP 2017517604 A JP2017517604 A JP 2017517604A JP 6467502 B2 JP6467502 B2 JP 6467502B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- coupling agent
- containing coating
- silane coupling
- mass
- 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.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims description 119
- 238000000576 coating method Methods 0.000 title claims description 83
- 239000011248 coating agent Substances 0.000 title claims description 82
- 239000007788 liquid Substances 0.000 title claims description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000007822 coupling agent Substances 0.000 claims description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- 239000010419 fine particle Substances 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 230000001699 photocatalysis Effects 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 150000004645 aluminates Chemical class 0.000 claims description 7
- 239000011368 organic material Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 229920003002 synthetic resin Polymers 0.000 claims description 5
- 239000000057 synthetic resin Substances 0.000 claims description 5
- 150000004756 silanes Chemical class 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims 2
- 230000003796 beauty Effects 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 53
- -1 appliances Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 125000005595 acetylacetonate group Chemical group 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 230000000840 anti-viral effect Effects 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 229940093858 ethyl acetoacetate Drugs 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 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 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- RQAGEUFKLGHJPA-UHFFFAOYSA-N prop-2-enoylsilicon Chemical compound [Si]C(=O)C=C RQAGEUFKLGHJPA-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241001534160 Escherichia virus Qbeta Species 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- YEZHENDLEQKJRY-UHFFFAOYSA-J [Zr+4].CCCCOC(C([O-])=O)C(=O)C(CC)(OCCCC)OCCCC.CCCCOC(C([O-])=O)C(=O)C(CC)(OCCCC)OCCCC.CCCCOC(C([O-])=O)C(=O)C(CC)(OCCCC)OCCCC.CCCCOC(C([O-])=O)C(=O)C(CC)(OCCCC)OCCCC Chemical compound [Zr+4].CCCCOC(C([O-])=O)C(=O)C(CC)(OCCCC)OCCCC.CCCCOC(C([O-])=O)C(=O)C(CC)(OCCCC)OCCCC.CCCCOC(C([O-])=O)C(=O)C(CC)(OCCCC)OCCCC.CCCCOC(C([O-])=O)C(=O)C(CC)(OCCCC)OCCCC YEZHENDLEQKJRY-UHFFFAOYSA-J 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- MQPPCKJJFDNPHJ-UHFFFAOYSA-K aluminum;3-oxohexanoate Chemical compound [Al+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O MQPPCKJJFDNPHJ-UHFFFAOYSA-K 0.000 description 1
- KEBBHXFLBGHGMA-UHFFFAOYSA-K aluminum;4-ethyl-3-oxohexanoate Chemical compound [Al+3].CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O.CCC(CC)C(=O)CC([O-])=O KEBBHXFLBGHGMA-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- RDASHQZXQNLNMG-UHFFFAOYSA-N butan-2-olate;di(propan-2-yloxy)alumanylium Chemical compound CCC(C)O[Al](OC(C)C)OC(C)C RDASHQZXQNLNMG-UHFFFAOYSA-N 0.000 description 1
- FEHMLIGHNBIRGD-UHFFFAOYSA-N butyl acetate;pentane Chemical compound CCCCC.CCCCOC(C)=O FEHMLIGHNBIRGD-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 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
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940105570 ornex Drugs 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-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
- 239000005022 packaging material Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 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
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 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
- 150000003608 titanium Chemical class 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
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- 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
- C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
Description
本発明は、光触媒担持構造体及びそれを形成するための光触媒含有塗布液に関し、詳しくは、光触媒層が基材上に直接設けられている光触媒担持構造体及びそれを形成するための光触媒塗布液に関する。
本願は、２０１５年５月１２日に出願された日本国特許出願第２０１５−９７１９５号に対し優先権を主張し、その内容をここに援用する。The present invention relates to a photocatalyst-supporting structure and a photocatalyst-containing coating liquid for forming the same, and more specifically, a photocatalyst-supporting structure in which a photocatalyst layer is directly provided on a substrate and a photocatalyst coating liquid for forming the photocatalyst layer About.
This application claims priority with respect to the Japan patent application 2015-97195 for which it applied on May 12, 2015, and uses the content here.
建築資材、内装材、器具、包装材等の用途で、プラスチックの表面に光触媒を担持させた材料は多数知られている。
また、光触媒効果を有する代表的な物質として知られる酸化チタン（チタニア）ゾルは、その効果とは別の用途として、透明のハードコート層を形成させるためのコーティング剤成分としても用いられる。
特許文献１には、有機溶媒に分散したチタニアゾルと、アクリルシリコン樹脂又はエポキシシリコン樹脂、及びテトラアルコキシシランの部分加水分解生成物を含有する塗布液を、ガラス等の基材に直接塗布してなる光触媒担持構造体が記載されている。
しかしプラスチック基材は有機材料であるため、酸化チタンなどの光触媒をその表面に直接担持させると、紫外線照射により基材が分解を受け、チョーキング（白化）などの劣化を起こすという問題がある。そのため、基材と光触媒層との間に中間層を設ける方法も多く提案されている。例えば特許文献２等には、光触媒層と中間層との接着を向上させるために、光触媒層にエポキシシランカップリング剤を含有させた例が記載されている。
特許文献３には、光触媒、光酸発生剤及びγ−グリシドキシプロピルトリメトキシシランを含有する光硬化性組成物を光硬化してなる硬化物が記載されている。
特許文献４には、紫外線重合性官能基を有するシランカップリング剤と、光重合開始剤とを含有する、光触媒塗膜形成用塗料が記載されている。
特許文献５には、酸化チタンナノ粒子、３−メタクリロキシプロピルトリメトキシシランや３−グリシドキシプロピルトリメトキシシラン等を含むシラン化合物の縮合物、及びその他の機能性物質（光触媒性酸化チタン等）を含有する有機無機複合体が記載されている。
特許文献６には、酸化チタンを含む光触媒、４官能性シラン化合物、及びさらに場合によりエポキシ系又はアクリル系のシランカップリング剤を含む塗膜形成剤を塗布し、これを紫外線により硬化させてなる塗膜が記載されており、塗膜形成剤が更に金属アルコキシドを含むと、撥水性微粒子の凝縮による塗膜の白濁が抑制できることが記載されている。Many materials are known in which a photocatalyst is supported on the surface of a plastic for applications such as building materials, interior materials, appliances, and packaging materials.
Further, a titanium oxide (titania) sol known as a representative substance having a photocatalytic effect is also used as a coating agent component for forming a transparent hard coat layer as a use different from the effect.
In Patent Document 1, a coating solution containing a titania sol dispersed in an organic solvent, an acrylic silicone resin or an epoxy silicone resin, and a partial hydrolysis product of tetraalkoxysilane is directly applied to a substrate such as glass. A photocatalyst carrying structure is described.
However, since the plastic substrate is an organic material, there is a problem that when a photocatalyst such as titanium oxide is directly supported on the surface, the substrate is decomposed by irradiation with ultraviolet rays to cause deterioration such as choking (whitening). Therefore, many methods for providing an intermediate layer between the substrate and the photocatalyst layer have been proposed. For example, Patent Document 2 and the like describe an example in which an epoxysilane coupling agent is contained in the photocatalyst layer in order to improve the adhesion between the photocatalyst layer and the intermediate layer.
Patent Document 3 describes a cured product obtained by photocuring a photocurable composition containing a photocatalyst, a photoacid generator, and γ-glycidoxypropyltrimethoxysilane.
Patent Document 4 describes a coating composition for forming a photocatalytic coating film containing a silane coupling agent having an ultraviolet polymerizable functional group and a photopolymerization initiator.
Patent Document 5 discloses titanium oxide nanoparticles, condensates of silane compounds including 3-methacryloxypropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, and other functional substances (such as photocatalytic titanium oxide). Organic-inorganic composites containing are described.
In Patent Document 6, a photocatalyst containing titanium oxide, a tetrafunctional silane compound, and a coating film forming agent containing an epoxy or acrylic silane coupling agent as the case may be applied and cured with ultraviolet rays. A coating film is described, and it is described that when the coating film forming agent further contains a metal alkoxide, the cloudiness of the coating film due to condensation of water-repellent fine particles can be suppressed.
特許文献３〜６の各方法により基材に直接塗布して得られる塗膜では、ある程度の強度が得られているが、有機基材に紫外線照射によるチョーキングを起こすことが問題として残されており、特に光触媒活性とチョーキング防止とを両立させることが課題とされていた。本願発明は、十分な光触媒活性を発揮しながら、基材に劣化を起こすことのない、光触媒担持構造体を提供することを目的とする。 In the coating film obtained by directly applying to the base material by each method of Patent Documents 3 to 6, a certain degree of strength is obtained, but the problem remains that the organic base material is choked by ultraviolet irradiation. In particular, it has been a problem to achieve both photocatalytic activity and prevention of choking. It is an object of the present invention to provide a photocatalyst-supporting structure that exhibits sufficient photocatalytic activity and does not cause deterioration of the substrate.
本発明者らは、光触媒含有塗布液として、エポキシシランカップリング剤又はアクリルシランカップリング剤であるシランカップリング剤、及び中心金属としてケイ素を有しない金属カップリング剤を含有し、かつ前記シランカップリング剤以外のシラン化合物を含有しない塗布液を用い、基材に直接塗布することにより、上記課題を解決した光触媒担持構造体が得られることを見出し、さらに上記課題を解決すべく鋭意検討した結果、本発明を完成するに至った。 The present inventors include, as a photocatalyst-containing coating solution, a silane coupling agent that is an epoxy silane coupling agent or an acrylic silane coupling agent, and a metal coupling agent that does not have silicon as a central metal, and the silane cup As a result of finding out that a photocatalyst-supporting structure that solves the above problems can be obtained by directly applying the coating liquid containing no silane compound other than the ring agent to the base material, and further studying to solve the above problems The present invention has been completed.
すなわち、本発明は、
（１）光触媒材料微粒子、エポキシシランカップリング剤及びアクリルシランカップリング剤から選ばれる少なくとも１種であるシランカップリング剤及び／又は該シランカップリング剤の加水分解縮合物、金属元素としてケイ素を有しない金属カップリング剤、及び溶媒を含有し、光触媒材料微粒子１００質量部に対して、前記シランカップリング剤及び該シランカップリング剤の加水分解縮合物の合計を３００質量部以上の比率で含有する、光触媒含有塗布液、
（２）前記シランカップリング剤以外のシラン化合物を含有しない、（１）に記載の光触媒含有塗布液、
（３）さらに微粒子シリカを含有する、（１）又は（２）に記載の光触媒含有塗布液、
（４）金属元素としてケイ素を有しない金属カップリング剤が、チタネート系カップリング剤、アルミネート系カップリング剤及びジルコネート系カップリング剤から選ばれる少なくとも１種である、（１）又は（２）に記載の光触媒含有塗布液、
（５）光触媒材料が二酸化チタンを含有するものである、（１）又は（２）に記載の光触媒含有塗布液、
（６）シランカップリング剤としてアクリルシランカップリング剤を含有し、さらに光重合開始剤を含有する、（１）又は（２）に記載の光触媒含有塗布液、及び
（７）シランカップリング剤の加水分解縮合物として、エポキシシランカップリング剤の加水分解縮合物を含有し、金属カップリング剤がアルミネート系カップリング剤である、（１）又は（２）に記載の光触媒含有塗布液に関する。
また、本発明は、
（８）基材上に、（１）〜（７）のいずれかに記載の光触媒含有塗布液を塗布し乾燥してなる、光触媒層が基材上に直接設けられている光触媒担持構造体、
（９）基材が有機材料である、（８）に記載の光触媒担持構造体、及び
（１０）有機材料が合成樹脂である、（９）に記載の光触媒担持構造体に関する。
さらに、本発明は、
（１１）（１）〜（７）のいずれかに記載の光触媒含有塗布液を基材に直接塗布し、乾燥することにより、光触媒担持構造体を形成する方法に関する。 That is, the present invention
(1) Photocatalyst material fine particles, epoxy silane coupling agent and acrylic silane coupling agent selected from at least one silane coupling agent and / or hydrolysis condensate of the silane coupling agent, silicon as a metal element A total amount of the silane coupling agent and hydrolysis condensate of the silane coupling agent in a ratio of 300 parts by mass or more with respect to 100 parts by mass of the photocatalyst material fine particles. , Photocatalyst-containing coating solution,
(2) The photocatalyst-containing coating solution according to (1), which does not contain a silane compound other than the silane coupling agent,
(3) The photocatalyst-containing coating solution according to (1) or (2), further containing fine-particle silica,
(4) The metal coupling agent having no silicon as a metal element is at least one selected from a titanate coupling agent, an aluminate coupling agent and a zirconate coupling agent, (1) or (2) A photocatalyst-containing coating solution according to claim 1,
(5) The photocatalyst-containing coating liquid according to (1) or (2), wherein the photocatalyst material contains titanium dioxide,
(6) A photocatalyst-containing coating solution according to (1) or (2), which contains an acrylic silane coupling agent as a silane coupling agent and further contains a photopolymerization initiator, and (7) of the silane coupling agent The hydrolytic condensate relates to a photocatalyst-containing coating solution according to (1) or (2), which contains a hydrolytic condensate of an epoxy silane coupling agent and the metal coupling agent is an aluminate coupling agent.
The present invention also provides:
(8) A photocatalyst-supporting structure in which a photocatalyst layer is directly provided on a substrate, the photocatalyst-containing coating solution according to any one of (1) to (7) being applied and dried on the substrate,
(9) The photocatalyst carrying structure according to (8), wherein the substrate is an organic material, and (10) the photocatalyst carrying structure according to (9), wherein the organic material is a synthetic resin.
Furthermore, the present invention provides
(11) The present invention relates to a method for forming a photocatalyst-supporting structure by directly applying the photocatalyst-containing coating solution according to any one of (1) to (7) to a substrate and drying it.
本発明の光触媒担持構造体は、十分な光触媒活性を発揮しながら、基材との密着性に優れ、しかも基材にチョーキング等の劣化を起こすことがない。 The photocatalyst carrying structure of the present invention exhibits excellent photocatalytic activity, is excellent in adhesion to the base material, and does not cause deterioration such as choking on the base material.
本発明の光触媒含有塗布液は、光触媒材料微粒子、溶媒、エポキシシランカップリング剤及びアクリルシランカップリング剤から選ばれる少なくとも１種であるシランカップリング剤及び／又は該シランカップリング剤の加水分解縮合物、中心金属元素としてケイ素を有しない金属カップリング剤、及び溶媒を含有する液状組成物である。 The photocatalyst-containing coating liquid of the present invention is a silane coupling agent that is at least one selected from photocatalyst material fine particles, a solvent, an epoxy silane coupling agent, and an acrylic silane coupling agent, and / or hydrolytic condensation of the silane coupling agent. And a liquid composition containing a metal coupling agent having no silicon as a central metal element, and a solvent.
本発明の光触媒含有塗布液に用いる光触媒材料微粒子は、光触媒活性を有する金属酸化物等を含む無機材料からなる微粒子である。
光触媒材料の主成分としては、酸化チタン、酸化亜鉛、酸化錫、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、酸化鉄、酸化ニッケル、酸化ルテニウム、酸化バナジウム、酸化ニオブ、酸化タンタル、酸化ロジウム、酸化レニウム等が挙げられる。これらの中でも、酸化チタン、酸化タングステン等、特にアナターゼ型又はルチル型の酸化チタンが好ましい。The photocatalyst material fine particles used in the photocatalyst-containing coating solution of the present invention are fine particles made of an inorganic material containing a metal oxide having photocatalytic activity.
The main components of the photocatalytic material are titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, iron oxide, nickel oxide, ruthenium oxide, vanadium oxide, niobium oxide, tantalum oxide, rhodium oxide, Examples include rhenium oxide. Among these, titanium oxide, tungsten oxide and the like, particularly anatase type or rutile type titanium oxide are preferable.
また、これらに、Ｐｔ、Ｒｈ、Ｒｕ、Ｎｂ、Ｃｕ、Ｓｎ、Ｎｉ、Ｆｅ、Ａｇ等の金属若しくはこれらの酸化物を添加したものも用いることができる。
特に、ＣｕＯが担持されたルチル型酸化チタンは、紫外線のみならず可視光にも応答して光触媒機能を発揮することから好ましい。
光触媒材料微粒子の粒子径は特に限定されないが、特に填料としてシリカ等の金属酸化物を併用する場合には、十分な光触媒活性を発揮させる意味から、填料の平均粒子径より大きい平均粒子径を有することが好ましく、平均粒子径が４０〜５００ｎｍであることがより好ましい。Moreover, what added metals, such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe, Ag, or these oxides, can also be used for these.
In particular, rutile titanium oxide carrying CuO is preferable because it exhibits a photocatalytic function in response to not only ultraviolet rays but also visible light.
The particle diameter of the photocatalyst material fine particles is not particularly limited, but in particular, when a metal oxide such as silica is used in combination as a filler, it has an average particle diameter larger than the average particle diameter of the filler from the viewpoint of exerting sufficient photocatalytic activity. The average particle size is more preferably 40 to 500 nm.
本発明の光触媒含有塗布液に用いるシランカップリング剤としては、一般式：Ｒ１Ｓｉ（Ｘ）３、Ｒ１（Ｒ２）Ｓｉ（Ｘ）２、又はＲ１（Ｒ２）２ＳｉＸ（ただし各式中、Ｒ１はＳｉで示されるケイ素原子に直結した炭素原子と、エポキシ基及び（メタ）アクリロキシ基から選ばれる少なくとも１種の官能基とを有する有機基を表し、Ｒ２は非加水分解性の有機基を表し、Ｘはフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、アルコキシ基、フェノキシ基、又はアシルオキシ基を表す。Ｒ２で示される基又はＸで示される基が２個以上ある場合には、Ｒ２又はＸはそれぞれ同じものであっても互いに異なっていてもよい。）で示されるものが使用可能である。
ここで、Ｒ１がエポキシ基を有するシランカップリング剤をエポキシシランカップリング剤、Ｒ１が（メタ）アクリロキシ基を有するシランカップリング剤をアクリルシランカップリング剤、と称する。
前記Ｒ１は、置換基及び／又は−Ｏ−基を有していても良いアルキル基等の有機基にエポキシ基又は（メタ）アクリロキシ基を有する基であり、具体的には、γ−グリシドキシプロピル基、β−（３，４−エポキシシクロヘキシル）エチル基、γ−アクリロキシプロピル基、γ−メタクリロキシプロピル基などが例示され、前記Ｒ２としては、メチル基、エチル基などのＣ１〜Ｃ５のアルキル基、及び前記Ｒ１として例示した有機基などが例示され、前記Ｘとしては、塩素原子の他、メトキシ基、エトキシ基、β−メトキシエトキシ基などのＣ１〜Ｃ５のアルコキシ基、ホルミルオキシ基、アセチルオキシ基、プロピオニルオキシ基などのＣ１〜Ｃ６のアシルオキシ基などが例示される。
本発明の光触媒含有塗布液に用いるシランカップリング剤は、特に一般式：Ｒ１Ｓｉ（ＯＲ３）3（式中、Ｒ１は前記と同じものを表し、Ｒ３はＣ１〜３アルキル基を示し、Ｒ３は同じものであっても互いに異なっていてもよい。）
で表される化合物であることが好ましい。
また、本発明の光触媒含有塗布液には、少なくとも１種のエポキシシランカップリング剤またはその加水分解縮合物、及び、少なくとも１種のアクリルシランカップリング剤またはその加水分解縮合物のいずれか一方のみを含有することが好ましい。As a silane coupling agent used for the photocatalyst containing coating liquid of the present invention, a general formula: R 1 Si (X) 3 , R 1 (R 2 ) Si (X) 2 , or R 1 (R 2 ) 2 SiX (however, In each formula, R 1 represents an organic group having a carbon atom directly connected to a silicon atom represented by Si, and at least one functional group selected from an epoxy group and a (meth) acryloxy group, and R 2 represents a non-hydrolyzed group. Represents a decomposable organic group, and X represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group, a phenoxy group or an acyloxy group, a group represented by R 2 or a group represented by X When there are two or more, R 2 or X may be the same or different from each other.
Here, the silane coupling agent in which R 1 has an epoxy group is referred to as an epoxy silane coupling agent, and the silane coupling agent in which R 1 has a (meth) acryloxy group is referred to as an acrylic silane coupling agent.
R 1 is a group having an epoxy group or a (meth) acryloxy group in an organic group such as an alkyl group which may have a substituent and / or —O— group, and specifically, γ-glycol. Sidoxypropyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ-acryloxypropyl group, γ-methacryloxypropyl group, etc. are exemplified, and as R 2 , C1 such as methyl group, ethyl group, etc. And an organic group exemplified as the R 1 , and the X is a chlorine atom, a C1-C5 alkoxy group such as a methoxy group, an ethoxy group, and a β-methoxyethoxy group, Examples thereof include C1-C6 acyloxy groups such as formyloxy group, acetyloxy group and propionyloxy group.
The silane coupling agent used in the photocatalyst-containing coating solution of the present invention is particularly represented by the general formula: R 1 Si (OR 3 ) 3 (wherein R 1 represents the same as described above, and R 3 represents a C1-3 alkyl group. And R 3 may be the same or different from each other.)
It is preferable that it is a compound represented by these.
In addition, the photocatalyst-containing coating liquid of the present invention includes at least one of at least one epoxysilane coupling agent or a hydrolysis condensate thereof, and at least one acrylic silane coupling agent or a hydrolysis condensate thereof. It is preferable to contain.
本発明の光触媒含有塗布液には、前記シランカップリング剤以外のシラン化合物を含有しないことが好ましい。これにより、ハードコート性をさらに高めることができる。
前記シランカップリング剤以外のシラン化合物としては、一般式：Ｓｉ（Ｘ）４、Ｒ４Ｓｉ（Ｘ）３、（Ｒ４）２Ｓｉ（Ｘ）２、（Ｒ４）３ＳｉＸ、これらの縮合物、又は（Ｒ４）４Ｓｉ（ただし各式中、Ｒ４は非加水分解性であり、かつエポキシ基、アクリロキシ基及びメタクリロキシ基のいずれも有しない有機基を表し、Ｒ４で示される基が２個以上ある場合には、Ｒ４は同じものであっても互いに異なっていてもよい。Ｘは前記と同じものを表す。）で示されるものが挙げられ、より具体的には、有機物と反応しない、ジアルコキシジアルキルシラン、ジアルコキシジフェニルシラン、トリアルコキシアルキルシラン、トリアルコキシフェニルシラン、テトラアルコキシシラン、テトラフェノキシシラン等の化合物が例示される。The photocatalyst-containing coating solution of the present invention preferably contains no silane compound other than the silane coupling agent. Thereby, hard coat property can further be improved.
Examples of silane compounds other than the silane coupling agent include general formulas: Si (X) 4 , R 4 Si (X) 3 , (R 4 ) 2 Si (X) 2 , (R 4 ) 3 SiX, and their condensations. Or (R 4 ) 4 Si (wherein R 4 represents a non-hydrolyzable organic group having no epoxy group, acryloxy group or methacryloxy group, and represented by R 4) R 4 may be the same or different from each other, X represents the same as above, and more specifically, an organic substance. Does not react with dialkoxydialkylsilane, dialkoxydiphenylsilane, trialkoxyalkylsilane, trialkoxyphenylsilane, tetraalkoxysilane, tetraphenoxysilane, etc. It is shown.
本発明の光触媒含有塗布液に含有されるシランカップリング剤は、加水分解縮合させることによって、塗膜の強度を高めることができる。
特に、シランカップリング剤としてエポキシ系シランカップリング剤を用いる場合、シランカップリング剤を加水分解縮合してからその他の成分と混合することが好ましい。この場合には、後記の金属カップリング剤としては、アルミネート系カップリング剤を用いるのが好ましい。チタネート系カップリング剤やジルコネート系カップリング剤を用いる場合には、水が存在するとこれらが加水分解を受け金属カップリング剤による塗膜強化効果が却って損なわれることがある。The strength of the coating film can be increased by hydrolytic condensation of the silane coupling agent contained in the photocatalyst-containing coating solution of the present invention.
In particular, when an epoxy silane coupling agent is used as the silane coupling agent, it is preferable to hydrolyze and condense the silane coupling agent before mixing with other components. In this case, it is preferable to use an aluminate coupling agent as a metal coupling agent described later. In the case of using a titanate coupling agent or a zirconate coupling agent, if water is present, these undergo hydrolysis and the coating strengthening effect by the metal coupling agent may be impaired.
また、本発明の光触媒含有塗布液には、シランカップリング剤としてアクリルシランカップリング剤を用いる場合、さらに光重合開始剤を含有することが好ましい。光重合開始剤は、紫外線を照射した際に（メタ）アクリロキシ基間において重合反応を開始させることが可能な化合物であればよい。これにより、アクリルシランカップリング剤の重合が促進され、塗膜の強度を高めることができる。
光重合開始剤として具体的には、紫外線の照射によりラジカルを発生し、そのラジカルが重合のきっかけとなる、ベンゾイン誘導体等が挙げられる。特に、アルキルフェノン系光重合開始剤である、Ｉｒｇａｃｕｒｅ（登録商標）６５１、１８４、９０７、３６９、３７９（ＢＡＳＦ社製）等が好適である。Moreover, when using an acrylic silane coupling agent as a silane coupling agent, it is preferable to contain a photoinitiator further in the photocatalyst containing coating liquid of this invention. The photopolymerization initiator may be a compound that can start a polymerization reaction between (meth) acryloxy groups when irradiated with ultraviolet rays. Thereby, superposition | polymerization of an acrylsilane coupling agent is accelerated | stimulated and the intensity | strength of a coating film can be raised.
Specific examples of the photopolymerization initiator include benzoin derivatives that generate radicals by irradiation with ultraviolet rays, and the radicals cause polymerization. In particular, Irgacure (registered trademark) 651, 184, 907, 369, 379 (manufactured by BASF), which is an alkylphenone photopolymerization initiator, is suitable.
本発明の光触媒塗布液に用いる、金属元素としてケイ素を有しない金属カップリング剤とは、加水分解性基を有し、これにより架橋反応する、金属化合物である。より具体的には、金属元素に配位子が配位してなる金属錯体、金属元素にアルコキシ基が結合してなる金属アルコラートのいずれか（両方に分類される化合物も含む。）が挙げられる。
このうち、チタネート系カップリング剤、アルミネート系カップリング剤及びジルコネート系カップリング剤が好ましい。The metal coupling agent having no silicon as a metal element used in the photocatalyst coating solution of the present invention is a metal compound having a hydrolyzable group and thereby undergoing a crosslinking reaction. More specifically, any of a metal complex in which a ligand is coordinated to a metal element and a metal alcoholate in which an alkoxy group is bonded to the metal element (including compounds classified into both) is also included. .
Of these, titanate coupling agents, aluminate coupling agents and zirconate coupling agents are preferred.
チタネート系カップリング剤としては、例えば、テトライソプロピルチタネート、テトラ−ｎ−ブチルチタネート、テトラキス（２−エチルヘキシルオキシ）チタン、チタニウム−ｉ−プロポキシオクチレングリコレート等のチタンアルコキシド；チタンアセチルアセトナート、チタンテトラアセチルアセトナート、ジ−ｉ−プロポキシ・ビス（アセチルアセトナート）チタン、ジ−ｎ−プロポキシ・ビス（アセチルアセトナート）チタン、ジ−ｎ−ブトキシ・ビス（アセチルアセトナート）チタン、ジエトキシ・ビス（アセチルアセトナート）チタン、プロパンジオキシチタンビス（エチルアセトアセテート）等のチタン錯体等がある。 Examples of titanate coupling agents include titanium alkoxides such as tetraisopropyl titanate, tetra-n-butyl titanate, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate; titanium acetylacetonate, titanium Tetraacetylacetonate, di-i-propoxy bis (acetylacetonato) titanium, di-n-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, diethoxy bis There are titanium complexes such as (acetylacetonato) titanium and propanedioxytitanium bis (ethylacetoacetate).
アルミネート系カップリング剤としては、例えば、アルミニウムイソプロピレート、モノ−ｓｅｃ−ブトキシアルミニウムジイソプロピレート、アルミニウムエチレート等のアルミニウムアルコレート；エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムビスエチルアセトアセテート・モノアセチルアセトナート、アルミニウムトリス（エチルアセトアセテート）、アルミニウムトリス（アセチルアセトナート）、ジエトキシモノ（アセチルアセトナート）アルミニウム、ジ−ｉ−プロポキシモノ（アセチルアセトナート）アルミニウム、ジ−ｎ−プロポキシモノ（アセチルアセトナート）アルミニウム、ジ−ｎ−ブトキシモノ（アセチルアセトナート）アルミニウム、エトキシビス（アセチルアセトナート）アルミニウム、ｉ−プロポキシビス（アセチルアセトナート）アルミニウム、ｎ−プロポキシビス（アセチルアセトナート）アルミニウム、ｎ−ブトキシビス（アセチルアセトナート）アルミニウム等のアルミニウム錯体；環状アルミニウムオリゴマー等がある。 Examples of aluminate coupling agents include aluminum alcoholates such as aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, aluminum ethylate; ethyl acetoacetate aluminum diisopropylate, aluminum bisethylacetoacetate monoacetyl Acetonate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), diethoxymono (acetylacetonato) aluminum, di-i-propoxymono (acetylacetonato) aluminum, di-n-propoxymono (acetylacetonate) ) Aluminum, di-n-butoxymono (acetylacetonato) aluminum, ethoxybis (acetylacetonato) aluminum Arm, i- Puropokishibisu (acetylacetonate) aluminum, n- Puropokishibisu (acetylacetonate) aluminum, n- butoxy bis aluminum complexes such as (acetylacetonate) aluminum; an annular aluminum oligomers.
ジルコネート系カップリング剤としては、ジルコニウムテトラキス（アセチルアセトナート）、ジ−ｎ−ブトキシビス（アセチルアセトナート）ジルコニウム、ジルコニウムテトラキス（エチルアセトアセテート）、ジエトキシビスアセチルアセトナートジルコニウム、ジ−ｉ−プロポキシビス（アセチルアセトナート）ジルコニウム、ジ−ｎ−プロポキシビス（アセチルアセトナート）ジルコニウム、トリ−ｎ−ブトキシモノエチルアセトアセテートジルコニウム、トリ−ｎ−ブトキシモノアセチルアセトナートジルコニウム等がある。 Zirconate coupling agents include zirconium tetrakis (acetylacetonate), di-n-butoxybis (acetylacetonato) zirconium, zirconium tetrakis (ethylacetoacetate), diethoxybisacetylacetonatozirconium, di-i-propoxybis (Acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, tri-n-butoxymonoethylacetoacetate zirconium, tri-n-butoxymonoacetylacetonatozirconium and the like.
アセチルアセトナート系カップリング剤としては、前記のチタネート系カップリング剤、アルミネート系カップリング剤、及びジルコネート系カップリング剤のうちアセチルアセトナート系カップリング剤であるものが挙げられる。 Examples of the acetylacetonate coupling agent include those that are acetylacetonate coupling agents among the titanate coupling agents, aluminate coupling agents, and zirconate coupling agents.
本発明の光触媒含有塗布液には溶媒が含有される。溶媒は特に限定されないが、例えば、水；メタノール、エタノール、プロピルアルコール、イソプロピルアルコール、ブタノール、ｔ−ブタノール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノン等のケトン類；ジエチルエーテル、メチルセルソルブ、テトラヒドロフラン等のエーテル類；ベンゼン、トルエン、キシレン等の芳香族炭化水素；ジクロロメタン、クロロホルム等のハロゲン化炭化水素；酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル類；ペンタン、ヘキサン、シクロヘキサン等の飽和炭化水素等を挙げることができる。また、これらの２種以上を混合して用いることもできる。これらの内、アルコール類が特に好ましい。 The photocatalyst-containing coating solution of the present invention contains a solvent. Although the solvent is not particularly limited, for example, water; alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, and t-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, and cyclohexanone; diethyl ether, Ethers such as methyl cellosolve and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate, propyl acetate and butyl acetate; pentane, hexane and cyclohexane And saturated hydrocarbons. Moreover, these 2 types or more can also be mixed and used. Of these, alcohols are particularly preferred.
本発明の光触媒含有塗布液には、前記各成分のほかに、成膜助剤、増粘剤、消泡剤、顔料、填料、分散剤、染料、防腐剤などを、本発明の効果を損なわない範囲で任意に配合することができる。
特に、微粒子からなる金属酸化物を填料として用いることにより、耐光性を高めるなどの効果が得られる。
填料として用いる金属酸化物としては、マグネシウム、アルミニウム、ケイ素、チタン、バナジウム、鉄、ニッケル、銅、亜鉛、イットリウム、ジルコニウム、ニオブ、モリブデン、ルテニウム、インジウム、錫、アンチモン、タンタル、タングステン、セリウム等の元素を含む酸化物（ただし光触媒材料を除く。）が挙げられる。In addition to the above-mentioned components, the photocatalyst-containing coating solution of the present invention includes a film forming aid, a thickener, an antifoaming agent, a pigment, a filler, a dispersant, a dye, a preservative, and the like, and the effects of the present invention are impaired. It can mix | blend arbitrarily in the range which is not.
In particular, by using a metal oxide composed of fine particles as a filler, effects such as enhancement of light resistance can be obtained.
Metal oxides used as fillers include magnesium, aluminum, silicon, titanium, vanadium, iron, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, indium, tin, antimony, tantalum, tungsten, cerium, etc. Examples thereof include oxides containing elements (excluding photocatalytic materials).
本発明の光触媒含有塗布液には、特に微粒子シリカを含有することが好ましい。これによりチョーキング防止効果が高められる。これは、光触媒粒子表面をシリカが覆い、光触媒による有機成分への攻撃が緩和されるためと考えられる。微粒子シリカとしては、平均粒子径が１００ｎｍ以下であることが好ましい。また微粒子シリカの形状としては、球状シリカ粒子、若しくは球状シリカ粒子が細長い形状に結合してなる粒子（その全体の平均粒子径は１００ｎｍ以下であることが好ましい。）が好ましい。ここに言う球状シリカ粒子の平均粒子径は４０ｎｍ以下であることが好ましく、５〜２０ｎｍであることがより好ましい。平均粒子径が１００ｎｍより大きいと、スチールウールや爪による擦り耐性が劣る。 The photocatalyst-containing coating solution of the present invention preferably contains fine particle silica. Thereby, the anti-choking effect is enhanced. This is presumably because silica covers the surface of the photocatalyst particles, and the attack on the organic component by the photocatalyst is mitigated. The fine particle silica preferably has an average particle diameter of 100 nm or less. Further, the shape of the fine particle silica is preferably spherical silica particles or particles formed by bonding spherical silica particles in an elongated shape (the average particle diameter of the whole is preferably 100 nm or less). The average particle diameter of the spherical silica particles mentioned here is preferably 40 nm or less, and more preferably 5 to 20 nm. When the average particle diameter is larger than 100 nm, the abrasion resistance due to steel wool or nails is inferior.
本発明の光触媒含有塗布液は、光触媒材料微粒子１００質量部に対して、前記シランカップリング剤及び該シランカップリング剤の加水分解縮合物の合計を３００質量部以上の比率で含有する。前記シランカップリング剤及び該シランカップリング剤の加水分解縮合物の合計は３００〜１０００質量部の比率で含有されることがより好ましい。
また、光触媒１００質量部に対して、その他の成分を以下の比率で含有することが好ましい。
金属カップリング剤：２０質量部以上、より好ましくは５０〜３００質量部。
金属酸化物からなる填料、好ましくは微粒子シリカ：０〜４００質量部、より好ましくは５０〜４００質量部。
また、本発明の光触媒含有塗布液は、固形成分中の質量％として、光触媒を０．５〜２０質量％、シランカップリング剤及び／又はシランカップリング剤の加水分解縮合物を合計で５〜８０質量％、より好ましくは２０〜８０質量％、金属カップリング剤を２〜６０質量％、より好ましくは２〜３０質量％、金属酸化物からなる填料、好ましくは微粒子シリカを、０〜４０質量％、より好ましくは１〜２０質量％含有することが好ましい。The photocatalyst-containing coating solution of the present invention contains 300 parts by mass or more of the total of the silane coupling agent and the hydrolysis condensate of the silane coupling agent with respect to 100 parts by mass of the photocatalyst material fine particles. The total of the silane coupling agent and the hydrolysis condensate of the silane coupling agent is more preferably contained in a ratio of 300 to 1000 parts by mass.
Moreover, it is preferable to contain another component with the following ratio with respect to 100 mass parts of photocatalysts.
Metal coupling agent: 20 parts by mass or more, more preferably 50 to 300 parts by mass.
Filler made of metal oxide, preferably fine-particle silica: 0 to 400 parts by mass, more preferably 50 to 400 parts by mass.
Moreover, the photocatalyst containing coating liquid of this invention is 5-20 mass% of photocatalysts as a mass% in a solid component, and the hydrolysis condensate of a silane coupling agent and / or a silane coupling agent is 5 in total. 80% by mass, more preferably 20-80% by mass, 2-60% by mass of metal coupling agent, more preferably 2-30% by mass, filler consisting of metal oxide, preferably 0-40% by mass of fine silica. %, More preferably 1 to 20% by mass.
本発明の光触媒担持構造体は、本発明の光触媒含有塗布液を基材上に塗布し乾燥してなる、基材上に光触媒層が直接接している光触媒担持構造体である。
基材は特に限定されないが、無機材料としては、金属、ガラス、セラミックス、セメント等、有機材料としては、木材；紙；天然繊維；ゴム；皮革；ポリエチレン、ポリプロピレン、アクリル樹脂、ポリエチレンテレフタラート、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリカーボネート、ポリスチレン、ＡＢＳ樹脂、フェノール樹脂、尿素樹脂、ポリウレタン、エポキシ樹脂、メラミン樹脂等の合成樹脂等を例示することができる。
このうち、光触媒層を直接設けることが従来困難であった、有機材料、なかでも合成樹脂が好ましい。
合成樹脂の光触媒層が接する表面には、光触媒含有塗布液を塗布する前に、易接着処理を施すことが好ましい。この易接着処理としては、例えば、表面にコロナ放電処理や、ＵＶ−オゾン処理を施す方法が挙げられる。The photocatalyst carrying structure of the present invention is a photocatalyst carrying structure in which the photocatalyst layer is in direct contact with the base material, which is obtained by applying the photocatalyst-containing coating liquid of the present invention onto the base material and drying it.
The base material is not particularly limited, but inorganic materials include metal, glass, ceramics, cement, etc., and organic materials include wood; paper; natural fibers; rubber; leather; polyethylene, polypropylene, acrylic resin, polyethylene terephthalate, poly Examples thereof include synthetic resins such as vinyl chloride, polyvinylidene chloride, polycarbonate, polystyrene, ABS resin, phenol resin, urea resin, polyurethane, epoxy resin, and melamine resin.
Of these, organic materials, particularly synthetic resins, which have conventionally been difficult to directly provide a photocatalytic layer are preferred.
It is preferable to subject the surface of the synthetic resin photocatalyst layer to contact with the surface before applying the photocatalyst-containing coating solution. Examples of the easy adhesion treatment include a method of performing corona discharge treatment or UV-ozone treatment on the surface.
本発明の光触媒含有塗布液を基材に塗布する方法は、特に限定されず、スプレーコーティング法、フローコーティング法、スピンコーティング法、メイヤバー工法、ディップコーティング法、ロールコーティング法等の公知の方法により、所定の塗工量で塗工した後乾燥し、所定の厚みで光触媒層を形成させればよい。 The method for applying the photocatalyst-containing coating solution of the present invention to the substrate is not particularly limited, and is a known method such as a spray coating method, a flow coating method, a spin coating method, a Meyer bar method, a dip coating method, or a roll coating method. What is necessary is just to dry after apply | coating with a predetermined coating amount, and to form a photocatalyst layer with predetermined thickness.
本発明の光触媒担持構造体における光触媒層の厚みは、特に限定されないが、乾燥後の厚みが通常０．０１〜１０μｍであり、０．５〜５．０μｍがより好ましい。 Although the thickness of the photocatalyst layer in the photocatalyst carrying structure of the present invention is not particularly limited, the thickness after drying is usually 0.01 to 10 μm, and more preferably 0.5 to 5.0 μm.
本発明の光触媒含有塗布液がアクリルシランカップリング剤及び光重合開始剤を含有する場合には、前記の乾燥工程の後、さらに紫外線を照射することが好ましく、該紫外線は３５０ｎｍ以下の波長を含むことがより好ましい。
この紫外線照射には、超高圧水銀ランプ、高圧水銀ランプ、低圧水銀ランプ、メタルはライドランプ、エキシマ―ランプ、カーボンアークランプ、キセノンアークランプ等の装置を用いることができる。また紫外線照射量としては、０．１〜１００Ｊ／ｃｍ２が好ましい。When the photocatalyst-containing coating solution of the present invention contains an acrylic silane coupling agent and a photopolymerization initiator, it is preferable to further irradiate ultraviolet rays after the drying step, and the ultraviolet rays include a wavelength of 350 nm or less. It is more preferable.
For this ultraviolet irradiation, an apparatus such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal lamp, an excimer lamp, a carbon arc lamp, or a xenon arc lamp can be used. Moreover, as an ultraviolet irradiation amount, 0.1-100 J / cm < 2 > is preferable.
以下に本発明の実施例を示すが、本発明の技術的範囲はこれらに限定されるものではない。 Examples of the present invention are shown below, but the technical scope of the present invention is not limited thereto.
［製造例１］（光触媒材料微粒子）
蒸留水１０００ｇに６０ｇ（１００質量部）のルチル型酸化チタンＡ（昭和電工セラミックス社製、ルチル化率９５．９モル％）を懸濁させ、さらに４．９７９ｇ（銅換算で３．０質量部）のＣｕＣｌ２・２Ｈ２Ｏ（関東化学株式会社製）を添加して、１０分攪拌した。ｐＨが１０になるように、１ｍｏｌ／Ｌの水酸化ナトリウム（関東化学社製）水溶液を添加し、３０分間攪拌混合を行ってスラリーを得た。
このスラリーをろ過し、得られた固形分を純水で洗浄し、８０℃で乾燥し、ミキサーで粉砕した。この粉砕物を大気中、４５０℃で、３時間熱処理し、試料１を得た。
なお、この試料１を、フッ酸溶液中で加熱して全溶解し、抽出液をＩＣＰ発光分光分析により定量したところ、酸化チタン１００質量部に対して、銅イオンが３．０質量部であった。すなわち、仕込みの銅イオン（ＣｕＣｌ２・２Ｈ２Ｏ由来）の全量がＣｕＯとして酸化チタン表面に担持されていた。また試料１の平均粒子径は約１５０ｎｍであった。
イソプロピルアルコールに一定量の試料１を添加して懸濁させ、固形分含量０．２５〜５．０質量％の光触媒懸濁液を作製した。[Production Example 1] (Photocatalyst material fine particles)
60 g (100 parts by mass) of rutile-type titanium oxide A (manufactured by Showa Denko Ceramics Co., Ltd., 95.9 mol%) is suspended in 1000 g of distilled water, and further 4.979 g (3.0 parts by mass in terms of copper). ) CuCl 2 · 2H 2 O (manufactured by Kanto Chemical Co., Inc.) was added and stirred for 10 minutes. A 1 mol / L sodium hydroxide (manufactured by Kanto Chemical Co.) aqueous solution was added so that the pH was 10, and the mixture was stirred and mixed for 30 minutes to obtain a slurry.
This slurry was filtered, and the obtained solid content was washed with pure water, dried at 80 ° C., and pulverized with a mixer. This pulverized product was heat-treated at 450 ° C. for 3 hours in the air to obtain Sample 1.
The sample 1 was heated and dissolved in a hydrofluoric acid solution, and the extract was quantified by ICP emission spectroscopic analysis. As a result, the copper ion was 3.0 parts by mass with respect to 100 parts by mass of titanium oxide. It was. That is, the total amount of charged copper ions (derived from CuCl 2 · 2H 2 O) was supported on the titanium oxide surface as CuO. The average particle size of Sample 1 was about 150 nm.
A certain amount of Sample 1 was added to isopropyl alcohol and suspended therein to prepare a photocatalyst suspension having a solid content of 0.25 to 5.0% by mass.
（金属カップリング剤の効果）
［実施例１、２、３、４、比較例１］
製造例１で得られた、固形分含量が０．２５質量％（実施例１）、０．５質量％（実施例２）、１．０質量％（実施例３）、２．５質量％（実施例４）、又は５．０質量％（比較例１）の光触媒懸濁液２１．６７ｇに、ＫＢＭ−５１０３（γ−アクリロキシプロピルトリメトキシシラン、信越シリコーン社製）２．２７ｇを添加して５分間撹拌し、Ｔ−５０（ジ−ｉ−プロポキシ・ビス（アセチルアセトナート）チタン、日本曹達社製）０．８６ｇを添加して５分間撹拌し、さらにＩｒｇａｃｕｒｅ（登録商標）９０７（光重合開始剤２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン、ＢＡＳＦ社製）０．２３ｇを添加して５分間撹拌し、光触媒塗布液を得た。(Effect of metal coupling agent)
[Examples 1, 2, 3, 4 and Comparative Example 1]
The solid content obtained in Production Example 1 was 0.25% by mass (Example 1), 0.5% by mass (Example 2), 1.0% by mass (Example 3), 2.5% by mass. (Example 4) or 2.27 g of KBM-5103 (γ-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone) was added to 21.67 g of the photocatalyst suspension of 5.0% by mass (Comparative Example 1). The mixture was stirred for 5 minutes, 0.86 g of T-50 (di-i-propoxy bis (acetylacetonato) titanium, manufactured by Nippon Soda Co., Ltd.) was added, and the mixture was stirred for 5 minutes, and further Irgacure (registered trademark) 907 ( 0.23 g of photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (manufactured by BASF) was added and stirred for 5 minutes to obtain a photocatalyst coating solution. It was.
［比較例２、３、４、５］
固形分含量が０．２５質量％（比較例２）、０．５質量％（比較例３）、１．０質量％（比較例４）、又は２．５質量％（比較例５）の光触媒懸濁液２１．６７ｇに、ＫＢＭ−５１０３（γ−アクリロキシプロピルトリメトキシシラン、信越シリコーン社製）２．２７ｇを添加して５分間撹拌し、さらにＩｒｇａｃｕｒｅ（登録商標）９０７ ０．２３ｇを添加して５分間撹拌し、光触媒含有塗布液を得た。[Comparative Examples 2, 3, 4, 5]
A photocatalyst having a solid content of 0.25% by mass (Comparative Example 2), 0.5% by mass (Comparative Example 3), 1.0% by mass (Comparative Example 4), or 2.5% by mass (Comparative Example 5) 2.27 g of KBM-5103 (γ-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone) was added to 21.67 g of the suspension and stirred for 5 minutes, and 0.23 g of Irgacure (registered trademark) 907 was further added. And stirred for 5 minutes to obtain a photocatalyst-containing coating solution.
［試験例１］
コスモシャイン（登録商標）Ａ４３００（易接着処理されたポリエチレンテレフタラートフィルム、東洋紡社製）上に、実施例１〜５及び比較例１〜４で得られた各光触媒塗布液をバーコート成膜し、１００℃で５分乾燥させた。
これらの成膜サンプルに、ＵＶ照射（４００ｍＪ／ｃｍ２）を行った後、表１に示した期間にわたってＢＬＢ照射（１ｍＷ／ｃｍ２）を行い、その後、スチールウール擦り試験（２００ｇ荷重、２０往復）、及び爪ひっかき試験を行った。結果を表１に示した。結果を表す記号は次の通り。
スチールウール擦り・・・◎：ほぼ無傷、○：傷わずか、△：傷数本、×：傷多数
爪ひっかき・・・○：傷つかない、△：何度も擦ると傷つく、×：容易に傷つく
−：実施せず[Test Example 1]
Each photocatalyst coating solution obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was bar-coated on Cosmo Shine (registered trademark) A4300 (polyethylene terephthalate film subjected to easy adhesion treatment, manufactured by Toyobo Co., Ltd.). And dried at 100 ° C. for 5 minutes.
These film formation samples were subjected to UV irradiation (400 mJ / cm 2 ) and then subjected to BLB irradiation (1 mW / cm 2 ) over the period shown in Table 1, and then a steel wool rubbing test (200 g load, 20 reciprocations). ), And a nail scratch test. The results are shown in Table 1. The symbols representing the results are as follows.
Steel wool rubbing ◎: Almost intact, ○: Slightly scratched, △: Several scratches, ×: Many scratches Nail scratches ... ○: Not scratched, △: Scratched many times, ×: Scratched easily -: Not implemented
以上から、金属カップリング剤を添加すると、ＢＬＢ照射下でも長期間にわたり硬度が維持されること、また光触媒に比較してシランカップリング剤が多い方が硬度に優れることがわかる。 From the above, it can be seen that when a metal coupling agent is added, the hardness is maintained over a long period of time even under BLB irradiation, and that the more silane coupling agent is superior to the photocatalyst, the better the hardness is.
（微粒子シリカの効果）
［実施例５］
製造例１で得られた固形分含量２．５質量％の光触媒懸濁液２１．６７ｇに、ＫＢＭ−４０３（γ−グリシドキシプロピルトリエトキシシラン、信越シリコーン社製）２．２７ｇを添加して５分間撹拌し、さらにＴ−５０ ０．８６ｇを添加して５分間撹拌し、光触媒含有塗布液を得た。(Effect of fine particle silica)
[Example 5]
2.27 g of KBM-403 (γ-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Silicone) was added to 21.67 g of the photocatalyst suspension having a solid content of 2.5% by mass obtained in Production Example 1. Then, 0.86 g of T-50 was added and stirred for 5 minutes to obtain a photocatalyst-containing coating solution.
［実施例６、７、８］
実施例５で得た光触媒含有塗布液に、さらにＩＰＡ−ＳＴ（微粒子シリカ、粒径１０〜１５ｎｍ、３０質量％でイソプロピルアルコール中に懸濁、日産化学工業社製）０．９ｇ（実施例６）、１．８ｇ（実施例７）又は３．６ｇ（実施例８）を添加して５分間混合し、光触媒含有塗布液を得た。[Examples 6, 7, and 8]
To the photocatalyst-containing coating solution obtained in Example 5, 0.9 g of IPA-ST (particulate silica, particle size 10 to 15 nm, suspended in isopropyl alcohol at 30% by mass, manufactured by Nissan Chemical Industries, Ltd.) ), 1.8 g (Example 7) or 3.6 g (Example 8) was added and mixed for 5 minutes to obtain a photocatalyst-containing coating solution.
［実施例９、１０、１１］
ＩＰＡ−ＳＴに代えて、ＩＰＡ−ＳＴ−ＵＰ（鎖状シリカ、粒径４０〜１００ｎｍ、１５質量％でイソプロピルアルコール中に懸濁、日産化学工業社製）を１．８ｇ（実施例９）、３．６ｇ（実施例１０）、又は７．２ｇ（実施例１１）混合した以外は、実施例６〜８と同様の方法で、光触媒含有塗布液を得た。[Examples 9, 10, and 11]
Instead of IPA-ST, 1.8 g (Example 9) of IPA-ST-UP (chain silica, particle size 40-100 nm, suspended in isopropyl alcohol at 15% by mass, manufactured by Nissan Chemical Industries, Ltd.) A photocatalyst-containing coating solution was obtained in the same manner as in Examples 6 to 8, except that 3.6 g (Example 10) or 7.2 g (Example 11) was mixed.
［実施例１２、１３、１４］
ＩＰＡ−ＳＴに代えて、セルナックス（登録商標）ＣＸ−Ｚ２１０（酸化アンチモンを含有する複酸化物、粒径１５ｎｍ、２１質量％でイソプロピルアルコール中に懸濁、日産化学工業社製）を１．２９ｇ（実施例１２）、２．５７ｇ（実施例１３）、又は５．１４ｇ（実施例１４）混合した以外は、実施例６〜８と同様の方法で、光触媒含有塗布液を得た。[Examples 12, 13, and 14]
In place of IPA-ST, Celnax (registered trademark) CX-Z210 (double oxide containing antimony oxide, particle size 15 nm, suspended in isopropyl alcohol at 21% by mass, manufactured by Nissan Chemical Industries, Ltd.) A photocatalyst-containing coating solution was obtained in the same manner as in Examples 6 to 8, except that 29 g (Example 12), 2.57 g (Example 13), or 5.14 g (Example 14) were mixed.
［試験例２］
コスモシャインＡ４３００上に、実施例５〜１４で得られた各光触媒含有塗布液をバーコート成膜し、１００℃で１５分乾燥させた。
これらの成膜サンプルに、表２に示した期間にわたってＢＬＢ照射（１ｍＷ／ｃｍ２）を行い、その後、試験例１と同様の方法で試験を行った。結果を表２に示した。結果を表す記号は表１と同じ。[Test Example 2]
Each photocatalyst-containing coating solution obtained in Examples 5 to 14 was bar-coated on Cosmo Shine A4300 and dried at 100 ° C. for 15 minutes.
These film formation samples were subjected to BLB irradiation (1 mW / cm 2 ) over the period shown in Table 2, and then tested in the same manner as in Test Example 1. The results are shown in Table 2. The symbols representing the results are the same as in Table 1.
以上から、エポキシ系シランカップリング剤を使用した場合に、微粒子シリカを添加すると、ＢＬＢ照射下でも長期間にわたり硬度が維持されることがわかる。 From the above, it can be seen that when an epoxy silane coupling agent is used, the addition of fine-particle silica maintains the hardness over a long period of time even under BLB irradiation.
（微粒子シリカの効果）
［実施例１５、１６、１７］
実施例４で得た光触媒含有塗布液に、さらにＩＰＡ−ＳＴを０．９ｇ（実施例１５）、１．８ｇ（実施例１６）、又は３．６ｇ（実施例１７）を添加して５分間混合し、光触媒含有塗布液を得た。(Effect of fine particle silica)
[Examples 15, 16, and 17]
To the photocatalyst-containing coating solution obtained in Example 4, 0.9 g (Example 15), 1.8 g (Example 16), or 3.6 g (Example 17) of IPA-ST was further added for 5 minutes. By mixing, a photocatalyst-containing coating solution was obtained.
［試験例３］
コスモシャインＡ４３００上に、実施例４及び１５〜１７で得られた各光触媒含有塗布液をバーコート成膜し、１００℃で５分乾燥させた。
これらの成膜サンプルに、ＵＶ照射（４００ｍＪ／ｃｍ２）を行った後、表３に示した期間にわたってＢＬＢ照射（１ｍＷ／ｃｍ２）を行い、その後、試験例１と同様の方法で試験を行った。結果を表３に示した。結果を表す記号は表１と同じ。[Test Example 3]
Each photocatalyst-containing coating solution obtained in Examples 4 and 15 to 17 was bar-coated on Cosmo Shine A4300 and dried at 100 ° C. for 5 minutes.
These film formation samples were irradiated with UV (400 mJ / cm 2 ), then subjected to BLB irradiation (1 mW / cm 2 ) over the period shown in Table 3, and then tested in the same manner as in Test Example 1. went. The results are shown in Table 3. The symbols representing the results are the same as in Table 1.
以上から、アクリル系シランカップリング剤を使用した場合でも、微粒子シリカを添加すると、ＵＶ照射下でも長期間にわたり硬度が維持されることがわかる。 From the above, it can be seen that even when an acrylic silane coupling agent is used, if fine particle silica is added, the hardness is maintained over a long period of time even under UV irradiation.
（微粒子シリカの効果：比較）
［比較例６、７］
製造例１において得られた固形分含量２．５質量％の光触媒懸濁液２１．６７ｇに、ＫＲＭ−８５２８Ｃ ２．２５ｇ（比較例６）、又はＥＢＥＣＲＹＬ８３１１（登録商標）２．１４ｇ（比較例７）を添加して５分間撹拌し、さらにＩｒｇａｃｕｒｅ９０７ ０．１１ｇを添加して５分間撹拌し、光触媒含有塗布液を得た。ＫＲＭ−８５２８Ｃ及びＥＢＥＣＲＹＬ８３１１は、いずれも、高耐候性ナノシリカ含有ウレタンアクリレート樹脂（ダイセル・オルネクス社製）である。(Effect of fine particle silica: comparison)
[Comparative Examples 6 and 7]
21.67 g of the photocatalyst suspension having a solid content of 2.5% by mass obtained in Production Example 1 was added to 2.25 g of KRM-8528C (Comparative Example 6) or 2.14 g of EBECRYL8311 (registered trademark) (Comparative Example 7). And 0.15 g of Irgacure 907 was added and stirred for 5 minutes to obtain a photocatalyst-containing coating solution. KRM-8528C and EBECRYL8311 are both highly weather-resistant nanosilica-containing urethane acrylate resins (manufactured by Daicel Ornex).
［試験例４］
コスモシャインＡ４３００上に、比較例５及び６で得られた各光触媒含有塗布液をバーコート成膜し、１００℃で５分乾燥させた。
これらの成膜サンプルに、ＵＶ照射（４００ｍＪ／ｃｍ２）を行った後、表４に示した期間にわたってＢＬＢ照射（１ｍＷ／ｃｍ２）を行い、その後、試験例１と同様の方法で試験を行った。結果を表４に示した。結果を表す記号は表１と同じ。[Test Example 4]
Each photocatalyst-containing coating solution obtained in Comparative Examples 5 and 6 was bar-coated on Cosmo Shine A4300 and dried at 100 ° C. for 5 minutes.
These film formation samples were irradiated with UV (400 mJ / cm 2 ), then subjected to BLB irradiation (1 mW / cm 2 ) over the period shown in Table 4, and then tested in the same manner as in Test Example 1. went. The results are shown in Table 4. The symbols representing the results are the same as in Table 1.
以上から、微粒子シリカを含有していても、ウレタンアクリレート系樹脂ではＢＬＢ照射により硬度が維持できなくなることがわかる。 From the above, it can be seen that the hardness cannot be maintained by BLB irradiation with urethane acrylate resin even if fine particle silica is contained.
［実施例１８、１９、２０］
製造例１で得られた、固形分濃度０．２５質量％（実施例１８）、０．５質量％（実施例１９）、又は１．０質量％（実施例２０）の光触媒懸濁液２１．６７ｇを用いた以外は、実施例６と同様の方法で、光触媒含有塗布液を得た。[Examples 18, 19, and 20]
Photocatalyst suspension 21 having a solid content concentration of 0.25 mass% (Example 18), 0.5 mass% (Example 19), or 1.0 mass% (Example 20) obtained in Production Example 1 A photocatalyst-containing coating solution was obtained in the same manner as in Example 6 except that .67 g was used.
（シランカップリング剤の加水分解の効果）
［実施例２１、２２、２３、２４］
ＫＢＭ−４０３ ２３６ｇに、室温で撹拌しながら０．０１Ｎ塩酸５４ｇを一度に添加したところ、直後に白濁及び液温の上昇が見られ、３０秒程度で溶液は透明となった。さらに３０分程度撹拌し、液温が室温に戻った点で撹拌を停止して、加水分解ＫＢＭ−４０３を得た。
この加水分解ＫＢＭ−４０３ ６０ｇに、イソプロピルアルコール１４０ｇ、次いでアルミニウムトリス（アセチルアセトナート）（アルドリッチ社製）２．６２ｇを加えて撹拌し、加水分解ＫＢＭ−４０３混合液を得た。
製造例１で得られた、固形分濃度０．２５質量％（実施例２１）、０．５質量％（実施例２２）、１．０質量％（実施例２３）、又は２．５質量％（実施例２４）の各光触媒懸濁液２１．６７ｇに、前記加水分解ＫＢＭ−４０３混合液９．４１ｇを添加して５分間撹拌し、光触媒含有塗布液を得た。(Effect of hydrolysis of silane coupling agent)
[Examples 21, 22, 23, 24]
To 236 g of KBM-403, 54 g of 0.01N hydrochloric acid was added at a time while stirring at room temperature. Immediately thereafter, white turbidity and an increase in liquid temperature were observed, and the solution became transparent in about 30 seconds. The mixture was further stirred for about 30 minutes, and when the liquid temperature returned to room temperature, the stirring was stopped to obtain hydrolysis KBM-403.
To 60 g of this hydrolyzed KBM-403, 140 g of isopropyl alcohol and then 2.62 g of aluminum tris (acetylacetonate) (manufactured by Aldrich) were added and stirred to obtain a hydrolyzed KBM-403 mixed solution.
The solid content concentration obtained in Production Example 1 was 0.25% by mass (Example 21), 0.5% by mass (Example 22), 1.0% by mass (Example 23), or 2.5% by mass. 9.41 g of the hydrolyzed KBM-403 mixed solution was added to 21.67 g of each photocatalyst suspension of Example 24 and stirred for 5 minutes to obtain a photocatalyst-containing coating solution.
［試験例５］
コスモシャインＡ４３００上に、実施例６及び１９〜２５で得られた各光触媒含有塗布液をバーコート成膜し、１００℃で５分乾燥させた。
これらの成膜サンプルに、表５に示した期間にわたってＢＬＢ照射（１ｍＷ／ｃｍ２）を行い、その後、試験例１と同様の方法で試験を行った。結果を表５に示した。結果を表す記号は表１と同じ。[Test Example 5]
Each photocatalyst-containing coating solution obtained in Examples 6 and 19 to 25 was bar-coated on Cosmo Shine A4300 and dried at 100 ° C. for 5 minutes.
These film formation samples were subjected to BLB irradiation (1 mW / cm 2 ) over the period shown in Table 5, and then tested in the same manner as in Test Example 1. The results are shown in Table 5. The symbols representing the results are the same as in Table 1.
以上から、エポキシシランカップリング剤を加水分解縮合して用いると強度が優れることがわかる。 From the above, it can be seen that the strength is excellent when the epoxysilane coupling agent is hydrolyzed and condensed.
（４官能性シラン化合物との比較）
［比較例８］
製造例１で得られた固形分含量２．５質量％の光触媒懸濁液２１．６７ｇに、ＭＫＣシリケートＭＳ−５１（テトラメトキシシランの部分加水分解縮合物、三菱化学社製）２．２７ｇを添加して５分間撹拌し、さらにＴ−５０ ０．８６ｇを添加して５分間撹拌し、光触媒含有塗布液を得た。(Comparison with tetrafunctional silane compound)
[Comparative Example 8]
2.27 g of MKC silicate MS-51 (partially hydrolyzed condensate of tetramethoxysilane, manufactured by Mitsubishi Chemical Corporation) was added to 21.67 g of the photocatalyst suspension having a solid content of 2.5% by mass obtained in Production Example 1. The mixture was added and stirred for 5 minutes, and 0.86 g of T-50 was further added and stirred for 5 minutes to obtain a photocatalyst-containing coating solution.
［比較例９］
比較例８の光触媒含有塗布液に、さらにＩＰＡ−ＳＴ ３．６ｇを添加して５分間混合し、光触媒含有塗布液を得た。[Comparative Example 9]
Further, 3.6 g of IPA-ST was added to the photocatalyst-containing coating solution of Comparative Example 8 and mixed for 5 minutes to obtain a photocatalyst-containing coating solution.
［比較例１０］
比較例８の光触媒含有塗布液に、さらにＩｒｇａｃｕｒｅ９０７ ０．４６ｇを添加して５分間撹拌し、光触媒含有塗布液を得た。[Comparative Example 10]
0.46 g of Irgacure 907 was further added to the photocatalyst-containing coating solution of Comparative Example 8 and stirred for 5 minutes to obtain a photocatalyst-containing coating solution.
［比較例１１］
比較例１０の光触媒含有塗布液に、さらにＩＰＡ−ＳＴ ３．６ｇを添加して５分間混合し、光触媒含有塗布液を得た。[Comparative Example 11]
To the photocatalyst-containing coating solution of Comparative Example 10, 3.6 g of IPA-ST was further added and mixed for 5 minutes to obtain a photocatalyst-containing coating solution.
［試験例６］
コスモシャインＡ４３００上に、実施例５、８、４、１７、比較例８、９、１０、及び１１で得られた各光触媒含有塗布液をバーコート成膜し、１００℃で５分乾燥させた。
実施例４、１７、比較例１０、及び１１の各光触媒含有塗布液を用いて得られた成膜サンプルには、その後さらにＵＶ照射（４００ｍＪ／ｃｍ２）を行った。
これらの成膜サンプルに、表６に示した期間にわたってＢＬＢ照射（１ｍＷ／ｃｍ２）を行い、その後、試験例１と同様の方法で試験を行った。結果を表６に示した。結果を表す記号は表１と同じ。[Test Example 6]
Each photocatalyst-containing coating solution obtained in Examples 5, 8, 4, 17 and Comparative Examples 8, 9, 10, and 11 was bar-coated on Cosmo Shine A4300 and dried at 100 ° C. for 5 minutes. .
The film formation samples obtained using the photocatalyst-containing coating solutions of Examples 4 and 17 and Comparative Examples 10 and 11 were further subjected to UV irradiation (400 mJ / cm 2 ).
These film formation samples were subjected to BLB irradiation (1 mW / cm 2 ) over the period shown in Table 6, and then tested in the same manner as in Test Example 1. The results are shown in Table 6. The symbols representing the results are the same as in Table 1.
以上から、本発明におけるエポキシシランカップリング剤又はアクリルシランカップリング剤に代えて４官能性シラン化合物加水分解物を用いても、十分な強度は得られないことがわかる。 From the above, it can be seen that sufficient strength cannot be obtained even when a tetrafunctional silane compound hydrolyzate is used instead of the epoxy silane coupling agent or the acrylic silane coupling agent in the present invention.
（抗ウイルス性試験）
［実施例２５、２６、２７］
製造例１で得られた、固形分含量１．０質量％（実施例２５：最終固形分中における酸化チタン含量７．０質量％）、０．５質量％（実施例２６：最終固形分中における酸化チタン含量３．６質量％）、又は０．２５質量％（実施例２７：最終固形分中における酸化チタン含量１．７質量％）の光触媒懸濁液２１．６７ｇに、ＫＢＭ−４０３ ２．２７ｇを添加して５分間撹拌し、さらにＴ−５０ ０．８６ｇを添加して５分間撹拌し、光触媒含有塗布液を得た。(Antiviral test)
[Examples 25, 26, and 27]
Solid content 1.0% by mass obtained in Production Example 1 (Example 25: Titanium oxide content 7.0% by mass in the final solid), 0.5% by mass (Example 26: in the final solid) KBM-403 2 was added to 21.67 g of the photocatalyst suspension having a titanium oxide content of 3.6% by mass) or 0.25% by mass (Example 27: titanium oxide content of 1.7% by mass in the final solid content). .27 g was added and stirred for 5 minutes, and 0.86 g of T-50 was further added and stirred for 5 minutes to obtain a photocatalyst-containing coating solution.
［試験例６］
コスモシャインＡ４３００上に、実施例２５〜２７で得られた各光触媒含有塗布液をバーコート成膜し、１００℃で５分乾燥させた。
これらの成膜サンプルについて、ＪＩＳ Ｒ １７５６に準拠し、Ｑβバクテリオファージを用いた抗ウイルス性試験を行った。光源は白色蛍光灯を用い、ＵＶカットフィルター（Ｎ１１３）を用いてλ≧４００ｎｍとした可視光をサンプル表面の照度が１０００Ｌｕｘとなるようにして、１時間又は４時間照射し、不活化度を評価した。また暗黒下（図中でdarkと表示した。）で評価時間を１時間又は４時間として同様に評価した。結果を図１に示した。[Test Example 6]
On the Cosmo Shine A4300, each photocatalyst containing coating liquid obtained in Examples 25 to 27 was formed into a bar coat film and dried at 100 ° C. for 5 minutes.
These film formation samples were subjected to an antiviral test using Qβ bacteriophage according to JIS R 1756. A white fluorescent lamp is used as the light source, and visible light with a wavelength of λ ≧ 400 nm using a UV cut filter (N113) is irradiated for 1 hour or 4 hours so that the illuminance of the sample surface is 1000 Lux, and the degree of inactivation is evaluated. did. Further, the evaluation was made in the same manner with the evaluation time being 1 hour or 4 hours under darkness (indicated as dark in the figure). The results are shown in FIG.
［実施例２８、２９、３０］
製造例１で得られた、固形分含量１．０質量％（実施例２８：最終固形分中における酸化チタン含量６．６質量％）、０．５質量％（実施例２９：最終固形分中における酸化チタン含量３．４質量％）、又は０．２５質量％（実施例３０：最終固形分中における酸化チタン含量１．６質量％）の光触媒懸濁液２１．６７ｇに、ＫＢＭ−５１０３ ２．２７ｇを添加して５分間撹拌し、Ｔ−５０ ０．８６ｇを添加して５分間撹拌し、Ｉｒｇａｃｕｒｅ９０７ ０．２３ｇを添加して５分間撹拌し、光触媒含有塗布液を得た。[Examples 28, 29, 30]
The solid content obtained in Production Example 1 was 1.0% by mass (Example 28: titanium oxide content in the final solid content was 6.6% by mass), 0.5% by mass (Example 29: in the final solid content) KBM-5103 2 was added to 21.67 g of the photocatalyst suspension having a titanium oxide content of 3.4% by mass) or 0.25% by mass (Example 30: titanium oxide content of 1.6% by mass in the final solid content). .27 g was added and stirred for 5 minutes, 0.850 g of T-50 was added and stirred for 5 minutes, 0.23 g of Irgacure 907 was added and stirred for 5 minutes, and a photocatalyst-containing coating solution was obtained.
［試験例７］
コスモシャインＡ４３００上に、実施例２８〜３０で得られた各光触媒含有塗布液をバーコート成膜し、１００℃で５分乾燥させ、さらにＵＶ照射（４００ｍＪ／ｃｍ２）を行った。
これらの成膜サンプルについて、試験例６と同様の方法で評価した。結果を図２に示した。[Test Example 7]
Each photocatalyst-containing coating solution obtained in Examples 28 to 30 was bar-coated on Cosmo Shine A4300, dried at 100 ° C. for 5 minutes, and further irradiated with UV (400 mJ / cm 2 ).
These film formation samples were evaluated in the same manner as in Test Example 6. The results are shown in FIG.
いずれも評価時間４時間では十分な抗ウイルス性を示し、特にＫＢＭ−５１０３（アクリルシランカップリング剤）を用いた場合には、１時間でも高い抗ウイルス性を示した。 All showed sufficient antiviral properties at an evaluation time of 4 hours, and particularly when KBM-5103 (acrylic silane coupling agent) was used, high antiviral properties were exhibited even at 1 hour.
Claims (9)
光触媒材料微粒子１００質量部に対して、前記シランカップリング剤及び該シランカップリング剤の加水分解縮合物の合計を３００質量部以上の比率で含有する、
光触媒含有塗布液。 Photocatalytic material particles, A hydrolysis condensation product of acrylic silane coupling agent及 beauty / or the silane coupling agent, without metal coupling agents silicon as the metal element, a photopolymerization initiator and a solvent,
The total of the silane coupling agent and the hydrolysis condensate of the silane coupling agent is contained at a ratio of 300 parts by mass or more with respect to 100 parts by mass of the photocatalytic material fine particles.
Photocatalyst-containing coating solution.
A method for forming a photocatalyst-supporting structure by directly applying the photocatalyst-containing coating liquid according to any one of claims 1 to 5 to a substrate and drying the substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015097195 | 2015-05-12 | ||
| JP2015097195 | 2015-05-12 | ||
| PCT/JP2016/002168 WO2016181622A1 (en) | 2015-05-12 | 2016-04-25 | Photocatalyst-containing coating liquid and photocatalyst-supporting structure |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018233854A Division JP6718497B2 (en) | 2015-05-12 | 2018-12-13 | Photocatalyst-containing coating liquid and photocatalyst supporting structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2016181622A1 JPWO2016181622A1 (en) | 2018-03-29 |
| JP6467502B2 true JP6467502B2 (en) | 2019-02-13 |
Family
ID=57248983
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017517604A Active JP6467502B2 (en) | 2015-05-12 | 2016-04-25 | Photocatalyst-containing coating liquid and photocatalyst carrying structure |
| JP2018233854A Active JP6718497B2 (en) | 2015-05-12 | 2018-12-13 | Photocatalyst-containing coating liquid and photocatalyst supporting structure |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018233854A Active JP6718497B2 (en) | 2015-05-12 | 2018-12-13 | Photocatalyst-containing coating liquid and photocatalyst supporting structure |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JP6467502B2 (en) |
| TW (1) | TWI582182B (en) |
| WO (1) | WO2016181622A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7223710B2 (en) * | 2017-05-09 | 2023-02-16 | シーカ テクノロジー アクチェンゲゼルシャフト | Aqueous pretreatment agent for joint joints with increased thermal stability |
| CN110678258A (en) | 2017-05-31 | 2020-01-10 | 国立大学法人北海道大学 | Functional structure and method for manufacturing functional structure |
| EP3632547A4 (en) | 2017-05-31 | 2020-12-16 | Furukawa Electric Co., Ltd. | Catalyst structure for catalytic cracking or hydrodesulfurization, catalytic cracking device and hydrodesulfurization device using said catalyst structure, and production method for catalyst structure for catalytic cracking or hydrodesulfurization |
| CN110678262A (en) | 2017-05-31 | 2020-01-10 | 古河电气工业株式会社 | Exhaust gas purifying oxidation catalyst structure, method for producing same, exhaust gas treatment device for automobile, catalyst molded body, and gas purifying method |
| JPWO2018221690A1 (en) | 2017-05-31 | 2020-05-21 | 国立大学法人北海道大学 | Functional structure and method for manufacturing functional structure |
| AU2018276618B2 (en) | 2017-05-31 | 2021-05-27 | Furukawa Electric Co., Ltd. | Functional structure and production method for functional structure |
| CN110678263A (en) | 2017-05-31 | 2020-01-10 | 古河电气工业株式会社 | Catalyst structure for hydrodesulfurization, hydrodesulfurization apparatus provided with same, and method for producing catalyst structure for hydrodesulfurization |
| WO2018221706A1 (en) | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | Methanol reforming catalyst structure, methanol reforming device, production method for methanol reforming catalyst structure, and production method for at least one of olefins and aromatic hydrocarbons |
| JPWO2018221702A1 (en) | 2017-05-31 | 2020-03-26 | 古河電気工業株式会社 | Photocatalyst structure, photocatalyst structure composition, photocatalyst coating material, method for producing photocatalyst structure, and method for decomposing aldehydes |
| WO2018221698A1 (en) | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | Co shift or reverse shift catalyst structure and production method thereof, co shift or reverse shift reaction device, production method of carbon dioxide and hydrogen, and production method of carbon monoxide and water |
| AU2018277967B2 (en) | 2017-05-31 | 2021-05-27 | Furukawa Electric Co., Ltd. | Functional structure and production method for functional structure |
| US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
| CN116716039B (en) * | 2023-08-11 | 2023-12-26 | 北京助天科技集团有限公司 | Photocatalytic radiation refrigeration coating, preparation method and application |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3474546B2 (en) * | 2001-02-22 | 2003-12-08 | 日新製鋼株式会社 | Photocatalytic coating composition |
| JP2003275601A (en) * | 2002-03-22 | 2003-09-30 | Janis Ltd | Photocatalyst coating agent |
| JP4001586B2 (en) * | 2004-03-29 | 2007-10-31 | ヨコタ量販株式会社 | Blinds with excellent antifouling properties |
| JP4210785B2 (en) * | 2004-09-17 | 2009-01-21 | テイカ株式会社 | Method for producing transparent coating agent for optical element containing rutile type titanium oxide sol |
| JP2006198466A (en) * | 2005-01-18 | 2006-08-03 | Jsr Corp | Photocatalytic sheet and illumination device using the same |
| JP4681483B2 (en) * | 2006-03-30 | 2011-05-11 | 新日本製鐵株式会社 | Surface-treated metal |
| JP5377820B2 (en) * | 2006-06-14 | 2013-12-25 | 日本曹達株式会社 | Organic-inorganic composite containing functional substances |
| JP5478856B2 (en) * | 2008-08-13 | 2014-04-23 | アキレス株式会社 | Photocatalytic coating film-forming coating material, photocatalytic coating film, and laminate comprising the photocatalytic coating film |
| CN104114622B (en) * | 2012-02-08 | 2016-02-10 | 日本曹达株式会社 | Organo-mineral complexing film |
| CN104478231B (en) * | 2014-11-20 | 2016-08-24 | 南阳理工学院 | A kind of preventing ultraviolet TiO2the preparation method of film |
-
2016
- 2016-04-25 WO PCT/JP2016/002168 patent/WO2016181622A1/en active Application Filing
- 2016-04-25 JP JP2017517604A patent/JP6467502B2/en active Active
- 2016-04-27 TW TW105113156A patent/TWI582182B/en not_active IP Right Cessation
-
2018
- 2018-12-13 JP JP2018233854A patent/JP6718497B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP6718497B2 (en) | 2020-07-08 |
| JPWO2016181622A1 (en) | 2018-03-29 |
| TWI582182B (en) | 2017-05-11 |
| JP2019089062A (en) | 2019-06-13 |
| TW201700636A (en) | 2017-01-01 |
| WO2016181622A1 (en) | 2016-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6467502B2 (en) | Photocatalyst-containing coating liquid and photocatalyst carrying structure | |
| TW473400B (en) | Modified photocatalyst sol | |
| KR101758934B1 (en) | Near-infrared shielding coating agent curable at ordinary temperatures, near-infrared shielding film using same, and manufacturing method therefor | |
| EP1849835B1 (en) | Organic-inorganic composite body | |
| JP6866596B2 (en) | Photocatalyst coating | |
| JP5614709B2 (en) | Photocatalyst paint | |
| WO1998025711A1 (en) | Functional coated articles, method of their production, and application thereof | |
| JP4823045B2 (en) | Water-based photocatalytic composition | |
| KR20150028979A (en) | Coating composition and uses thereof | |
| TWI457386B (en) | Photocatalyst-coated body and a photocatalyst coating liquid | |
| CN102105303A (en) | Object with photo-catalyst coating | |
| JPWO2014196386A1 (en) | Silicone coating composition and coated article | |
| JP2002146283A (en) | Photocatalytic coating fluid containing titanium oxide and its manufacturing method and titanium oxide photocatalytic structure | |
| JP2004143452A (en) | Self-cleaning aqueous coating composition and self- cleaning member | |
| JP2009039687A (en) | Composition for forming photocatalyst layer | |
| JPH09328336A (en) | Coating film having photocatalyst activity and composition forming the same coating film | |
| JP4155760B2 (en) | Modified titania sol composition | |
| JP2002273234A (en) | Method for manufacturing photocatalytic body | |
| WO2019239808A1 (en) | Photocatalyst composite material, display protection member for signage, protective member for touch panel, protective member for solar cell, protective member for sensor cover, display for signage, touch panel, solar cell, and sensor cover | |
| JP3346278B2 (en) | Method of forming photocatalytic film on organic base material and its use | |
| JP4820152B2 (en) | Composite coating structure and painted exterior materials | |
| JP2002079109A (en) | Optical semiconductor metal-organic substance mixed body, composition containing optical semiconductor metal, method for producing photocatalytic film and photocatalytic member | |
| JP2002356650A (en) | Photocatalytic film-forming composition and photocatalytic member obtained by applying it | |
| JPH10259320A (en) | Photocatalytic coating material, production thereof, and coating film formed therefrom | |
| JP2015160892A (en) | Antifouling composite coat with biofilm forming ability suppressed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20171013 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181018 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181213 |
|
| 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: 20190107 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190111 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6467502 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| 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 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |